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Sample records for precipitated iron fischer-tropsch

  1. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Dr. Dragomir B. Bukur; Dr. X. Lang; Dr. S. Chokkaram; Dr. L. Nowicki; G. Wei; Dr. Y. Ding; Dr. B. Reddy; Dr. S. Xiao

    1999-07-22

    Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

  2. The role of catalyst activation on the activity and attrition of precipitated iron Fischer-Tropsch catalysts

    SciTech Connect

    Datye, A.K.; Shroff, M.D.; Harrington, M.S.; Coulter, K.E.; Sault, A.G.; Jackson, N.B.

    1995-12-31

    The results of this work indicate that magnetite is not catalytically active for Fischer-Tropsch Synthesis (FTS) in precipitated, unsupported iron catalysts, but the formation of the carbide phase is necessary to obtain FTS activity. The transformation of magnetite to carbide, though essential to obtain FTS activity, also causes the catalyst to break down. This can lead to severe problems during operation in a commercial slurry phase reactor. The results presented here imply that activation and attrition are simultaneous and complementary processes. In another study, we show that the catalyst can also under go attrition on a micron scale which is caused by lack of strength of the forces binding the catalyst primary particles in the agglomerates. Both these processes can make wax separation and product recovery extremely difficult. In this study, we have also shown that H{sub 2} reduction of this catalyst to metallic iron is detrimental to subsequent catalyst activity and causes a loss of surface area due to sintering of the iron crystallites. Reduction to metallic Fe also causes impurities such as S to segregate to the surface causing a complete loss of FTS activity. It has been shown that even submonolayer amounts of S can cause a dramatic decrease in FTS activity, hence reduction to metallic Fe should be avoided during activation of these catalysts. We have shown, however, that a mild H{sub 2} reduction to magnetite does not lead to S segregation to the surface, and is therefore acceptable.

  3. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 April 1996--30 June 1996

    SciTech Connect

    Bukur, D.B.; Lang, X.; Ding, Y.; Chokkaram, S.

    1996-09-02

    The overall contract objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University (TAMU) during the DOE Contract DE-AC22-89PC89868; (2) seek potential improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst synthesis; (3) investigate performance of catalysts in a small scale bubble column slurry reactor, and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer. The performance of an iron, and iron-copper-silica catalyst are described.

  4. Hydrocarbon selectivity model for gas-solid Fischer-Tropsch synthesis on precipitated iron catalysts

    SciTech Connect

    Laan, G.P. van der; Beenackers, A.A.C.M.

    1999-04-01

    The kinetics of the gas-solid Fischer-Tropsch (FT) synthesis over a commercial Fe-Cu-K-SiO{sub 2} catalyst was studied in a continuous spinning basket reactor. Experimental conditions were varied as follows: reactor pressure of 0.8--3.2 MPa, H{sub 2}/CO feed ratio = 0.5--2.0, and a space velocity of 0.5--2.0 {times} 10{sup {minus}3} Nm{sup 3}/kg{sub cat} s at a constant temperature of 523 K. A new product distribution model for linear hydrocarbons is proposed. Deviations from conventional Anderson-Schulz-Flory distribution can be quantitatively described with an {alpha}-olefin readsorption product distribution model. The experimentally observed relatively high yield of methane, relatively low yield of ethene, and both the exponential decrease of the olefin-to-paraffin ratio and the change of the chain growth parameter with chain length can all be predicted from this new model. It combines a mechanistic model of olefin readsorption with kinetics of chain growth and termination on the same catalytic sites. The hydrocarbon formation is based on the surface carbide mechanism by CH{sub 2} insertion. The olefin readsorption rate depends on the chain length because of increasing physisorption strength on the catalyst surface and increasing solubility in FT wax with increasing chain length. Interfacial concentrations of reactive olefins near the gas-wax and wax-catalyst surface are used in the kinetic model. With optimization of three parameters per experimental product distribution, the olefin readsorption product distribution model proved to predict product selectivities accurately over the entire range of experimental conditions. The relative deviations are 10.1% and 9.1% for the selectivity to paraffins and olefins with n < 11, respectively.

  5. Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

    DOEpatents

    Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

    1986-01-01

    A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

  6. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Davis, B.H.

    1998-07-22

    The goal of the proposed work described in this Final Report was the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The work described here has optimized the catalyst composition and pretreatment operation for a low-alpha catalyst. In parallel, work has been conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies have been conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors have been studied at the laboratory scale. Catalyst performance has been determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  7. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-22

    Objective is to develop producing active, stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to synthesize such catalysts on a large scale for process development and long-term testing in slurry bubble-column reactors. A mixed oxalate of Fe, Cu, and K was prepared; a catalyst will be prepared from this material. An evaluation run was performed on an Fe-based UCI catalyst, which was shown to produce low levels of C[sub 1] and C[sub 2] paraffins; e.g., at the end of the run, when the catalyst was converting 60% of the CO, the C[sub 1] and C[sub 2] paraffin selectivities were 4.2 and 1.0, respectively.

  8. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report for the period July 1, 1996--September 30, 1996

    SciTech Connect

    Bukur, D.B.

    1996-12-02

    Two slurry reactor tests were completed in continuation of our studies on the effect of pretreatment conditions on catalyst reactivity and selectivity. Exceptionally good performance was obtained in run SA-2186, using the new pretreatment developed at Texas A&M University. The work on catalyst characterization by temperature programmed and isothermal reduction on a variety of iron catalysts, with different amounts of promoters, has been continued. These studies are complementing our work on pretreatment effect research, and provide additional insights into the effect of pretreatment procedures on the reduction behavior of iron catalysts. The overall objectives are to: (1) demonstrate repeatability of performance and preparation procedure of two high activity, high alpha iron Fischer-Tropsch catalysts synthesized at Texas A&M University; (2) seek potential improvements in the catalysts performance through variation in process condition, pretreatment procedures and/or modifications in catalyst synthesis; (3) investigate performance of catalysts in a small bubble column slurry reactor; and (4) investigate feasibility of producing catalysts on a large scale in collaboration with a catalyst manufacturer.

  9. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    O`Brien, R.J.; Raje, A.; Keogh, R.A.

    1995-12-31

    The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alpha iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  10. Technology Development for Iron Fischer-Tropsch Catalysis.

    SciTech Connect

    Davis, B.H.

    1997-12-16

    The goal of the proposed work is the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The catalyst that is developed will be suitable for testing at the Advanced Fuels Development Facility at LaPorte, Texas or similar sized plant. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the `standard-catalyst` developed by German workers for slurry phase synthesis. The proposed work will optimize the catalyst composition and pretreatment operation for this low-alpha catalyst. In parallel, work will be conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  11. Technology development for iron Fischer-Tropsch catalysts

    SciTech Connect

    Frame, R.R.

    1991-01-01

    Objectives are to develop active, stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. For a H[sub 2]-CO in molar ratio of 0.5 to 1.0, catalyst performance target is 88% CO+H[sub 2] conversion at a minimum space velocity of 2.4 NL/hr/gFe, with no more than 4% methane/ethane selectivity and 1% conversion loss per week. During this period, it was found that the performance of the slurry-phase iron and copper oxide-based catalyst depends on the amount of K. Five catalysts with differing K contents were studied. The catalysts with the lowest K were more active than the ones with higher K levels. The one with the middle K level was judged best.

  12. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    Burtron H. Davis

    1999-01-30

    The effects of copper on Fischer-Tropsch activity, selectivity and water-gas shift activity were studied over a wide range of syngas conversion. Three catalyst compositions were prepared for this study: (a) 100Fe/4.6Si/1.4K, (b) 100Fe/4.6Si/0.10Cu/1.4K and (c) 100Fe/4.6Si/2.0Cu/1.4K. The results are reported in Task 2. The literature review for cobalt catalysts is approximately 90% complete. Due to the size of the document, it has been submitted as a separate report labeled Task 6.

  13. ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    SciTech Connect

    K. Jothimurugesan; James G. Goodwin, Jr.; Santosh K. Gangwal

    1999-10-01

    Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away from fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of FeFT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction.

  14. Iron Aerogel and Xerogel Catalysts for Fischer-Tropsch Synthesis of Diesel Fuel

    SciTech Connect

    Bali, S.; Huggins, F; Huffman, G; Ernst, R; Pugmire, R; Eyring, E

    2009-01-01

    Iron aerogels, potassium-doped iron aerogels, and potassium-doped iron xerogels have been synthesized and characterized and their catalytic activity in the Fischer-Tropsch (F-T) reaction has been studied. Iron aerogels and xerogels were synthesized by polycondensation of an ethanolic solution of iron(III) chloride hexahydrate with propylene oxide which acts as a proton scavenger for the initiation of hydrolysis and polycondensation. Potassium was incorporated in the iron aerogel and iron xerogel by adding aqueous K{sub 2}CO{sub 3} to the ethanolic solutions of the Fe(III) precursor prior to addition of propylene oxide. Fischer-Tropsch activities of the catalysts were tested in a fixed bed reactor at a pressure of 100 psi with a H{sub 2}:CO ratio of 2:1. Iron aerogels were found to be active for F-T synthesis, and their F-T activities increased on addition of a K containing promoter. Moessbauer spectroscopic data are consistent with an open, nonrigid iron(III) aerogel structure progressing to an iron carbide/metallic iron catalyst via agglomeration as the F-T synthesis proceeds in the course of a 35 h fixed bed reaction test.

  15. Fischer-Tropsch process

    DOEpatents

    Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

    1987-01-01

    A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

  16. ε-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst.

    PubMed

    Xu, Ke; Sun, Bo; Lin, Jun; Wen, Wen; Pei, Yan; Yan, Shirun; Qiao, Minghua; Zhang, Xiaoxin; Zong, Baoning

    2014-12-12

    ε-Iron carbide has been predicted to be promising for low-temperature Fischer-Tropsch synthesis (LTFTS) targeting liquid fuel production. However, directional carbidation of metallic iron to ε-iron carbide is challenging due to kinetic hindrance. Here we show how rapidly quenched skeletal iron featuring nanocrystalline dimensions, low coordination number and an expanded lattice may solve this problem. We find that the carbidation of rapidly quenched skeletal iron occurs readily in situ during LTFTS at 423-473 K, giving an ε-iron carbide-dominant catalyst that exhibits superior activity to literature iron and cobalt catalysts, and comparable to more expensive noble ruthenium catalyst, coupled with high selectivity to liquid fuels and robustness without the aid of electronic or structural promoters. This finding may permit the development of an advanced energy-efficient and clean fuel-oriented FTS process on the basis of a cost-effective iron catalyst.

  17. ε-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst.

    PubMed

    Xu, Ke; Sun, Bo; Lin, Jun; Wen, Wen; Pei, Yan; Yan, Shirun; Qiao, Minghua; Zhang, Xiaoxin; Zong, Baoning

    2014-01-01

    ε-Iron carbide has been predicted to be promising for low-temperature Fischer-Tropsch synthesis (LTFTS) targeting liquid fuel production. However, directional carbidation of metallic iron to ε-iron carbide is challenging due to kinetic hindrance. Here we show how rapidly quenched skeletal iron featuring nanocrystalline dimensions, low coordination number and an expanded lattice may solve this problem. We find that the carbidation of rapidly quenched skeletal iron occurs readily in situ during LTFTS at 423-473 K, giving an ε-iron carbide-dominant catalyst that exhibits superior activity to literature iron and cobalt catalysts, and comparable to more expensive noble ruthenium catalyst, coupled with high selectivity to liquid fuels and robustness without the aid of electronic or structural promoters. This finding may permit the development of an advanced energy-efficient and clean fuel-oriented FTS process on the basis of a cost-effective iron catalyst. PMID:25503569

  18. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    Amitava Sarkar; James K. Neathery; Burtron H. Davis

    2006-12-31

    A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of iron catalyst particles and the formation of ultra-fine particles.

  19. Preparation of Fischer-Tropsch catalysts from cobalt/iron hydrotalcites

    SciTech Connect

    Howard, B.H.; Boff, J.J.; Zarochak, M.F.

    1995-12-31

    Compounds with the (hydrotalcites) have properties that make them attractive as precursors for Fischer-Tropsch catalysts. A series of single-phase hydrotalcites with cobalt/iron atom ratios ranging from 75/25 to 25/75 has been synthesized. Mixed cobalt/iron oxides have been prepared from these hydrotalcites by controlled thermal decomposition. Thermal decomposition at temperatures below 600 {degrees}C typically produced a single-phase mixed metal oxide with a spinel structure. The BET surface areas of the spinal samples have been found to be as high as about 150 m{sup 2}/g. Appropriate reducing pretreatments have been developed for several of these spinels and their activity, selectivity, and activity and selectivity maintenance have been examined at 13 MPa in a fixed-bed microreactor.

  20. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    SciTech Connect

    Jackson, N.B.; Kohler, S.; Harrington, M.

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  1. Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy. [deuterium-carbon monoxide reaction catalysis

    NASA Technical Reports Server (NTRS)

    Nooner, D. W.; Gibert, J. M.; Gelpi, E.; Oro, J.

    1976-01-01

    Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

  2. Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

    PubMed

    Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

    2016-02-01

    Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

  3. Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

    PubMed

    Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

    2016-02-01

    Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS. PMID:27433720

  4. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2004-03-31

    In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.

  5. Zeolite supported iron-cobalt catalysts for the Fischer-Tropsch synthesis

    SciTech Connect

    Lin, T.

    1984-01-01

    A series of Fe, Co, FeCo catalysts on Y and ZSM-5 supports, prepared by impregnation and ion exchange, has been investigated. Characterization methods utilized were x-ray diffraction, H{sub 2}/CO chemisorption, Moessbauer spectroscopy, and atomic absorption. A differential reactor and as chromatographs were also employed to analyze the reaction activity and product selectivity. (i) Y supported catalysts: The oxidation, reduction, and carburization behavior of the iron-containing catalysts were observed via Moessbauer spectra. The reversibility of FeY (ion exchange) in oxidation-reduction cycles was confirmed in this experiment. Furthermore, ion exchange catalysts (FeY, FeCoY) do not show any iron metal, alloy or carbide phase after reduction or carburization. In contrast to silica supported catalysts, FeCo/HY (impregnated) reveals a Moessbauer spectra similar to Fe/HY. A 1/1 (CO/H{sub 2}) feed was used to investigate the Fischer-Tropsch reaction at 1 atm, 250{degree}C. (ii) ZSM-5 supported catalysts: Moessbauer results indicate similar patterns for impregnated and ion-exchanged catalysts, and reaction studies reveal similar catalytic behavior for the two preparation methods. This is in contrast to the rather widely different properties of these metals resulting from impregnation or ion exchange on Y zeolite. In generation, the ZSM-5 supported metals produce higher activity and selectivity for high molecular weight materials, and are particularly identified with significant aromatic content in the production distribution.

  6. Development of improved iron Fischer-Tropsch catalysts. Final technical report: Project 6464

    SciTech Connect

    Bukur, D.B.; Ledakowicz, S.; Koranne, M.

    1994-02-28

    Despite the current worldwide oil glut, the United States will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer Tropsch (FT) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Texas A&M University (TAMU) with sponsorship from the US Department of Energy, Center for Energy and Mineral Resources at TAMU, Texas Higher Education Coordinating Board, and Air Products and Chemicals, Inc., has been working on development of improved iron FT catalysts and characterization of hydrodynamic parameters in two- and three-phase bubble columns with FT derived waxes. Our previous studies have provided an improved understanding of the role of promoters (Cu and K), binders (silica) and pretreatment procedures on catalyst activity, selectivity and longevity (deactivation). The objective of the present contract was to develop improved catalysts with enhanced slurry phase activity and higher selectivity to liquid fuels and wax. This was accomplished through systematic studies of the effects of pretreatment procedures and variations in catalyst composition (promoters and binders). The major accomplishments and results in each of these two main areas of research are summarized here.

  7. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 7, April 1, 1992--June 30, 1992

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-31

    The objective of this contract are to develop a technology for the production of active and stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. With a feed containing H{sub 2} and CO in the molar ratio of 0.5 to 1.0 to the slurry bubble-column reactor, the catalyst performance target is 88% CO + H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on catalyst development.

  8. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 8, July 1, 1992--September 30, 1992

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-31

    The objectives of this contract are to develop a technology for the production of active and stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. With a feed containing hydrogen and carbon monoxide in the molar ratio of 0.5 to 1.0 to the slurry bubble-column reactor, the catalyst performance target is 88% CO + H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/gFe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on Task 1.

  9. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2005-03-31

    In this reporting period, a fundamental filtration study was continued to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. In this reporting period, a series of crossflow filtration experiments were initiated to study the effect of olefins and oxygenates on the filtration flux and membrane performance. Iron-based FTS reactor waxes contain a significant amount of oxygenates, depending on the catalyst formulation and operating conditions. Mono-olefins and aliphatic alcohols were doped into an activated iron catalyst slurry (with Polywax) to test their influence on filtration properties. The olefins were varied from 5 to 25 wt% and oxygenates from 6 to 17 wt% to simulate a range of reactor slurries reported in the literature. The addition of an alcohol (1-dodecanol) was found to decrease the permeation rate while the olefin added (1-hexadecene) had no effect on the permeation rate. A passive flux maintenance technique was tested that can temporarily increase the permeate rate for 24 hours.

  10. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2004-09-30

    In this reporting period, a fundamental filtration study was continued to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. The shakedown phase of the pilot-scale filtration platform was completed at the end of the last reporting period. A study of various molecular weight waxes was initiated to determine the effect of wax physical properties on the permeation rate without catalyst present. As expected, the permeation flux was inversely proportional to the nominal average molecular weight of the polyethylene wax. Even without catalyst particles present in the filtrate, the filtration membranes experience fouling during an induction period on the order of days on-line. Another long-term filtration test was initiated using a batch of iron catalyst that was previously activated with CO to form iron carbide in a separate continuous stirred tank reactor (CSTR) system. The permeation flux stabilized more rapidly than that experienced with unactivated catalyst tests.

  11. Exploring iron-based multifunctional catalysts for Fischer-Tropsch synthesis: a review.

    PubMed

    Abelló, Sònia; Montané, Daniel

    2011-11-18

    The continuous increase in oil prices together with an increase in carbon dioxide concentration in the atmosphere has prompted an increased interest in the production of liquid fuels from non-petroleum sources to ensure the continuation of our worldwide demands while maximizing CO(2) utilization. In this sense, the Fischer-Tropsch (FT) technology provides a feasible option to render high value-added hydrocarbons. Alternative sources, such as biomass or coal, offer a real possibility to realize these purposes by making use of H(2)-deficient or CO(2)-rich syngas feeds. The management of such feeds ideally relies on the use of iron catalysts, which exhibit the unique ability to adjust the H(2)/CO molar ratio to an optimum value for hydrocarbon synthesis through the water-gas-shift reaction. Taking advantage of the emerging attention to hybrid FT-synthesis catalysts based on cobalt and their associated benefits, an overview of the current state of literature in the field of iron-based multifunctional catalysts is presented. Of particular interest is the use of zeolites in combination with a FT catalyst in a one-stage operation, herein named multifunctional, which offer key opportunities in the modification of desired product distributions and selectivity, to eventually overcome the quality limitations of the fuels prepared under intrinsic FT conditions. This review focuses on promising research activities addressing the conversion of syngas to liquid fuels mediated by iron-based multifunctional materials, highlights their preparation and properties, and discusses their implication and challenges in the area of carbon utilization through H(2)/CO(+CO(2)) mixtures. PMID:22083868

  12. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Burtron H. Davis

    2005-09-30

    In this reporting period, a study of ultra-fine iron catalyst filtration was initiated to study the behavior of ultra-fine particles during the separation of Fischer-Tropsch Synthesis (FTS) liquids filtration. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. The change of particle size during the slurry-phase FTS has monitored by withdrawing catalyst sample at different TOS. The measurement of dimension of the HRTEM images of samples showed a tremendous growth of the particles. Carbon rims of thickness 3-6 nm around the particles were observed. This growth in particle size was not due to carbon deposition on the catalyst. A conceptual design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. The system will utilize a primary inertial hydroclone followed by a Pall Accusep cross-flow membrane. Provisions for cleaned permeate back-pulsing will be included to as a flux maintenance measure.

  13. Moessbauer study of iron-carbide growth and Fischer-Tropsch activity

    SciTech Connect

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P.

    1995-12-31

    There is a need to establish a correlation between the Fischer-Tropsch (FT) activity of an iron-based catalyst and the catalyst phase during FT synthesis. The nature of iron phases formed during activation and FT synthesis is influenced by the nature of the gas and pressure apart from other parameters like temperature, flow rate etc., used for activation. Moessbauer investigations of iron-based catalysts subjected to pretreatment at two different pressures in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been carried out. Studies on UCI 1185-57 (64%Fe{sub 2}O{sub 3}/5%CuO/1%K{sub 2}O/30% Kaolin) catalyst indicate that activation of the catalyst in CO at 12 atms. leads to the formation of 100% magnetite and the magnetite formed gets rapidly converted to at least 90% of {chi}-Fe{sub 5}C{sub 2} during activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation of the catalyst in synthesis gas at 12 atms. leads to formation of Fe{sub 3}O{sub 4} and it gets sluggishly converted to {chi}-Fe{sub 5}C{sub 2} and {epsilon}-Fe{sub 2.2}C during activation and both continue to grow slowly during FT synthesis. FT activity is found to be poor. Pretreatment of the catalyst, 100fe/3.6Si/0.71K at a low pressure of 1 atms. in syngas gave rise to the formation of {chi}-Fe{sub 5}C{sub 2} and good FT activity. On the other hand, pretreatment of the catalyst, 100Fe/3.6Si/0.71K at a relatively high pressure of 12 atms. in syngas did not give rise to the formation any carbide and FT activity was poor.

  14. Phase transformation of iron-based catalysts for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Jin, Yaming

    Fischer-Tropsch (F-T) synthesis is used to convert syngas to liquid hydrocarbons using iron-based catalysts. However, the nature of the active phase and phase transformations during F-T synthesis are not well understood. In this work, the phase transformations of Fe catalysts both during F-T synthesis and controlled treatment conditions have been studied using cross-section transmission electron microscopy, x-ray diffraction and Mossbauer spectroscopy. Catalyst samples were obtained from F-T synthesis runs at medium pressure (1.48 MPa) with a H2:CO ratio of 0.7. Samples were analyzed without removal of the wax to preserve the catalyst microstructure intact and prevent oxidation due to air exposure. In all active Fe catalysts, a highly dispersed chi-carbide (Fe5C2) phase with an average particle size <10 nm was seen to be present along with larger sized particles of hexagonal Fe 7C3. On the other hand, the carbide phase whose XRD pattern resembles that obtained by the Barton and Gale was found to be associated with catalysts of low activity. All carbide particles are covered with amorphous carbonaceous layers as seen by electron energy loss spectroscopy (EELS). In a series of separate experiments, phase transformations that occur during catalyst activation at atmospheric pressure were studied. During direct CO carburization of iron oxide at 250°C, multiple nucleation sites lead to formation of smaller Fe carbide particles predominantly of the Barton-Gale carbide. However, starting from metallic Fe we obtain a chi-carbide phase without significant change in particle size. Treatment in syngas (H 2:CO = 0.7) results in less complete carburization and larger particle sizes for both the carbide and the magnetite phases. The presence of trace amounts of water vapor during reduction appears to cause formation of large faceted magnetite crystals, which are difficult to further transform to the active carbide phase. The silica support is effective at keeping the Fe phases

  15. Enhanced Fischer-Tropsch synthesis performance of iron-based catalysts supported on nitric acid treated N-doped CNTs

    NASA Astrophysics Data System (ADS)

    Li, Zhenhua; Liu, Renjie; Xu, Yan; Ma, Xinbin

    2015-08-01

    Iron-based catalysts supported on N-doped CNTs (NCNTs) treated by various concentrations of nitric acid for Fischer-Tropsch synthesis (FTS) were investigated. An improved catalytic performance for the iron catalyst supported on acid treated NCNTs was obtained and the suitable nitric acid concentration was 10 M. The physiochemical properties of the NCNTs and the corresponding catalysts were characterized by BET, TEM, XRD, XPS, TGA and H2-TPR. The acid treatment removed the impurity and amorphous carbon, damaged the bamboo-like structure and increased the number of oxygen-containing functional groups and graphitization degree on the NCNTs. The more iron particles located inside the channels of NCNTs, the better catalytic FTS performance due to high dispersion and reducibility.

  16. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 12, June 26, 1993--September 26, 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-07-01

    The objectives of this contract are to develop a technology for the production of active and stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scale-up procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. With a feed containing hydrogen (H{sub 2}) and carbon monoxide (CO) in the molar ratio of 0.5 to 1.0 to the slurry bubble column reactor, the catalyst performance target is 88% CO + H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/g Fe. The desired sum of methane and ethane selectivities is no more than 4%, and the conversion loss per week is not to exceed 1%.

  17. Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 4, June 26, 1991--September 26, 1991

    SciTech Connect

    Frame, R.R.

    1991-12-31

    Objectives are to develop active, stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. For a H{sub 2}-CO in molar ratio of 0.5 to 1.0, catalyst performance target is 88% CO+H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/gFe, with no more than 4% methane/ethane selectivity and 1% conversion loss per week. During this period, it was found that the performance of the slurry-phase iron and copper oxide-based catalyst depends on the amount of K. Five catalysts with differing K contents were studied. The catalysts with the lowest K were more active than the ones with higher K levels. The one with the middle K level was judged best.

  18. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    SciTech Connect

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2006-03-03

    Efforts during this second year focused on four areas: (1) continued searching and summarizing of published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) investigation of CO adsorption/desorption and temperature programmed hydrogenation (TPH) of carbonaceous species after FTS on unsupported iron and alumina-supported iron catalysts; (3) activity tests of alumina-supported iron catalysts in a fixed bed reactor; (4) sequential design of experiments, for the collection of rate data in a Berty CSTR reactor, and nonlinear-regression analysis to obtain kinetic parameters. Literature sources describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts were compiled in a review. Temperature-programmed desorption/reaction methods (the latter using mass-spectrometry detection and also thermogravimetric analyzer (TGA)) were utilized to study CO adsorption/-desorption on supported and unsupported iron catalysts. Molecular and dissociative adsorptions of CO occur on iron catalysts at 25-150 C. The amounts adsorbed and bond strengths of adsorption are influenced by supports and promoters. That CO adsorbs dissociatively on polycrystalline Fe at temperatures well below those of FT reaction indicates that CO dissociation is facile and unlikely to be the rate-limiting step during FTS. Carbonaceous species formed after FT reaction for only 5 minutes at 200 C were initially hydrogenated under mild, isothermal condition (200 C and 1 atm), followed by TPH to 800 C. During the mild, isothermal hydrogenation, only about 0.1-0.2 mL of atomic carbon is apparently removed, while during TPH to 800 C multilayer equivalents of atomic, polymeric, carbidic, and graphitic carbons are removed. Rates of CO conversion on alumina-supported iron catalysts at 220-260 C and 20 atm are correlated well by a Langmuir-Hinshelwood expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be

  19. Iron oxide pillared clay with large gallery height: Synthesis and properties as a Fischer-Tropsch catalyst

    SciTech Connect

    Rightor, E.G.; Tsou, Mingshin; Pinnavaia, T.J. )

    1991-07-01

    New iron oxide pillared montmorillonites have been prepared by the reaction of Na{sup +} montmorillonite with base-hydrolyzed solutions of Fe{sup 3+} salts and subsequent thermal conversion of the intercalated polycations. Depending on the hydrolysis conditions used to generate the pillaring solutions, pillared products with basal spacings in the range 18 to 25 {angstrom} were obtained. Under optimum hydrolysis conditions (base/metal = 2.0 meq/mol, aging time = 23-147 hr) the pillared products contained 6.8-9.8 Fe{sup 3+} ions per O{sub 20}(OH){sub 4} unit cell and exhibited basal spacings of 25-29 {angstrom}. These latter spacings corresponded to exceptionally large gallery heights of 15-19 {angstrom}. Upon calcination at 300C, the spacings decreased to 23-27 {angstrom}. N{sub 2} BET surface areas after outgassing at 350C were in the range 270 to 350 m{sup 2}/g. The pillared products are active catalysts that have undergone Fischer-Tropsch synthesis of hydrocarbons at 275 C and 120 {minus}psi (CO:H{sub 2}=1:2). The hydrocarbon distribution in the C{sub 1}-C{sub 6} range (1.3% conversion) followed Anderson-Schulz-Flory statistics with a chain propagation probability of {alpha} = 0.49. X-ray energy dispersive analysis indicated that substantial amounts of the intercalated iron migrated to the edge sites of the clay particles under reaction conditions. The redistribution of iron resulted in a distribution of gallery heights sufficiently heterogeneous to preclude Bragg X-ray scattering along the 001 direction. Iron migration also occurred upon exposure of the pillared products to the ambient atmosphere for prolonged periods ({ge}3 months).

  20. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    SciTech Connect

    Manos Mavrikakis; James A. Dumesic; Rahul P. Nabar

    2006-09-29

    Work continued on the development of a microkinetic model of Fischer-Tropsch synthesis (FTS) on supported and unsupported Fe catalysts. The following aspects of the FT mechanism on unsupported iron catalysts were investigated on during this third year: (1) the collection of rate data in a Berty CSTR reactor based on sequential design of experiments; (2) CO adsorption and CO-TPD for obtaining the heat of adsorption of CO on polycrystalline iron; and (3) isothermal hydrogenation (IH) after Fischer Tropsch reaction to identify and quantify surface carbonaceous species. Rates of C{sub 2+} formation on unsupported iron catalysts at 220 C and 20 atm correlated well to a Langmuir-Hinshelwood type expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. From desorption of molecularly adsorbed CO at different temperatures the heat of adsorption of CO on polycrystalline iron was determined to be 100 kJ/mol. Amounts and types of carbonaceous species formed after FT reaction for 5-10 minutes at 150, 175, 200 and 285 C vary significantly with temperature. Mr. Brian Critchfield completed his M.S. thesis work on a statistically designed study of the kinetics of FTS on 20% Fe/alumina. Preparation of a paper describing this work is in progress. Results of these studies were reported at the Annual Meeting of the Western States Catalysis and at the San Francisco AIChE meeting. In the coming period, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on unsupported Fe catalysts with/without K and Pt promoters by SSITKA method. This study will help us to (1) understand effects of promoter and support on elementary kinetic parameters and (2) build a microkinetics model for FTS on iron. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on models of defected Fe surfaces, most significantly the stepped Fe(211) surface. Binding

  1. ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

    SciTech Connect

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2005-03-22

    Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts was compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on

  2. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    SciTech Connect

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  3. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Adam Crawford; Burtron H. Davis

    2006-09-30

    In the previous reporting period, modifications were completed for integrating a continuous wax filtration system for a 4 liter slurry bubble column reactor. During the current reporting period, a shakedown of the system was completed. Several problems were encountered with the progressive cavity pump used to circulate the wax/catalyst slurry though the cross-flow filter element and reactor. During the activation of the catalyst with elevated temperature (> 270 C) the elastomer pump stator released sulfur thereby totally deactivating the iron-based catalyst. Difficulties in maintaining an acceptable leak rate from the pump seal and stator housing were also encountered. Consequently, the system leak rate exceeded the expected production rate of wax; therefore, no online filtration could be accomplished. Work continued regarding the characterization of ultra-fine catalyst structures. The effect of carbidation on the morphology of iron hydroxide oxide particles was the focus of the study during this reporting period. Oxidation of Fe (II) sulfate results in predominantly {gamma}-FeOOH particles which have a rod-shaped (nano-needles) crystalline structure. Carbidation of the prepared {gamma}-FeOOH with CO at atmospheric pressure produced iron carbides with spherical layered structure. HRTEM and EDS analysis revealed that carbidation of {gamma}-FeOOH particles changes the initial nano-needles morphology and generates ultrafine carbide particles with irregular spherical shape.

  4. Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

    SciTech Connect

    James K. Neathery; Gary Jacobs; Amitava Sarkar; Burtron H. Davis

    2006-03-31

    The morphological and chemical nature of ultrafine iron catalyst particles (3-5 nm diameters) during activation/FTS was studied by HRTEM, EELS, and Moessbauer spectroscopy. With the progress of FTS, the carbide re-oxidized to magnetite and catalyst activity gradually decreased. The growth of oxide phase continued and average particle size also increased simultaneously. The phase transformation occurred in a ''growing oxide core'' manner with different nano-zones. The nano-range carbide particles did not show fragmentation or attrition as generally observed in micrometer range particles. Nevertheless, when the dimension of particles reached the micrometer range, the crystalline carbide phase appeared to be sprouted on the surface of magnetite single crystal. In the previous reporting period, a design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. During the current reporting period, we have started construction of the new filtration system and began modifications to the 4 liter slurry bubble column reactor (SBCR) reactor. The system will utilize a primary wax separation device followed by a Pall Accusep or Membralox ceramic cross-flow membrane. As of this writing, the unit is nearly complete except for the modification of a moyno-type pump; the pump was shipped to the manufacturer to install a special leak-free, high pressure seal.

  5. Supported fischer-tropsch catalyst and method of making the catalyst

    DOEpatents

    Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

    1987-01-01

    A Fischer-Tropsch catalyst and a method of making the catalyst for a Fischer-Tropsch process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas, is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

  6. Fischer-Tropsch Catalyst for Aviation Fuel Production

    NASA Technical Reports Server (NTRS)

    deLaRee, Ana B.; Best, Lauren M.; Hepp, Aloysius F.

    2011-01-01

    As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

  7. Fischer-Tropsch Catalyst for Aviation Fuel Production

    NASA Technical Reports Server (NTRS)

    DeLaRee, Ana B.; Best, Lauren M.; Bradford, Robyn L.; Gonzalez-Arroyo, Richard; Hepp, Aloysius F.

    2012-01-01

    As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

  8. Tailored fischer-tropsch synthesis product distribution

    DOEpatents

    Wang, Yong; Cao, Chunshe; Li, Xiaohong Shari; Elliott, Douglas C.

    2012-06-19

    Novel methods of Fischer-Tropsch synthesis are described. It has been discovered that conducting the Fischer-Tropsch synthesis over a catalyst with a catalytically active surface layer of 35 microns or less results in a liquid hydrocarbon product with a high ratio of C.sub.5-C.sub.20:C.sub.20+. Descriptions of novel Fischer-Tropsch catalysts and reactors are also provided. Novel hydrocarbon compositions with a high ratio of C.sub.5-C.sub.20:C.sub.20+ are also described.

  9. Moderated ruthenium fischer-tropsch synthesis catalyst

    DOEpatents

    Abrevaya, Hayim

    1991-01-01

    The subject Fischer-Tropsch catalyst comprises moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  10. Novel Fischer-Tropsch catalysts. [DOE patent

    DOEpatents

    Vollhardt, K.P.C.; Perkins, P.

    Novel compounds are described which are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO + H/sub 2/ to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  11. Fischer-Tropsch Wastewater Utilization

    DOEpatents

    Shah, Lalit S.

    2003-03-18

    The present invention is generally directed to handling the wastewater, or condensate, from a hydrocarbon synthesis reactor. More particularly, the present invention provides a process wherein the wastewater of a hydrocarbon synthesis reactor, such as a Fischer-Tropsch reactor, is sent to a gasifier and subsequently reacted with steam and oxygen at high temperatures and pressures so as to produce synthesis gas. The wastewater may also be recycled back to a slurry preparation stage, where solid combustible organic materials are pulverized and mixed with process water and the wastewater to form a slurry, after which the slurry fed to a gasifier where it is reacted with steam and oxygen at high temperatures and pressures so as to produce synthesis gas.

  12. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Final report

    SciTech Connect

    Bukur, D.B.; Mukesh, D.; Patel, S.A.; Zimmerman, W.H.; Rosynek, M.P.; Kellogg, L.J.

    1990-04-01

    This report describes results of a study aimed at developing and evaluating improved catalysts for a slurry Fischer-Tropsch (FT) process for converting synthesis gas to high quality transportation fuels (gasoline and distillate). The improvements in catalyst performance were sought by studying effects of pretreatment conditions, promoters and binders/supports. A total of 20 different, iron based, catalysts were evaluated in 58 fixed bed reactor tests and 10 slurry reactor tests. The major accomplishments and conclusions are summarized below. The pretreatment conditions (temperature, duration and the nature of reducing gas) have significant effect on catalyst performance (activity, selectivity and stability) during Fischer-Tropsch synthesis. One of precipitated unsupported catalysts had hydrocarbon selectivity similar to Mobil`s I-B catalyst in high wax mode operation, and had not experienced any loss in activity during 460 hours of testing under variable process conditions in a slurry reactor. The effect of promoters (copper and potassium) on catalyst performance during FT synthesis has been studied in a systematic way. It was found that potassium promotion increases activities of the FT and water-gas-shift (WGS) reactions, the average molecular weight of hydrocarbon products, and suppresses the olefin hydrogenation and isomerization reactions. The addition of binders/supports (silica or alumina) to precipitated Fe/Cu/K catalysts, decreased their activity but improved their stability and hydrocarbon selectivity. The performance of catalysts of this type was very promising and additional studies are recommended to evaluate their potential for use in commercial slurry reactors.

  13. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO

    SciTech Connect

    Warringham, Robbie; McFarlane, Andrew R.; Lennon, David; MacLaren, Donald A.; Webb, Paul B.; Tooze, Robert P.; Taylor, Jon; Ewings, Russell A.; Parker, Stewart F.

    2015-11-07

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe{sub 2}O{sub 3}) is distinguished by a relatively intense band at 810 cm{sup −1}, which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered.

  14. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO.

    PubMed

    Warringham, Robbie; McFarlane, Andrew R; MacLaren, Donald A; Webb, Paul B; Tooze, Robert P; Taylor, Jon; Ewings, Russell A; Parker, Stewart F; Lennon, David

    2015-11-01

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe2O3) is distinguished by a relatively intense band at 810 cm(-1), which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered. PMID:26547178

  15. Novel Fischer-Tropsch catalysts

    DOEpatents

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1981-01-01

    Novel polymer-supported metal complexes of the formula PS -R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS -H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS -Br; treating said PS -Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS -Li; substituting said PS - Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  16. Novel Fischer-Tropsch catalysts

    DOEpatents

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1981-01-01

    Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  17. Novel Fischer-Tropsch catalysts

    DOEpatents

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1980-01-01

    Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  18. Fischer-Tropsch synthesis in supercritical fluids. Final report

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1998-12-31

    The objective of this study was to investigate Fischer-Tropsch Synthesis (FTS) in the supercritical phase employing a commercial precipitated iron catalysts. As the supercritical fluid the authors used propane and n-hexane. The catalyst had a nominal composition of 100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis and was used in a fixed bed reactor under both normal (conventional) and supercritical conditions. Experimental data were obtained at different temperatures (235 C, 250 C, and 260 C) and synthesis gas feed compositions (H{sub 2}/CO molar feed ratio of 0.67, 1.0 and 2.0) in both modes of operation under steady state conditions. The authors compared the performance of the precipitated iron catalyst in the supercritical phase, with the data obtained in gas phase (fixed bed reactor) and slurry phase (STS reactor). Comparisons were made in terms of bulk catalyst activity and various aspects of product selectivity (e.g. lumped hydrocarbon distribution and olefin content as a function of carbon number). In order to gain better understanding of the role of intraparticle mass transfer during FTS under conventional or supercritical conditions, the authors have measured diffusivities of representative hydrocarbon products in supercritical fluids, as well as their effective diffusion rates into the pores of catalyst at the reaction conditions. They constructed a Taylor dispersion apparatus to measure diffusion coefficients of hydrocarbon products of FTS in sub and supercritical ethane, propane, and hexane. In addition, they developed a tracer response technique to measure the effective diffusivities in the catalyst pores at the same conditions. Based on these results they have developed an equation for prediction of diffusion in supercritical fluids, which is based on the rough hard sphere theory.

  19. Novel Attrition-Resistant Fischer Tropsch Catalyst

    SciTech Connect

    Weast, Logan, E.; Staats, William, R.

    2009-05-01

    There is a strong national interest in the Fischer-Tropsch synthesis process because it offers the possibility of making liquid hydrocarbon fuels from reformed natural gas or coal and biomass gasification products. This project explored a new approach that had been developed to produce active, attrition-resistant Fischer-Tropsch catalysts that are based on glass-ceramic materials and technology. This novel approach represented a promising solution to the problem of reducing or eliminating catalyst attrition and maximizing catalytic activity, thus reducing costs. The technical objective of the Phase I work was to demonstrate that glass-ceramic based catalytic materials for Fischer-Tropsch synthesis have resistance to catalytic deactivation and reduction of particle size superior to traditional supported Fischer-Tropsch catalyst materials. Additionally, these novel glass-ceramic-based materials were expected to exhibit catalytic activity similar to the traditional materials. If successfully developed, the attrition-resistant Fischer-Tropsch catalyst materials would be expected to result in significant technical, economic, and social benefits for both producers and public consumers of Fischer-Tropsch products such as liquid fuels from coal or biomass gasification. This program demonstrated the anticipated high attrition resistance of the glass-ceramic materials. However, the observed catalytic activity of the materials was not sufficient to justify further development at this time. Additional testing documented that a lack of pore volume in the glass-ceramic materials limited the amount of surface area available for catalysis and consequently limited catalytic activity. However, previous work on glass-ceramic catalysts to promote other reactions demonstrated that commercial levels of activity can be achieved, at least for those reactions. Therefore, we recommend that glass-ceramic materials be considered again as potential Fischer-Tropsch catalysts if it can be

  20. Cobalt Fischer-Tropsch catalysts having improved selectivity

    DOEpatents

    Miller, James G.; Rabo, Jule A.

    1989-01-01

    A cobalt Fischer-Tropsch catalyst having an improved steam treated, acid extracted LZ-210 support is taught. The new catalyst system demonstrates improved product selectivity at Fischer-Tropsch reaction conditions evidenced by lower methane production, higher C.sub.5.sup.+ yield and increased olefin production.

  1. F-T process using an iron on mixed zirconia-titania supported catalyst

    DOEpatents

    Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

    1987-01-01

    A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

  2. Amino acids in a Fischer Tropsch type synthesis

    NASA Technical Reports Server (NTRS)

    Brown, D. L.; Lawless, J. G.

    1974-01-01

    One postulation is described for the presence of organic compounds in meteorites which states that they were formed during the condensation of the solar nebula. A viable laboratory simulation of these conditions can be modeled after the industrial Fischer Tropsch reaction, which is known to produce organic compounds called hydrocarbons. In this simulation, a mixture of carbon monoxide, hydrogen and ammonia is heated in the presence of iron meteorite. The reaction products for amino acids, a class of organic compounds important to life, were examined. A large number of these compounds is found in meteorites and other chemical evolution experiments, but only small quantities of a few amino acids were found in the present simulation work. These results are at odds with the existing literature in which many amino acids were reported.

  3. Development and process evaluation of improved Fischer-Tropsch slurry catalysts

    SciTech Connect

    Withers, H.P. ); Bukur, D.B.; Rosynek, M.P. )

    1988-01-01

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst comparisons. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  4. Development and process evaluation of improved Fischer-Tropsch slurry catalysts

    SciTech Connect

    Withers, H.P. ); Bukur, D.B.; Rosynek, M.P. )

    1988-01-01

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  5. Liquid phase Fischer-Tropsch (II) demonstration in the Laporte Alternative Fuels Development Unit. Final topical report. Volume 7, Appendix. Task 1, Engineering modifications (Fischer-Tropsch II demonstration) and Task 2, AFDU shakedown, operations, deactivation and disposal (Fischer-Tropsch II demonstration)

    SciTech Connect

    Bhatt, B.L.

    1995-09-01

    This report presents results from a demonstration of Liquid Phase Fischer-Tropsch (LPFT) technology in DOE`s Alternative Fuels Development Unit (AFDU) at LaPorte, Texas. The run was conducted in a bubble column at the AFDU in May--June 1994. The 10-day run demonstrated a very high level of reactor productivity for LPFT, more than five times the previously demonstrated productivity (1). The productivity was constrained by mass transfer limitations, perhaps due to slurry thickening as a result of carbon formation on the catalyst. With a cobalt catalyst or an improved iron catalyst, if the carbon formation can be avoided, there is significant room for further improvements. This volume contains appendices for: reactor temperature stability; Mott Cross-flow filter test for F-T II; Fischer-Tropsch II run authorizations; Fischer-Tropsch II run chronology; liquid compositions; and F-T II / IIA Demonstration Mass Balances.

  6. INTEGRATED FISCHER TROPSCH MODULAR PROCESS MODEL

    SciTech Connect

    Donna Post Guillen; Richard Boardman; Anastasia M. Gribik; Rick A. Wood; Robert A. Carrington

    2007-12-01

    With declining petroleum reserves, increased world demand, and unstable politics in some of the world’s richest oil producing regions, the capability for the U.S. to produce synthetic liquid fuels from domestic resources is critical to national security and economic stability. Coal, biomass and other carbonaceous materials can be converted to liquid fuels using several conversion processes. The leading candidate for large-scale conversion of coal to liquid fuels is the Fischer Tropsch (FT) process. Process configuration, component selection, and performance are interrelated and dependent on feed characteristics. This paper outlines a flexible modular approach to model an integrated FT process that utilizes a library of key component models, supporting kinetic data and materials and transport properties allowing rapid development of custom integrated plant models. The modular construction will permit rapid assessment of alternative designs and feed stocks. The modeling approach consists of three thrust areas, or “strands” – model/module development, integration of the model elements into an end to end integrated system model, and utilization of the model for plant design. Strand 1, model/module development, entails identifying, developing, and assembling a library of codes, user blocks, and data for FT process unit operations for a custom feedstock and plant description. Strand 2, integration development, provides the framework for linking these component and subsystem models to form an integrated FT plant simulation. Strand 3, plant design, includes testing and validation of the comprehensive model and performing design evaluation analyses.

  7. Improved Fischer-Tropsch catalysts for indirect coal liquefaction

    SciTech Connect

    Wilson, R.B. Jr.; Tong, G.T.; Chan, Y.W.; Huang, H.W.; McCarty, J.G.

    1989-02-01

    The Fischer-Tropsch synthesis (FTS)reaction is the established technology for the production of liquid fuels from coal by an indirect route using coal-derived syngas (CO + H{sub 2}). Modern FTS catalysts are potassium- and copper-promoted iron preparations. These catalysts exhibit moderate activity with carbon monoxide-rich feedstocks such as the syngas produced by advanced coal gasification processes. However, the relatively large yields of by-product methane and high-molecular-weight hydrocarbon waxes detract from the production of desired liquid products in the C{sub 5}-C{sub 16} range needed for motor and aviation fuel. The goal of this program is to decrease undesirable portions of the FTS hydrocarbon yield by altering the Schultz-Flory polymerization product distribution through design and formulation of improved catalysts. Two approaches were taken: (1) reducing the yield of high-molecular-weight hydrocarbon waxes by using highly dispersed catalysts produced from surface-confined multiatomic clusters on acid supports and (2) suppressing methane production by uniformly pretreating active, selective conventional FTS catalysts with submonolayer levels of sulfur.

  8. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Quarterly technical progress report, 1 October--31 December 1988

    SciTech Connect

    Withers, H.P.; Bukur, D.B.; Rosynek, M.P.

    1988-12-31

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst compositions. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  9. Alternative Fuel Research in Fischer-Tropsch Synthesis

    NASA Technical Reports Server (NTRS)

    Surgenor, Angela D.; Klettlinger, Jennifer L.; Yen, Chia H.; Nakley, Leah M.

    2011-01-01

    NASA Glenn Research Center has recently constructed an Alternative Fuels Laboratory which is solely being used to perform Fischer-Tropsch (F-T) reactor studies, novel catalyst development and thermal stability experiments. Facility systems have demonstrated reliability and consistency for continuous and safe operations in Fischer-Tropsch synthesis. The purpose of this test facility is to conduct bench scale Fischer-Tropsch (F-T) catalyst screening experiments while focusing on reducing energy inputs, reducing CO2 emissions and increasing product yields within the F-T process. Fischer-Tropsch synthesis is considered a gas to liquid process which reacts syn-gas (a gaseous mixture of hydrogen and carbon monoxide), over the surface of a catalyst material which is then converted into liquids of various hydrocarbon chain length and product distributions1. These hydrocarbons can then be further processed into higher quality liquid fuels such as gasoline and diesel. The experiments performed in this laboratory will enable the investigation of F-T reaction kinetics to focus on newly formulated catalysts, improved process conditions and enhanced catalyst activation methods. Currently the facility has the capability of performing three simultaneous reactor screening tests, along with a fourth fixed-bed reactor used solely for cobalt catalyst activation.

  10. Fischer-Tropsch wax characterization and upgrading: Final report

    SciTech Connect

    Shah, P.P.; Sturtevant, G.C.; Gregor, J.H.; Humbach, M.J.; Padrta, F.G.; Steigleder, K.Z.

    1988-06-06

    The characterization and upgrading of Fischer-Tropsch wax was studied. The focus of the program was to maximize the yield of marketable transportation fuels from the Fischer-Tropsch process. The wax was characterized using gel permeation chromatography (GPC), high resolution mass spectrometry (HRMS), infrared spectroscopy (IR), gas chromatography (GC), nuclear magnetic resonance (NMR) and various other physical analyses. Hydrocracking studies conducted in a pilot plant indicate that Fischer-Tropsch wax is an excellent feedstock. A high yield of excellent quality diesel fuel was produced with satisfactory catalyst performance at relatively mild operating conditions. Correlations for predicting key diesel fuel properties were developed and checked against actual laboratory blend data. The blending study was incorporated into an economic evaluation. Finally, it is possible to take advantage of the high quality of the Fischer-Tropsch derived distillate by blending a lower value light cycle oil (produced from a refinery FCC unit) representing a high aromatic and low cetane number. The blended stream meets diesel pool specifications (up to 60 wt % LCO addition). The value added to this blending stream further enhances the upgrading complex return. 22 refs., 39 figs., 48 tabs.

  11. Separation of catalyst from Fischer-Tropsch slurry

    SciTech Connect

    White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

    1998-04-01

    This paper describes a process for the separation of catalysts used in Fischer-Tropsch synthesis. The separation is accomplished by extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic. The purified catalyst can be upgraded by various methods.

  12. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, Hayim

    1990-01-01

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  13. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, H.

    1990-07-31

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation. 1 fig.

  14. Simulation models and designs for advanced Fischer-Tropsch technology

    SciTech Connect

    Choi, G.N.; Kramer, S.J.; Tam, S.S.

    1995-12-31

    Process designs and economics were developed for three grass-roots indirect Fischer-Tropsch coal liquefaction facilities. A baseline and an alternate upgrading design were developed for a mine-mouth plant located in southern Illinois using Illinois No. 6 coal, and one for a mine-mouth plane located in Wyoming using Power River Basin coal. The alternate design used close-coupled ZSM-5 reactors to upgrade the vapor stream leaving the Fischer-Tropsch reactor. ASPEN process simulation models were developed for all three designs. These results have been reported previously. In this study, the ASPEN process simulation model was enhanced to improve the vapor/liquid equilibrium calculations for the products leaving the slurry bed Fischer-Tropsch reactors. This significantly improved the predictions for the alternate ZSM-5 upgrading design. Another model was developed for the Wyoming coal case using ZSM-5 upgrading of the Fischer-Tropsch reactor vapors. To date, this is the best indirect coal liquefaction case. Sensitivity studies showed that additional cost reductions are possible.

  15. Process for upgrading wax from Fischer-Tropsch synthesis

    DOEpatents

    Derr, Jr., W. Rodman; Garwood, William E.; Kuo, James C.; Leib, Tiberiu M.; Nace, Donald M.; Tabak, Samuel A.

    1987-01-01

    The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel.

  16. Process for upgrading wax from Fischer-Tropsch synthesis

    DOEpatents

    Derr, W.R. Jr.; Garwood, W.E.; Kuo, J.C.; Leib, T.M.; Nace, D.M.; Tabak, S.A.

    1987-08-04

    The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel. 2 figs.

  17. Cobalt Fischer-Tropsch catalysts having improved selectivity

    DOEpatents

    Miller, James G.; Rabo, Jule A.

    1989-01-01

    The promoter(s) Mn oxide or Mn oxide and Zr oxide are added to a cobalt Fischer-Tropsch catalyst combined with the molecular sieve TC-103 or TC-123 such that the resultant catalyst demonstrates improved product selectivity, stability and catalyst life. The improved selectivity is evidenced by lower methane production, higher C5+ yield and increased olefin production.

  18. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 January 1995--31 March 1995

    SciTech Connect

    Bukur, D.B.; Lang, X.; Reddy, B.

    1995-05-23

    During the reporting period we completed synthesis of about 100 g of catalyst with nominal composition 100 Fe/3 Cu/4 K/16 SiO{sub 2} (S-3416-2), and of another batch (173 g) of the same catalyst (S-3416-3). Also, we synthesized two additional batches of catalyst with nominal composition 100 Fe/5 Cu/6 K/24 SiO{sub 2}, in the amounts of 240 g (S-5624-3) and 200 g (S-5624-4). These amounts are sufficient for all planned tests with these two catalysts for the entire duration of this contract. The synthesized catalysts were characterized by atomic absorption, and BET surface area and pore size distribution measurements.

  19. Development of precipitated iron Fischer-Tropsch catalysts. Quarterly technical progress report, 1 July 1995--30 September 1995

    SciTech Connect

    Bukur, D.B.

    1995-12-20

    The following accomplishments were made on task 4. Reproducibility of Catalyst Preparation: (1) Five slurry reactor tests were completed. Three tests were conducted using catalyst C (100 Fe/3 Cu/4 K/16 SiO{sub 2}) from three different batches (runs SB-2695, SB-2145 and SA-2715), and two tests were conducted with catalyst B (100 Fe/5 Cu/6 K/24 SiO{sub 2}) from two different preparation batches (runs SA-2615 and SB-2585). Performance of catalysts from different batches (activity, selectivity and deactivation rates) was similar to that of catalysts from the original batch (synthesized during DOE Contract DE- AC22-89PC89868). Thus, another major objective of the present contract, demonstration of reproducibility of catalyst preparation procedure and performance, has been accomplished. With these tests the work on Task 4 has been successfully completed. Two fixed bed reactor tests of catalysts B and C synthesized using potassium silicate solution as the source of potassium promoter were completed during this period (Task 5. The Effect of Source of Potassium and Basic Oxide Promoter). Activity of catalysts prepared using potassium silicate as the source of potassium promotion was somewhat higher, and their methane selectivities were higher than those of the corresponding catalysts prepared by incipient wetness impregnation using KHCO{sub 3} as the source of potassium promoter. However, these differences were not large, and may have been caused by experimental artifacts (e.g. existence of local hot spots in a reactor). A slurry reactor test (SA-2405) of catalyst with nominal composition 100 Fe/5 Cu/2 Ca/24 SiO{sub 2} was completed (Task 5). In general, the catalyst activity, space-time-yield, and hydrocarbon selectivities in this run during testing at:260{degrees}C, 2.17 MPa (300 psig), 2-2.6 Nl/g-cat/h and H{sub 2}CO=0.67 were quite good, and comparable to the best results obtained in our Laboratory.

  20. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-05

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  1. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  2. Separation of catalyst from Fischer-Tropsch slurry

    DOEpatents

    White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

    1998-10-27

    In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

  3. Separation of catalyst from Fischer-Tropsch slurry

    DOEpatents

    White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

    1998-10-27

    In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

  4. Attrition resistant bulk iron catalysts and processes for preparing and using same

    DOEpatents

    Jothimurugesan, Kandaswamy; Goodwin, Jr., James G.; Gangwal, Santosh K.

    2007-08-21

    An attrition resistant precipitated bulk iron catalyst is prepared from iron oxide precursor and a binder by spray drying. The catalysts are preferably used in carbon monoxide hydrogenation processes such as Fischer-Tropsch synthesis. These catalysts are suitable for use in fluidized-bed reactors, transport reactors and, especially, slurry bubble column reactors.

  5. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYSTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2005-09-29

    This report covers the third year of this research grant under the University Coal Research program. The overall objective of this project is to develop a comprehensive kinetic model for slurry phase Fischer-Tropsch synthesis (FTS) on iron catalysts. This model will be validated with experimental data obtained in a stirred tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (H{sub 2}O, CO{sub 2}, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the reporting period we utilized experimental data from the STSR, that were obtained during the first two years of the project, to perform vapor-liquid equilibrium (VLE) calculations and estimate kinetic parameters. We used a modified Peng-Robinson (PR) equation of state (EOS) with estimated values of binary interaction coefficients for the VLE calculations. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Occasional discrepancies (for some of the experimental data) between calculated and experimental values of the liquid phase composition were ascribed to experimental errors. The VLE calculations show that the vapor and the liquid are in thermodynamic equilibrium under reaction conditions. Also, we have successfully applied the Levenberg-Marquardt method (Marquardt, 1963) to estimate parameters of a kinetic model proposed earlier by Lox and Froment (1993b) for FTS on an iron catalyst. This kinetic model is well suited for initial studies where the main goal is to learn techniques for parameter estimation and statistical analysis of estimated values of model parameters. It predicts that the chain growth parameter ({alpha}) and olefin to paraffin ratio are independent of carbon number, whereas our experimental data show that they vary with the carbon number

  6. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2006-09-29

    This report covers the fourth year of a research project conducted under the University Coal Research Program. The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (water, carbon dioxide, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the fourth year of the project, an analysis of experimental data collected during the second year of this project was performed. Kinetic parameters were estimated utilizing product distributions from 27 mass balances. During the reporting period two kinetic models were employed: a comprehensive kinetic model of Dr. Li and co-workers (Yang et al., 2003) and a hydrocarbon selectivity model of Van der Laan and Beenackers (1998, 1999) The kinetic model of Yang et al. (2003) has 24 parameters (20 parameters for hydrocarbon formation, and 4 parameters for the water-gas-shift (WGS) reaction). Kinetic parameters for the WGS reaction and FTS synthesis were estimated first separately, and then simultaneously. The estimation of these kinetic parameters employed the Levenberg-Marquardt (LM) method and the trust-region reflective Newton large-scale (LS) method. A genetic algorithm (GA) was incorporated into estimation of parameters for FTS reaction to provide initial estimates of model parameters. All reaction rate constants and activation energies were found to be positive, but at the 95% confidence level the intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons are predicted fairly accurately, whereas the model underpredicts values of higher molecular weight

  7. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  8. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  9. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  10. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  11. Trapping Planetary Noble Gases During the Fischer-Tropsch-Type Synthesis of Organic Materials

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.; Johnson, N. M.; Meshik, A.

    2010-01-01

    When hydrogen, nitrogen and CO arc exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions!, Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these rcactions:u . The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic materiaL Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  12. Baseline design/economics for advanced Fischer-Tropsch technology

    SciTech Connect

    Not Available

    1992-04-27

    The objectives of the study are to: Develop a baseline design for indirect liquefaction using advanced Fischer-Tropsch (F-T) technology. Prepare the capital and operating costs for the baseline design. Develop a process flowsheet simulation (PFS) model. The baseline design, the economic analysis, and the computer model will be the major research planning tools that Pittsburgh Energy Technology Center will use to plan, guide, and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction for the manufacture of synthetic liquid fuels from coal.

  13. Separation of Fischer-Tropsch from Catalyst by Supercritical Extraction.

    SciTech Connect

    Joyce, P.C.; Thies, M.C.

    1997-10-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300{degrees}C. Initial work is being performed using n-hexane as the solvent.

  14. Development and process evaluation of improved Fischer-Tropsch slurry catalysts. Sixth quarterly technical progress report, 1 January--31 March 1988

    SciTech Connect

    Withers, H.P.; Bukur, D.B.; Rosynek, M.P.

    1988-12-31

    The objective of this contract is to develop a consistent technical data base on the use of iron-based catalysts in Fischer-Tropsch (FT) synthesis reactions. This data base will be developed to allow the unambiguous comparison of the performance of these catalysts with each other and with state-of-the-art iron catalyst comparisons. Particular attention will be devoted to generating reproducible kinetic and selectivity data and to developing reproducible improved catalyst compositions.

  15. CHAIN-LIMITING OPERATION OF FISCHER-TROPSCH REACTOR

    SciTech Connect

    Apostolos A. Nikolopoulos; Santosh K. Gangwal

    2003-06-01

    The use of pulsing in Fischer-Tropsch (FT) synthesis to limit the hydrocarbon chain growth and maximize the yield of diesel-range (C{sub 10}-C{sub 20}) products was examined on high-chain-growth-probability ({alpha} {ge} 0.9) FT catalysts. Pulsing experiments were conducted using a stainless-steel fixed-bed micro-reactor, equipped with both on-line (for the permanent gases and light hydrocarbons, C{sub 1}-C{sub 15}) and off-line (for the heavier hydrocarbons, C{sub 10}-C{sub 65}) gas chromatography analysis. Additional experiments were performed using a highly active attrition-resistant iron-based FT synthesis catalyst in a 1-liter continuous stirred-tank rector (CSTR). On both a Co-ZrO{sub 2}/SiO{sub 2} and a Co/Al{sub 2}O{sub 3} FT synthesis catalyst application of H{sub 2} pulsing causes significant increase in CO conversion, and only an instantaneous increase in undesirable selectivity to CH{sub 4}. Increasing the frequency of H{sub 2} pulsing enhances the selectivity to C{sub 10}-C{sub 20} compounds but the chain-growth probability {alpha} remains essentially unaffected. Increasing the duration of H{sub 2} pulsing results in enhancing the maximum obtained CO conversion and an instantaneous selectivity to CH{sub 4}. An optimum set of H{sub 2} pulse parameters (pulse frequency, pulse duration) is required for maximizing the yield of desirable diesel-range C{sub 10}-C{sub 20} products. Application of a suitable H{sub 2} pulse in the presence of added steam in the feed is a simple method to overcome the loss in activity and the shift in paraffin vs. olefin selectivity (increase in the olefin/paraffin ratio) caused by the excess steam. A decrease in syngas concentration has a strong suppressing effect on the olefin/paraffin ratio of the light hydrocarbon products. Higher syngas concentration can increase the chain growth probability {alpha} and thus allow for better evaluation of the effect of pulsing on FT synthesis. On a high-{alpha} Fe/K/Cu/SiO{sub 2} FT

  16. Kinetics of Slurry Phase Fischer-Tropsch Synthesis

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski; Lech Nowicki; Madhav Nayapati

    2006-12-31

    The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. Three STSR tests of the Ruhrchemie LP 33/81 catalyst were conducted to collect data on catalyst activity and selectivity under 25 different sets of process conditions. The observed decrease in 1-olefin content and increase in 2-olefin and n-paraffin contents with the increase in conversion are consistent with a concept that 1-olefins participate in secondary reactions (e.g. 1-olefin hydrogenation, isomerization and readsorption), whereas 2-olefins and n-paraffins are formed in these reactions. Carbon number product distribution showed an increase in chain growth probability with increase in chain length. Vapor-liquid equilibrium calculations were made to check validity of the assumption that the gas and liquid phases are in equilibrium during FTS in the STSR. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Discrepancies between the calculated and experimental values for the liquid-phase composition (for some of the experimental data) are ascribed to experimental errors in the amount of wax collected from the reactor, and the relative amounts of hydrocarbon wax and Durasyn 164 oil (start-up fluid) in the liquid samples. Kinetic parameters of four kinetic models (Lox and Froment, 1993b; Yang et al., 2003; Van der Laan and Beenackers, 1998, 1999; and an extended kinetic model of Van der Laan and Beenackers) were estimated from experimental data in the STSR tests. Two of these kinetic models (Lox and Froment, 1993b; Yang et al., 2003) can predict a complete product distribution (inorganic species and hydrocarbons), whereas the kinetic model of Van der Laan and Beenackers (1998, 1999) can

  17. Synthesis gas solubility in Fischer-Tropsch slurry: Final report

    SciTech Connect

    Chao, K.C.; Lin, H.M.

    1988-01-01

    The objective is to investigate the phase equilibrium behavior of synthesis gases and products in a Fischer-Tropsch slurry reactor. A semi-flow apparatus has been designed and constructed for this purpose. Measurements have been made for hydrogen, cabon monoxide, methane, ethane, ethylene, and carbon dioxide in a heavy n-paraffin at temperatures from 100 to 300)degree)C and pressures 10 to 50 atm. Three n-paraffin waxes: n-eicosane (n-C/sub 20/), n-octacosane )n-C/sub 28/), and n-hexatriacontane (n-C/sub 36/), were studied to model the industrial wax. Solubility of synthesis gas mixtures of H/sub 2/ and CO in n-C/sub 28/ was also determined at two temperatures (200 and 300)degree)C) for each of three gas compositions (40.01, 50.01, and 66.64 mol%) of hydrogen). Measurements were extended to investigate the gas solubility in two industrial Fischer-Tropsch waxes: Mobilwax and SASOL wax. Observed solubility increases in the order: H/sub 2/, CO, CH/sub 4/, CO/sub 2/, C/sub 2/H/sub 4/, C/sub 2/H/sub 6/, at a given temperature pressure, and in the same solvent. Solubility increases with increasing pressure for all the gases. Lighter gases H/sub 2/ and CO show increased solubility with increasing temperature, while the heavier gases CO/sub 2/, ethane, and ethylene show decreased solubility with increasing temperature. The solubility of methane, the intermediate gas, changes little with temperature, and shows a shallow minimum at about 200)degrees)C or somewhat above. Henry's constant and partial molal volume of the gas solute at infinite dilution are determinedfrom the gas solubility data. A correlation is developed from the experimental data in the form on an equation of state. A computer program has been prepared to implement the correlation. 19 refs., 66 figs., 39 tabs.

  18. Selectivity to olefins of Fe/SiO{sub 2}-MgO catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Gallegos, N.G.; Alvarez, A.M.; Cagnoli, M.V.; Bengoa, J.F.

    1996-06-01

    SiO{sub 2} covered with MgO has been used as support of iron catalysts in the Fischer-Tropsch reaction. Catalysts of 5% (w/w) iron concentration and 2, 4, and 8% (w/w) of MgO on SiO{sub 2} were prepared. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to characterize the type of iron species and the metallic crystal sizes. MgO covers the SiO{sub 2} surface and modifies the metallic crystal size. The activity to total hydrocarbons increases with the amount of MgO added. An optimal concentration of about 4% (w/w) was found to have the highest selectivity to olefins. 45 refs., 13 figs., 3 tabs.

  19. Metal (Fe, Co, Ni) supported on different aluminas as Fischer-Tropsch catalyst

    NASA Astrophysics Data System (ADS)

    Dahlan, Marsih, I. Nyoman; Makertihartha, I. G. B. N.; Praserthdam, Piyasan; Panpranot, Joongjai; Ismunandar

    2015-09-01

    This research aimed to compare the physico-chemical properties of the same metal M (M = iron, cobalt, nickel) supported on aluminas with different morphology and pore size as Fischer-Tropsch catalyst. The aluminas applied as support were alumina synthesized through hydrothermal process, alumina formed by pretreatment of catapal and commercial alumina which named as Ahy, Aca, and Aco respectively. Ahy has uniform morphology of nanotubes while Aca and Aco showed non-uniform morphology of particle lumps. The particle lumps of Aca were larger than those of Aco. Ahy, Aca, and Aco respectively has average pore diameter of 2.75, 2.86 and 2.9 nm. Metals were deposited on the supports by incipient-wetness impregnation method. The catalysts were characterized by XRD, H2-TPR, and H2 chemisorption. Catalyst acitivity test for Fischer-Tropsch reaction was carried out in a micro reactor at 200 °C and 1 atm, and molar ratio of H2/CO = 2:1. The metal oxide particle size increased in the order M/Aco < M/Aca < M/Ahy. The catalysts reducibility also increased according to the order M/Aco < M/Aca < M/Ahy suggesting that the larger metal oxide particles are more reducible. The number of active site was not proportional to the reducibility because during the reduction, larger metal oxide particles were converted into larger metal particles. On the other hand, the number of active sites was inversely proportional to the particle sizes. The number of active site increased in the order M/Ahy < M/Aco < M/Aca. The catalytic activity also increased in the following order M/Ahy < M/Aco < M/Aca. The activity per active site increased according to the order M/Aca < M/Aco < M/Ahy meaning that for M/Ahy, a little increase in active site will lead to a significance increase in catalytic activity. It showed that Ahy has potential for the better support.

  20. Metal (Fe, Co, Ni) supported on different aluminas as Fischer-Tropsch catalyst

    SciTech Connect

    Dahlan; Marsih, I. Nyoman Ismunandar; Makertihartha, I. G. B. N.; Praserthdam, Piyasan; Panpranot, Joongjai

    2015-09-30

    This research aimed to compare the physico-chemical properties of the same metal M (M = iron, cobalt, nickel) supported on aluminas with different morphology and pore size as Fischer-Tropsch catalyst. The aluminas applied as support were alumina synthesized through hydrothermal process, alumina formed by pretreatment of catapal and commercial alumina which named as Ahy, Aca, and Aco respectively. Ahy has uniform morphology of nanotubes while Aca and Aco showed non-uniform morphology of particle lumps. The particle lumps of Aca were larger than those of Aco. Ahy, Aca, and Aco respectively has average pore diameter of 2.75, 2.86 and 2.9 nm. Metals were deposited on the supports by incipient-wetness impregnation method. The catalysts were characterized by XRD, H{sub 2}-TPR, and H{sub 2} chemisorption. Catalyst acitivity test for Fischer-Tropsch reaction was carried out in a micro reactor at 200 °C and 1 atm, and molar ratio of H{sub 2}/CO = 2:1. The metal oxide particle size increased in the order M/Aco < M/Aca < M/Ahy. The catalysts reducibility also increased according to the order M/Aco < M/Aca < M/Ahy suggesting that the larger metal oxide particles are more reducible. The number of active site was not proportional to the reducibility because during the reduction, larger metal oxide particles were converted into larger metal particles. On the other hand, the number of active sites was inversely proportional to the particle sizes. The number of active site increased in the order M/Ahy < M/Aco < M/Aca. The catalytic activity also increased in the following order M/Ahy < M/Aco < M/Aca. The activity per active site increased according to the order M/Aca < M/Aco < M/Ahy meaning that for M/Ahy, a little increase in active site will lead to a significance increase in catalytic activity. It showed that Ahy has potential for the better support.

  1. LIQUID PHASE FISCHER-TROPSCH (III & IV) DEMONSTRATION IN THE LAPORTE ALTERNATIVE FUELS DEVELOPMENT UNIT. Final Topical Report. Volume I/II: Main Report. Task 1: Engineering Modifications (Fischer-Tropsch III & IV Demonstration) and Task 2: AFDU Shakedown, Operations, Deactivation (Shut-Down) and Disposal (Fischer-Tropsch III & IV Demonstration).

    SciTech Connect

    Bharat L. Bhatt

    1999-06-01

    Slurry phase Fischer-Tropsch technology was successfully demonstrated in DOE's Alternative Fuels Development Unit (AFDU) at LaPorte, Texas. Earlier work at LaPorte, with iron catalysts in 1992 and 1994, had established proof-of-concept status for the slurry phase process. The third campaign (Fischer-Tropsch III), in 1996, aimed at aggressively extending the operability of the slurry reactor using a proprietary cobalt catalyst. Due to an irreversible plugging of catalyst-wax separation filters as a result of unexpected catalyst fines generation, the operations had to be terminated after seven days on-stream. Following an extensive post-run investigation by the participants, the campaign was successfully completed in March-April 1998, with an improved proprietary cobalt catalyst. These runs were sponsored by the U. S. Department of Energy (DOE), Air Products & Chemicals, Inc., and Shell Synthetic Fuels, Inc. (SSFI). A productivity of approximately 140 grams (gm) of hydrocarbons (HC)/ hour (hr)-liter (lit) of expanded slurry volume was achieved at reasonable system stability during the second trial (Fischer-Tropsch IV). The productivity ranged from 110-140 at various conditions during the 18 days of operations. The catalyst/wax filters performed well throughout the demonstration, producing a clean wax product. For the most part, only one of the four filter housings was needed for catalyst/wax filtration. The filter flux appeared to exceed the design flux. A combination of use of a stronger catalyst and some innovative filtration techniques were responsible for this success. There was no sign of catalyst particle attrition and very little erosion of the slurry pump was observed, in contrast to the Fischer-Tropsch III operations. The reactor operated hydrodynamically stable with uniform temperature profile and gas hold-ups. Nuclear density and differential pressure measurements indicated somewhat higher than expected gas hold-up (45 - 50 vol%) during Fischer-Tropsch IV

  2. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260[degrees]C). The SCF medium to be employed is n-Hexane (P[sub c] = 29.7 bar; [Tc] = 233.7[degrees]C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H[sub 2]/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  3. Synthesis of adenine, guanine, cytosine, and other nitrogen organic compounds by a Fischer-Tropsch-like process.

    NASA Technical Reports Server (NTRS)

    Yang, C. C.; Oro, J.

    1971-01-01

    Study of the formation of purines, pyrimidines, and other bases from CO, H2, and NH3 under conditions similar to those used in the Fischer-Tropsch process. It is found that industrial nickel/iron alloy catalyzes the synthesis of adenine, guanine, cytosine, and other nitrogenous compounds from mixtures of CO, H2, and NH3 at temperatures of about 600 C. Sufficient sample was accumulated to isolate as solid products adenine, guanine, and cytosine, which were identified by infrared spectrophotometry. In the absence of nickel/iron catalyst, at 650 C, or in the presence of this catalyst, at 450 C, no purines or pyrimidines were synthesized. These results confirm and extend some of the work reported by Kayatsu et al. (1968).

  4. The selective catalytic cracking of Fischer-Tropsch liquids to high value transportation fuels. Final report

    SciTech Connect

    Schwartz, M.M.; Reagon, W.J.; Nicholas, J.J.; Hughes, R.D.

    1994-11-01

    Amoco Oil Company, investigated a selective catalytic cracking process (FCC) to convert the Fischer-Tropsch (F-T) gasoline and wax fractions to high value transportation fuels. The primary tasks of this contract were to (1) optimize the catalyst and process conditions of the FCC process for maximum conversion of F-T wax into reactive olefins for later production of C{sub 4}{minus}C{sub 8} ethers, and (2) use the olefin-containing light naphtha obtained from FCC processing of the F-T wax as feedstock for the synthesis of ethers. The catalytic cracking of F-T wax feedstocks gave high conversions with low activity catalysts and low process severities. HZSM-5 and beta zeolite catalysts gave higher yields of propylene, isobutylene, and isoamylenes but a lower gasoline yield than Y zeolite catalysts. Catalyst selection and process optimization will depend on product valuation. For a given catalyst and process condition, Sasol and LaPorte waxes gave similar conversions and product selectivities. The contaminant iron F-T catalyst fines in the LaPorte wax caused higher coke and hydrogen yields.

  5. Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

    SciTech Connect

    Gormley, R.J.; Zarochak, M.F.; Deffenbaugh, P.W.; Rao, K.R.P.M.

    1995-12-31

    The purpose of this research was to measure activity, selectivity, and the maintenance of these properties in slurry autoclave experiments with a Fischer-Tropsch (FT) catalyst that was used in the {open_quotes}FT II{close_quotes} bubble-column test, conducted at the Alternative Fuels Development Unit (AFDU) at LaPorte, Texas during May 1994. The catalyst contained iron, copper, and potassium and was formulated to produce mainly hydrocarbons in the gasoline range with lesser production of diesel-range products and wax. The probability of chain growth was thus deliberately kept low. Principal goals of the autoclave work have been to find the true activity of this catalyst in a stirred tank reactor, unhindered by heat or mass transfer effects, and to obtain a steady conversion and selectivity over the approximately 15 days of each test. Slurry autoclave testing of the catalyst in heavier waxes also allows insight into operation of larger slurry bubble column reactors. The stability of reactor operation in these experiments, particularly at loadings exceeding 20 weight %, suggests the likely stability of operations on a larger scale.

  6. Improved Fischer-Tropsch catalysts for indirect coal liquefaction. Final report

    SciTech Connect

    Wilson, R.B. Jr.; Tong, G.T.; Chan, Y.W.; Huang, H.W.; McCarty, J.G.

    1989-02-01

    The Fischer-Tropsch synthesis (FTS)reaction is the established technology for the production of liquid fuels from coal by an indirect route using coal-derived syngas (CO + H{sub 2}). Modern FTS catalysts are potassium- and copper-promoted iron preparations. These catalysts exhibit moderate activity with carbon monoxide-rich feedstocks such as the syngas produced by advanced coal gasification processes. However, the relatively large yields of by-product methane and high-molecular-weight hydrocarbon waxes detract from the production of desired liquid products in the C{sub 5}-C{sub 16} range needed for motor and aviation fuel. The goal of this program is to decrease undesirable portions of the FTS hydrocarbon yield by altering the Schultz-Flory polymerization product distribution through design and formulation of improved catalysts. Two approaches were taken: (1) reducing the yield of high-molecular-weight hydrocarbon waxes by using highly dispersed catalysts produced from surface-confined multiatomic clusters on acid supports and (2) suppressing methane production by uniformly pretreating active, selective conventional FTS catalysts with submonolayer levels of sulfur.

  7. Process design and solvent recycle for the supercritical Fischer-Tropsch synthesis

    SciTech Connect

    Wensheng Linghu; Xiaohong Li; Kenji Asami; Kaoru Fujimoto

    2006-02-01

    A recycle reactor system for supercritical Fischer-Tropsch synthesis was successfully designed and tested. The new reactor system has these characteristics: (1) integration of supercritical Fischer-Tropsch reactions, natural separation of produced wax from liquid phase, and recycle of the solvent and (2) natural recycle of solvent driven by self-gravity. A 20% Co/SiO{sub 2} catalyst and n-hexane were used as a catalyst and supercritical fluid, respectively. The results show that the average CO conversion at the steady state was 45% with recycle and 58% without recycle. The lumped hydrocarbon products distribution did not have any obvious difference between with and without recycle operation; however, {alpha}-olefin content of products with recycle was lower than that without recycle. The XRD result indicates that most of the reduced cobalt remains in the metallic state during the Fischer-Tropsch reactions for both cases. 22 refs., 3 figs., 1 tab.

  8. Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

    PubMed Central

    2011-01-01

    This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

  9. Thermal Stability Testing of a Fischer-Tropsch Fuel and Various Blends with Jet A

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Suder; Surgenor, Angela; Yen, Chia

    2010-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer-Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline conventional Jet A, a commercial grade F-T jet fuel, and various blends of this F-T fuel in Jet A. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  10. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch

    SciTech Connect

    Marcelin, G.

    1991-10-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butytl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; (2) addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and, (3) addition of methanol to slurry phase FT synthesis making iso-olefins.

  11. Development of Detailed Kinetic Models for Fischer-Tropsch Fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Carstensen, H; Dean, A M

    2008-10-28

    Fischer-Tropsch (FT) fuels can be synthesized from a syngas stream generated by the gasification of biomass. As such they have the potential to be a renewable hydrocarbon fuel with many desirable properties. However, both the chemical and physical properties are somewhat different from the petroleum-based hydrocarbons that they might replace, and it is important to account for such differences when considering using them as replacements for conventional fuels in devices such as diesel engines and gas turbines. FT fuels generally contain iso-alkanes with one or two substituted methyl groups to meet the pour-point specifications. Although models have been developed for smaller branched alkanes such as isooctane, additional efforts are required to properly capture the kinetics of the larger branched alkanes. Recently, Westbrook et al. developed a chemical kinetic model that can be used to represent the entire series of n-alkanes from C{sub 1} to C{sub 16} (Figure 1). In the current work, the model is extended to treat 2,2,4,4,6,8,8-heptamethylnonane (HMN), a large iso-alkane. The same reaction rate rules used in the iso-octane mechanism were incorporated in the HMN mechanism. Both high and low temperature chemistry was included so that the chemical kinetic model would be applicable to advanced internal combustion engines using low temperature combustion strategies. The chemical kinetic model consists of 1114 species and 4468 reactions. Concurrently with this effort, work is underway to improve the details of specific reaction classes in the mechanism, guided by high-level electronic structure calculations. Attention is focused upon development of accurate rate rules for abstraction of the tertiary hydrogens present in branched alkanes and properly accounting for the pressure dependence of the ?-scission, isomerization, and R + O{sub 2} reactions.

  12. The development of precipitated iron catalysts with improved stability

    SciTech Connect

    Not Available

    1990-01-01

    The goal of this program is to identify the chemical principles governing the deactivation of precipitated iron catalysts during Fischer-Tropsch synthesis and to use these chemical principles in the design of catalysts suitable for slurry reactors. This report covers testing an iron catalyst. During the last quarter, a new precipitated iron catalyst was prepared and tested in the slurry autoclave reactor at various conditions. This catalyst did not noticeably deactivate during 1250 hours of testing. This quarter, the test was extended to include performance evaluations at different conversion levels ranging from 35 to 88% at 265 and 275{degree}C. The conversion levels were varied by changing the feed rate. The catalytic performance at different conversion intervals was then integrated to approximately predict performance in a bubble column reactor. The run was shut down at the end of 1996 hours because of a 24-hour-power outage. When the power was back on, the run was restarted from room temperature. Catalytic performance during the first 300 hours after the restart-up was monitored. Overall product distributions are being tabulated as analytical laboratory data are obtained. 34 figs., 3 tabs.

  13. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objectives for this quarter were: (1) to install and test the temperature probe and the flammable gas detector: (2) to conduct Fischer-Tropsch synthesis experiments at baseline conditions and at a high pressure in order to test the newly constructed fixed bed reactor assembly.

  14. The facile fabrication of magnetite nanoparticles and their enhanced catalytic performance in Fischer-Tropsch synthesis.

    PubMed

    Zheng, Shenke; Sun, Jiaqiang; Song, Dechen; Chen, Zheng; Chen, Jiangang

    2015-07-14

    Uniform and crystalline magnetite nanoparticles are facilely fabricated and utilized as an efficient catalyst in Fischer-Tropsch synthesis (FTS). The catalyst exhibits a high and stable activity with low methane selectivity, attributed to its remarkable structural and chemical stability at the realistic conditions of FTS. PMID:26074335

  15. Critique of Fischer-Tropsch type reactions in the solar nebula

    NASA Astrophysics Data System (ADS)

    Ramadurai, S.; Hoyle, F.; Wickramasinghe, N. C.

    1993-09-01

    The paucity of kinetic data for the operation of Fischer-Tropsch Type (FTT) reactions, at the appropriate conditions for the primitive solar nebula, is highlighted. The observed isotopic abundances of D, C-13 and N-15 in the meteoritic kerogen are summarized. These are shown to be against the operation of FTT reactions in the primitive solar nebula.

  16. Fly ash zeolite catalyst support for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Campen, Adam

    This dissertation research aimed at evaluating a fly ash zeolite (FAZ) catalyst support for use in heterogeneous catalytic processes. Gas phase Fischer-Tropsch Synthesis (FTS) over a fixed-bed of the prepared catalyst/FAZ support was identified as an appropriate process for evaluation, by comparison with commercial catalyst supports (silica, alumina, and 13X). Fly ash, obtained from the Wabash River Generating Station, was first characterized using XRD, SEM/EDS, particle size, and nitrogen sorption techniques. Then, a parametric study of a two-step alkali fusion/hydrothermal treatment process for converting fly ash to zeolite frameworks was performed by varying the alkali fusion agent, agent:flyash ratio, fusion temperature, fused ash/water solution, aging time, and crystallization time. The optimal conditions for each were determined to be NaOH, 1.4 g NaOH: 1 g fly ash, 550 °C, 200 g/L, 12 hours, and 48 hours. This robust process was applied to the fly ash to obtain a faujasitic zeolite structure with increased crystallinity (40 %) and surface area (434 m2/g). Following the modification of fly ash to FAZ, ion exchange of H+ for Na+ and cobalt incipient wetness impregnation were used to prepare a FTS catalyst. FTS was performed on the catalysts at 250--300 °C, 300 psi, and with a syngas ratio H2:CO = 2. The HFAZ catalyst support loaded with 11 wt% cobalt resulted in a 75 % carbon selectivity for C5 -- C18 hydrocarbons, while methane and carbon dioxide were limited to 13 and 1 %, respectively. Catalyst characterization was performed by XRD, N2 sorption, TPR, and oxygen pulse titration to provide insight to the behavior of each catalyst. Overall, the HFAZ compared well with silica and 13X supports, and far exceeded the performance of the alumina support under the tested conditions. The successful completion of this research could add value to an underutilized waste product of coal combustion, in the form of catalyst supports in heterogeneous catalytic processes.

  17. CHAIN-LIMITING OPERATION OF FISCHER-TROPSCH REACTOR

    SciTech Connect

    Apostolos A. Nikolopoulos; Santosh K. Gangwal

    2000-11-01

    The use of pulsing to limit the chain growth of the hydrocarbon products of the Fischer-Tropsch (FT) synthesis in order to maximize the yield of diesel-range (C{sub 10}-C{sub 20}) products was examined on three high-chain-growth-probability ({alpha} {ge} 0.9) FT catalysts. On a Co-ZrO{sub 2}/SiO{sub 2} FT synthesis catalyst the application of H{sub 2} pulsing causes significant increase in CO conversion, and only an instantaneous increase in undesirable selectivity to CH{sub 4}. Increasing the frequency of H{sub 2} pulsing enhances the selectivity to C{sub 10}-C{sub 20} compounds but the chain-growth probability {alpha} remains essentially unaffected. Increasing the duration of H{sub 2} pulsing results in enhancing the maximum obtained CO conversion and the instantaneous selectivity to CH{sub 4}. An optimum set of H{sub 2} pulse parameters (pulse frequency and duration) is required for maximizing the yield of desirable diesel-range C{sub 10}-C{sub 20} products. On a high-{alpha} Fe/K/Cu/SiO{sub 2} FT synthesis catalyst H{sub 2} pulsing enhances the yield of C{sub 10}-C{sub 20} but at the same time decreases the catalyst activity (CO conversion) and increases the selectivity to CH{sub 4}. On the other hand, pulsing with CO also increases the yield of C{sub 10}-C{sub 20} but has no impact on the selectivity to CH{sub 4} or CO{sub 2} and decreases catalytic activity only moderately. In contrast to these catalysts, H{sub 2} pulsing on a high-{alpha} Ru/alumina FT synthesis catalyst has only minimal effect on activity and product distribution, showing enhanced activity towards methanation and water-gas-shift at the expense of FT synthesis. However, these observations are based on experiments performed at a significantly lower reaction pressure (ca. 26 atm) and higher reaction temperature (210-250 C) than those commonly used for supported-Ru FT catalysts (typically 100-1000 atm, 160-170 C).

  18. Subtask 3.4 - Fischer - Tropsch Fuels Development

    SciTech Connect

    Strege, Joshua; Snyder, Anthony; Laumb, Jason; Stanislowski, Joshua; Swanson, Michael

    2012-05-01

    Under Subtask 3.4, the Energy & Environmental Research Center (EERC) examined the opportunities and challenges facing FischerTropsch (FT) technology in the United States today. Work was completed in two distinct budget periods (BPs). In BP1, the EERC examined the technical feasibility of using modern warm-gas cleanup techniques for FT synthesis. FT synthesis is typically done using more expensive and complex cold-gas sweetening. Warm-gas cleanup could greatly reduce capital and operating costs, making FT synthesis more attractive for domestic fuel production. Syngas was generated from a variety of coal and biomass types; cleaned of sulfur, moisture, and condensables; and then passed over a pilot-scale FT catalyst bed. Laboratory and modeling work done in support of the pilot-scale effort suggested that the catalyst was performing suboptimally with warm-gas cleanup. Long-term trends showed that the catalyst was also quickly deactivating. In BP3, the EERC compared FT catalyst results using warm-gas cleanup to results using cold-gas sweetening. A gas-sweetening absorption system (GSAS) was designed, modeled, and constructed to sweeten syngas between the gasifier and the pilot-scale FT reactor. Results verified that the catalyst performed much better with gas sweetening than it had with warm-gas cleanup. The catalyst also showed no signs of rapid deactivation when the GSAS was running. Laboratory tests in support of this effort verified that the catalyst had deactivated quickly in BP1 because of exposure to syngas, not because of any design flaw with the pilot-scale FT reactor itself. Based on these results, the EERC concludes that the two biggest issues with using syngas treated with warm-gas cleanup for FT synthesis are high concentrations of CO{sub 2} and volatile organic matter. Other catalysts tested by the EERC may be more tolerant of CO{sub 2}, but volatile matter removal is critical to ensuring long-term FT catalyst operation. This subtask was funded through

  19. Effect of Aromatic Concentration of a Fischer-Tropsch Fuel on Thermal Stability

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Lindsey Suder

    2012-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer­ Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline commercial grade F-T jet fuel, and various blends of this F-T fuel with an aromatic solution. The goal of this research is to determine the effect of aromatic content on the thermal stability of Fischer-Tropsch fuel. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  20. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, January 1, 1994--March 31, 1994

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1994-06-01

    We have successfully completed our first Fischer-Tropsch synthesis test with propane as the supercritical fluid. The catalyst activity and hydrocarbon product distribution under the SFT conditions were similar to those obtained during the normal Fischer-Tropsch synthesis, however, the use of supercritical fluid resulted in higher selectivity of the primary products. The use of a new trap with larger inside surface area, improved the collection of liquid products and thus enabling us to achieve better atomic and overall mass balance closures. This has also improved results from on-line GC analysis. However, further improvement are needed to achieve more stable and reproducible gas phase analysis, including the capability of the on-line analysis of the feed gas (mixture of hydrogen, carbon monoxide and propane).

  1. Effect of potassium promoter on cobalt nano-catalysts for fischer-tropsch reaction

    NASA Astrophysics Data System (ADS)

    Ali, Sardar; Mohd Zabidi, Noor Asmawati; Subbarao, Duvvuri

    2012-09-01

    In the present work effect of potassium on cobalt nano-catalysts for Fischer-Tropsch reaction has been presented. The catalysts were prepared using a wet impregnation method and promoted with potassium. Samples were characterized by nitrogen adsorption, H2-TPR, and TEM. The Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor 220 δC, 1 atm, H2/CO = 2 and a velocity (SV) =12 L/g.h. for 5 h. Addition of potassium into Co/CNTs decreased the average size of cobalt nanoparticles and the catalyst reducibility. Potassium-promoted Co catalyst resulted in appreciable increase in the selectivity of C5+ hydrocarbons and suppressed methane formation. The 0.06%KCo/CNTs catalyst enhanced the C5+ hydrocarbons selectivity by a factor of 23.5% and reduced the methane selectivity by a factor of 39.6%

  2. A techno-economic comparison of the different Fischer-Tropsch technologies used by SASOL

    SciTech Connect

    Vosloo, A.C.

    1996-12-31

    The Fischer-Tropsch process is used to convert synthesis gas (H{sub 2} + CO) via a polymerization mechanism to hydrocarbon products. The major driving force behind the development of the process was the production of liquid fuels and it was discovered by Fischer and Tropsch in 1925. The first commercial plant was built in Germany in 1936 and today Fischer-Tropsch plants are in operation in South Africa, Malaysia and Russia. A very important characteristic of this process is that it is not specific in nature in that the product spectrum can contain products ranging from methane to solid waxy products. Furthermore, for a specific carbon number, different types of hydrocarbon products are produced eg alkanes, alkenes, acids, alcohols and aldehydes. This wide product spectrum can be controlled to a degree by varying the operating temperature, the partial pressures of CO and H{sub 2} and the type of catalyst used. 4 refs., 2 figs., 3 tabs.

  3. Design of generic coal conversion facilities: Indirect coal liquefaction, Fischer-Tropsch synthesis

    SciTech Connect

    Not Available

    1991-10-01

    A comprehensive review of Fischer-Tropsch (F-T) technology, including fixed, fluidized, and bubble column reactors, was undertaken in order to develop an information base before initiating the design of the Fischer-Tropsch indirect liquefaction PDU as a part of the Generic Coal Conversion Facilities to be built at the Pittsburgh Energy Technology Center (PETC). The pilot plant will include a fixed bed and slurry bubble column reactor for the F-T mode of operation. The review encompasses current status of both these technologies, their key variables, catalyst development, future directions, and potential improvement areas. However, more emphasis has been placed on the slurry bubble column reactor since this route is likely to be the preferred technology for commercialization, offering process advantages and, therefore, better economics than fixed and fluidized bed approaches.

  4. Incorporation of catalytic dehydrogenation into fischer-tropsch synthesis to significantly reduce carbon dioxide emissions

    DOEpatents

    Huffman, Gerald P.

    2012-11-13

    A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO.sub.2 emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H.sub.2 level of coal-derived syngas for FTS. Additionally, the FTS-CDH process saves large amounts of water used by the WGS reaction and produces a valuable by-product, MWCNT.

  5. Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor

    DOEpatents

    Singleton, A.H.; Oukaci, R.; Goodwin, J.G.

    1999-08-17

    Processes and catalysts are disclosed for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided. 1 fig.

  6. Processes and catalysts for conducting fischer-tropsch synthesis in a slurry bubble column reactor

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    1999-01-01

    Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided.

  7. Emissions characteristics of Military Helicopter Engines Fueled with JP-8 and a Fischer-Tropsch Fuel

    SciTech Connect

    Corporan, E.; DeWitt, M.; Klingshirn, Christopher D; Striebich, Richard; Cheng, Mengdawn

    2010-01-01

    The rapid growth in aviation activities and more stringent U.S. Environmental Protection Agency regulations have increased concerns regarding aircraft emissions, due to their harmful health and environmental impacts, especially in the vicinity of airports and military bases. In this study, the gaseous and particulate-matter emissions of two General Electric T701C engines and one T700 engine were evaluated. The T700 series engines power the U.S. Army's Black Hawk and Apache helicopters. The engines were fueled with standard military JP-8 fuel and were tested at three power settings. In addition, one of the T701C engines was operated on a natural-gas-derived Fischer-Tropsch synthetic paraffinic kerosene jet fuel. Test results show that the T701C engine emits significantly lower particulate-matter emissions than the T700 for all conditions tested. Particulate-matter mass emission indices ranged from 0.2-1.4 g/kg fuel for the T700 and 0.2-0.6 g/kg fuel for the T701C. Slightly higher NOx and lower CO emissions were observed for the T701C compared with the T700. Operation of the T701C with the Fischer-Tropsch fuel rendered dramatic reductions in soot emissions relative to operation on JP-8, due primarily to the lack of aromatic compounds in the alternative fuel. The Fischer-Tropsch fuel also produced smaller particles and slight reductions in CO emissions.

  8. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2005-06-13

    As petroleum prices continue to rise and the United States seeks to reduce its dependency on foreign oil, there is a renewed interest in the research and development of more efficient and alternative energy sources, such as fuel cells. One approach is to utilize processes that can produce long-chain hydrocarbons from other sources. One such reaction is Fischer-Tropsch synthesis. Fischer-Tropsch synthesis is a process by which syngas (CO and H{sub 2}) is converted to higher molecular weight hydrocarbons. The reaction involves a complex set of bond-breaking and bond-making reactions, such as CO and H{sub 2} activation, hydrocarbon hydrogenation reactions, and hydrocarbon coupling reactions. This report details our initial construction of an ab initio based kinetic Monte Carlo code that can be used to begin to simulate Fischer-Tropsch synthesis over model Co(0001) surfaces. The code is based on a stochastic kinetic formalism that allows us to explicitly track the transformation of all reactants, intermediates and products. The intrinsic kinetics for the simulations were derived from the ab initio results that we reported in previous year summaries.

  9. Characterization of catalysts by Mossbauer spectroscopy: An application to the study of Fischer-Tropsch, hydrotreating and super Claus catalysts

    NASA Astrophysics Data System (ADS)

    van der Kraan, A. M.; Boellaard, E.; Crajé, M. W. J.

    1993-04-01

    Mössbauer spectroscopy is an excellent in-situ technique for the identification of phases present in catalysts. Applied to metallic iron catalysts used in the Fischer-Tropsch reaction it reveals a detailed picture of the carburization process and provides insight into the relation between the properties of the catalytic material and its activity. The influence of a support and the effect of alloying iron with an (in)active metal on the catalytic performance is discussed for Fe, CuFe and NiFe systems. In addition, Mössbauer spectroscopy is used for the identification of "Co-sulfide" species present in sulfided Co and CoMo catalysts applied in one of the largest chemical processes in the world, the hydrotreatment of crude oil. A structural model is proposed. Finally, the contribution of Mössbauer spectroscopic studies to the development of a new catalyst for cleaning of Claus tail gas via selective oxidation of hydrogen sulfide to elemental sulfur is discussed.

  10. [Determination of low-carbon alcohols, aldehydes and ketones in aqueous products of Fischer-Tropsch synthesis by gas chromatography].

    PubMed

    Gai, Qingqing; Wu, Peng; Shi, Yulin; Bai, Yu; Long, Yinhua

    2015-01-01

    A method for the determination of low-carbon (C1-C8) alcohols, aldehydes and ketones in aqueous products of Fischer-Tropsch synthesis was developed by gas chromatography. It included the optimization of separation conditions, the precision and accuracy of determination, and the use of correction factors of the analytes to ethanol for quantification. The aqueous products showed that the correlation coefficients for ethanol in different content ranges were above 0.99, which means it had good linear correlations. The spiked recoveries in the aqueous samples of Fischer-Tropsch synthesis were from 93.4% to 109.6%. The accuracy of the method can satisfy the requirement for the analysis of the aqueous samples of Fischer-Tropsch synthesis. The results showed that the total mass fractions of the major low-carbon alcohols, aldehydes, ketones in aqueous products of Fischer-Tropsch synthesis were about 3%-12%, and the contents of ethanol were the highest (about 1.7%-7.3%). The largest share of the total proportion was n-alcohols, followed by isomeric alcohols, aldehydes and ketones were the lowest. This method is simple, fast, and has great significance for the analysis of important components in aqueous products of Fischer-Tropsch synthesis.

  11. A chemical route to the formation of water in circumstellar envelopes around carbon-rich asymptotic branch stars: Fischer-Tropsch catalysis

    NASA Technical Reports Server (NTRS)

    Willacy, K.

    2004-01-01

    Fischer-Tropsch catalysis has been suggested as a means of driving hydrocarbon chemistry in oxygen rich regions such as the protosolar nebula. In addition to producing hydrocarbons, Fischer-Tropsch catalysis also produces water, and it is therefore possible that such processes could account for the recent observations of water in the circumstellar envelope of asymptotic giant branch star IRC +10216.

  12. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock; David A. Walthall

    2006-05-07

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various different energy sources potentially including fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch synthesis involves the initiation or activation of CO and H{sub 2} bonds, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. Commercially viable catalysts include supported Co and Co-alloys. Over the first two years of this project we have used ab initio methods to determine the adsorption energies for all reactants, intermediates, and products along with the overall reaction energies and their corresponding activation barriers over the Co(0001) surface. Over the third year of the project we developed and advanced an ab initio-based kinetic Monte Carlo simulation code to simulate Fischer Tropsch synthesis. This report details our work over the last year which has focused on the derivation of kinetic parameters for the elementary steps involved in FT synthesis from ab initio density functional theoretical calculations and the application of the kinetic Monte Carlo algorithm to simulate the initial rates of reaction for FT over the ideal Co(0001) surface. The results from our simulations over Co(0001) indicate the importance of stepped surfaces for the activation of adsorbed CO. In addition, they demonstrate that the dominant CH{sub x}* surface intermediate under steady state conditions is CH*. This strongly suggests that hydrocarbon coupling

  13. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burtron Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Dennis Sparks; Wilson Shafer

    2010-09-30

    The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on iron and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.

  14. Thermal Stability Testing of Fischer-Tropsch Fuel and Various Blends with Jet A, as Well as Aromatic Blend Additives

    NASA Technical Reports Server (NTRS)

    Klettlinger, J.; Rich, R.; Yen, C.; Surgenor, A.

    2011-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. Fischer-Tropsch fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal parafins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline conventional Jet A, a commercial grade F-T jet fuel, and various blends of this F-T fuel in Jet A. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  15. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, October--December 1991

    SciTech Connect

    Not Available

    1992-04-27

    The objectives of the study are to: Develop a baseline design for indirect liquefaction using advanced Fischer-Tropsch (F-T) technology. Prepare the capital and operating costs for the baseline design. Develop a process flowsheet simulation (PFS) model. The baseline design, the economic analysis, and the computer model will be the major research planning tools that Pittsburgh Energy Technology Center will use to plan, guide, and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction for the manufacture of synthetic liquid fuels from coal.

  16. Comparison of hydrocracking Fischer-Tropsch wax with VGO hydrocracking and pure component mechanisms

    SciTech Connect

    Ekwall, G.R.; Yuh, E.; McArdle, J.C.; Steigleder, K.

    1987-01-01

    Hydrocracking pilot plant tests have been conducted on Fischer-Tropsch wax. Analytical results show that the feedstock is less complex than typical hydrocracking feedstocks, hence the test results can be used to gain understanding of the reaction mechanisms of hydrocracking normal paraffins. Data from process variable surveys changing pressure, combined feed ratio, liquid hourly space velocity and recycle hydrogen rate all support the carbonium ion mechanism of normal paraffin hydrocracking. The data show a consistent relationship between the degree of secondary vs. primary cracking proposed in the mechanism and product distribution.

  17. The chemical oxidation and refinement of raw Fischer-Tropsch wax

    SciTech Connect

    Zhu Jisheng; Chen Languang; Sun Shuhe; Cheng Shaoxin

    1995-12-31

    Raw Fischer-Tropsch wax (FT wax) produced from the pilot plant (100t/a, Daixian, Shanxi Province) and the demonstration plant (2,000t/a, Jincheng, Shanxi Province) of coal-based synthetic gasoline process was refined by chemical oxidation. The properties of refined FT wax were greatly improved. The results show that the refined wax with very high melting point (108 C) and satisfactory hardness (penetration about 5, 25 C 100g/5s) consists of a large amount of paraffins, but a minute amount of acids, alcohols and other organic compounds.

  18. Structural framework of a medium Fischer-Tropsch wax fraction determined by electron crystallography

    NASA Astrophysics Data System (ADS)

    Dorset, Douglas L.; Basson, Ilsa

    2000-10-01

    The structural framework of a medium hardness Fischer-Tropsch wax distillate is established quantitatively by electron crystallography and compared to model paraffin assemblies with a similar Gaussian distribution of chain lengths. The lamellar packing closely resembles the crystal structure of refined petroleum waxes with a similar distribution of defects near the lamellar interface. Nevertheless, clear differences associated with the absorption of smaller chains within the lamellar interface, detected by NMR, are not resolved by these diffraction measurements, perhaps due to artefacts induced by the high vacuum of the experiment and/or specimen preparation.

  19. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-01-01

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240[degrees]C, 0.5 to 1.5 MPa, H[sub 2]/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R[sub H[sub 2+Co

  20. Fischer-Tropsch synthesis over MOF-supported cobalt catalysts (Co@MIL-53(Al)).

    PubMed

    Isaeva, V I; Eliseev, O L; Kazantsev, R V; Chernyshev, V V; Davydov, P E; Saifutdinov, B R; Lapidus, A L; Kustov, L M

    2016-07-26

    Novel nanohybrid materials were prepared by immobilizing Co nanoparticles on a microporous framework MIL-53(Al) as a porous host matrix. The synthesized cobalt-containing materials were characterized by XRD, STEM, and oxygen titration. The catalytic performance of Co@MIL-53(Al) nanohybrids was examined in Fischer-Tropsch synthesis (FTS) for the first time. A higher selectivity to C5+ hydrocarbons and lower selectivity to methane for Co@MIL-53(Al) as compared to conventional Co/Al2O3 were observed. PMID:27389315

  1. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2002-09-11

    As the US seeks to develop an energy strategy that reduces the reliance on foreign oil, there is a renewed interest in research and development of the Fischer Tropsch synthesis of converting syngas into long chain hydrocarbon products. This report investigates some of the basic elementary steps for Fischer-Tropsch synthesis over ideal Co and Ru metal surfaces by using ab initio density functional theoretical calculations. This includes activation of CO of CO, the hydrogenation of CH{sub x} intermediates, and the adsorption and dissociation of water. The activation of CO is studied in detail showing a strong dependence on the surface coverage, defect sites and Co-Ru alloy formation. The barriers for CO activation over the ideal (0001) surfaces are quite high making CO activation at the terrace sites unlikely under operating conditions. The calculations for the overall reaction energies at the step edges indicate that these sites are much more reactive. The hydrogenation of the CHx intermediates occurs in a sequential fashion. CH1 was found to be the most stable intermediate over various surfaces. The barriers to form both CH* as well as CH{sub 4} are both found to be highly activated and potentially difficult steps. Water which is a reaction product was found to be weakly adsorbed on Co. Analysis of the microscopic reverse reaction of water activation indicates that this process has a very low activation barrier. Consequently, any water which forms desorbs or is activated to form surface hydroxyl intermediates.

  2. Nano-sized cobalt based Fischer-Tropsch catalysts for gas-to-liquid process applications.

    PubMed

    Kang, Jung Shik; Awate, S V; Lee, Yun Ju; Kim, So Jung; Park, Moon Ju; Lee, Sang Deuk; Hong, Suk-In; Moon, Dong Ju

    2010-05-01

    Nano-sized cobalt supported catalysts were prepared for Fischer-Tropsch synthesis in gas-to-liquid (GTL) process. The dependence of crystallite size and reducibility of Co3O4 on the supports were investigated with FTS activity. XRD peaks revealed nano crystallites (< 5.47 nm) of Co3O4 crystallites. TEM showed round shaped particles with size less than 5 nm. Support with higher acidity decreased crystallite size of Co3O4. XRD data of used catalysts showed Co3O4 crystallites smaller than 3.5 nm which do not reduce easily to Co(0) state. The crystallite size of Co3O4 plays a role in its reduction to Co(0). TPR results showed that the reduction temperature shifts to higher temperature due to metal-support interaction. The variation in the activity of the catalysts depends on the support which in turn affects the crystallite size, dispersion, reducibility and activity of Co species in Fischer-Tropsch Synthesis (FTS). In this study, Co/Al2O3 showed higher CO conversion than the other catalysts. However, the C5+ production was in order Co/SiO2 (78.1%) > Co/Al2O3 (70.0%) > Co/R_TiO2 (61%) > Co/A_TiO2 (57.5%).

  3. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    A Co/MgO/SiO[sub 2] Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al[sub 2]O[sub 3] water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240[degrees]C, a pressure of 0.79 MPa, and a 1.1 H[sub 2]/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO[sub 2] catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO[sub 2] operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts's operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  4. Chain length dependence of {alpha}-olefin readsorption in Fischer-Tropsch synthesis

    SciTech Connect

    Kuipers, E.W.; Vinkenburg, I.H.; Oosterbeek, H.

    1995-03-01

    The total product concentration and the paraffin/olefin ratio have been measured up to C{sub 14} for Fischer-Tropsch synthesis on polycrystalline Co foils. The influences due to surface area, a wax coating, the H{sub 2}/CO ratio and flow velocity on concentration and selectivity have been determined. The paraffin/olefin ratio increases exponentially with chain length which is attributed to a chain-length-dependent olefin readsorption mechanism. The probability of readsorption depends on the heat of physisorption of the olefins on the catalyst as well as on their heat of dissolution in and their diffusivity through the product wax. All three factors predict an increase of the paraffin/olefin ratio with carbon number. Physisorption and dissolution are shown to cause a much stronger chain-length dependence than diffusion and will usually dominate. 36 refs., 9 figs.

  5. Separation of Fischer-Tropsch Wax from Catalyst by Supercritical Extraction

    SciTech Connect

    Joyce, P.C.; Thies, M.C.

    1997-01-31

    The proposed process of using supercritical fluid extraction in conjunction with the Fischer-Tropsch slurry bubble column reactor has been examined using the ASPEN Plus simulator by the research group at North Carolina State University. Qualitative results have been obtained for varying the following process parameters: solvent-to-wax ratio, solvent type (pentane or hexane), extraction temperature and pressure, and recovery unit temperature and pressure. The region of retrograde behavior was determined for pentane and hexane. Initial results show hexane to be the superior solvent; compared to pentane, hexane requires lower quantities of solvent makeup (the amount of solvent which needs to be added to account for solvent that cannot be recycled), and also results in a lower average molecular weight of slurry in the reactor. Studies indicate that increasing the extraction temperature, extraction pressure, recovery temperature, or solvent to wax ratio decreases the amount solvent makeup required. Decreasing the recovery pressure was found to decrease the makeup flowrate.

  6. Optimisation of the Fischer-Tropsch process using zeolites for tail gas separation.

    PubMed

    Perez-Carbajo, J; Gómez-Álvarez, P; Bueno-Perez, R; Merkling, P J; Calero, S

    2014-03-28

    This work is aimed at optimizing a Fischer-Tropsch Gas To Liquid (GTL) process by recycling compounds of the expelled gas mixture using zeolites for the separation. To that end, we have performed a computational study on four structures widely used in industry. A range of Si/Al ratios have been explored and the effects of their distribution assessed. The ability of the considered force fields and molecular models to reproduce experimental results has been widely proved in previously reported studies. Since this tail gas is formed by a five-component mixture, namely carbon dioxide, methane, carbon monoxide, nitrogen and hydrogen, molecular simulations present clear advantages over experiments. In addition, the viability of the Ideal Adsorption Solution Theory (IAST) has been evaluated to easily handle further separation steps. On the basis of the obtained results, we provide a separation scheme to perform sequentially the separation of CO2, CH4, CO, N2 and H2.

  7. Fischer-Tropsch synthesis on hierarchically structured cobalt nanoparticle/carbon nanofiber/carbon felt composites.

    PubMed

    Zarubova, Sarka; Rane, Shreyas; Yang, Jia; Yu, Yingda; Zhu, Ye; Chen, De; Holmen, Anders

    2011-07-18

    The hierarchically structured carbon nanofibers (CNFs)/carbon felt composites, in which CNFs were directly grown on the surface of microfibers in carbon felt, forming a CNF layer on a micrometer range that completely covers the microfiber surfaces, were tested as a novel support material for cobalt nanoparticles in the highly exothermic Fischer-Tropsch (F-T) synthesis. A compact, fixed-bed reactor, made of disks of such composite materials, offered the advantages of improved heat and mass transfer, relatively low pressure drop, and safe handling of immobilized CNFs. An efficient 3-D thermal conductive network in the composite provided a relatively uniform temperature profile, whereas the open structure of the CNF layer afforded an almost 100 % effectiveness of Co nanoparticles in the F-T synthesis in the fixed bed. The greatly improved mass and heat transport makes the compact reactor attractive for applications in the conversion of biomass, coal, and natural gas to liquids. PMID:21563315

  8. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  9. Monetization of Nigeria coal by conversion to hydrocarbon fuels through Fischer-Tropsch process

    SciTech Connect

    Oguejiofor, G.C.

    2008-07-01

    Given the instability of crude oil prices and the disruptions in crude oil supply chains, this article offers a complementing investment proposal through diversification of Nigeria's energy source and dependence. Therefore, the following issues were examined and reported: A comparative survey of coal and hydrocarbon reserve bases in Nigeria was undertaken and presented. An excursion into the economic, environmental, and technological justifications for the proposed diversification and roll-back to coal-based resource was also undertaken and presented. The technology available for coal beneficiation for environmental pollution control was reviewed and reported. The Fischer-Tropsch synthesis and its advances into Sasol's slurry phase distillate process were reviewed. Specifically, the adoption of Sasol's advanced synthol process and the slurry phase distillate process were recommended as ways of processing the products of coal gasification. The article concludes by discussing all the above-mentioned issues with regard to value addition as a means of wealth creation and investment.

  10. Fischer-Tropsch synthesis on hierarchically structured cobalt nanoparticle/carbon nanofiber/carbon felt composites.

    PubMed

    Zarubova, Sarka; Rane, Shreyas; Yang, Jia; Yu, Yingda; Zhu, Ye; Chen, De; Holmen, Anders

    2011-07-18

    The hierarchically structured carbon nanofibers (CNFs)/carbon felt composites, in which CNFs were directly grown on the surface of microfibers in carbon felt, forming a CNF layer on a micrometer range that completely covers the microfiber surfaces, were tested as a novel support material for cobalt nanoparticles in the highly exothermic Fischer-Tropsch (F-T) synthesis. A compact, fixed-bed reactor, made of disks of such composite materials, offered the advantages of improved heat and mass transfer, relatively low pressure drop, and safe handling of immobilized CNFs. An efficient 3-D thermal conductive network in the composite provided a relatively uniform temperature profile, whereas the open structure of the CNF layer afforded an almost 100 % effectiveness of Co nanoparticles in the F-T synthesis in the fixed bed. The greatly improved mass and heat transport makes the compact reactor attractive for applications in the conversion of biomass, coal, and natural gas to liquids.

  11. Hydrodynamics of Fischer-Tropsch synthesis in slurry bubble column reactors: Final report

    SciTech Connect

    Bukur, D.B.; Daly, J.G.; Patel, S.A.; Raphael, M.L.; Tatterson, G.B.

    1987-06-01

    This report describes studies on hydrodynamics of bubble columns for Fischer-Tropsch synthesis. These studies were carried out in columns of 0.051 m and 0.229 m in diameter and 3 m tall to determine effects of operating conditions (temperature and gas flow rate), distributor type (sintered metal plate and single and multi-hole perforated plates) and liquid media (paraffin and reactor waxes) on gas hold-up and bubble size distribution. In experiments with the Fischer-Tropsch (F-T) derived paraffin wax (FT-300) for temperatures between 230 and 280/sup 0/C there is a range of gas velocities (transition region) where two values of gas hold-up (i.e., two flow regimes) are possible. Higher hold-ups were accompanied by the presence of foam (''foamy'' regime) whereas lower values were obtained in the absence of foam (''slug flow'' in the 0.051 m column, or ''churn-turbulent'' flow regime in the 0.229 m column). This type of behavior has been observed for the first time in a system with molten paraffin wax as the liquid medium. Several factors which have significant effect on foaming characteristics of this system were identified. Reactor waxes have much smaller tendency to foam and produce lower hold-ups due to the presence of larger bubbles. Finally, new correlations for prediction of the gas hold-up and the specific gas-liquid interfacial area were developed on the basis of results obtained in the present study. 49 refs., 99 figs., 19 tabs.

  12. Isotopic tracer studies of Fischer-Tropsch Synthesis over Ru/TiO{sub 2} catalysts

    SciTech Connect

    Krishna, K.R.

    1992-01-01

    Fischer-Tropsch synthesis is a process in which CO and H{sub 2} react to give predominantly liquid hydrocarbons. The reaction can be considered a special type of polymerization in which the monomer is produced in situ, and chain growth occurs by a sequence of independently repeated additions of the monomer to the growing chain. A investigation has been conducted to study the CO hydrogenation reaction in order to better understand catalyst deactivation and the elementary surface processes involved in chain growth. Isotopic tracers are used in conjunction with transient-response techniques in this study of Fischer-Tropsch synthesis over Ru/TiO{sub 2} catalysts. Experiments are conducted at a total pressure of 1 atmosphere, reaction temperatures of 453--498 K and D{sub 2}/CO (or H{sub 2}/CO) ratios of 2--5. Synthesis products are analyzed by gas chromatography or isotope-ratio gas chromatography-mass spectrometry. Rate constants for chain initiation, propagation and termination are evaluated under steady-state reaction conditions by using transients in isotopic composition. The activation energy for chain termination is much higher than that for propagation, accounting for the observed decrease in the chain growth parameter are also estimated. Coverages by reaction intermediates are also estimated. When small amounts of {sup 12}C-labelled ethylene are added to {sup 13}CO/H{sub 2} synthesis gas, ethylene acts as the sole chain initiator. Ethylene-derived carbon also accounts for 45% of the C{sub 1} monomer pool. 102 refs., 29 figs., 11 tabs.

  13. Isotopic tracer studies of Fischer-Tropsch Synthesis over Ru/TiO sub 2 catalysts

    SciTech Connect

    Krishna, K.R.

    1992-01-01

    Fischer-Tropsch synthesis is a process in which CO and H{sub 2} react to give predominantly liquid hydrocarbons. The reaction can be considered a special type of polymerization in which the monomer is produced in situ, and chain growth occurs by a sequence of independently repeated additions of the monomer to the growing chain. A investigation has been conducted to study the CO hydrogenation reaction in order to better understand catalyst deactivation and the elementary surface processes involved in chain growth. Isotopic tracers are used in conjunction with transient-response techniques in this study of Fischer-Tropsch synthesis over Ru/TiO{sub 2} catalysts. Experiments are conducted at a total pressure of 1 atmosphere, reaction temperatures of 453--498 K and D{sub 2}/CO (or H{sub 2}/CO) ratios of 2--5. Synthesis products are analyzed by gas chromatography or isotope-ratio gas chromatography-mass spectrometry. Rate constants for chain initiation, propagation and termination are evaluated under steady-state reaction conditions by using transients in isotopic composition. The activation energy for chain termination is much higher than that for propagation, accounting for the observed decrease in the chain growth parameter are also estimated. Coverages by reaction intermediates are also estimated. When small amounts of {sup 12}C-labelled ethylene are added to {sup 13}CO/H{sub 2} synthesis gas, ethylene acts as the sole chain initiator. Ethylene-derived carbon also accounts for 45% of the C{sub 1} monomer pool. 102 refs., 29 figs., 11 tabs.

  14. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock; Siddharth Chopra

    2003-09-11

    As the US seeks to develop an energy strategy that reduces the reliance on foreign oil, there is a renewed interest in the research and development of the Fischer Tropsch synthesis for converting syngas into long chain hydrocarbon products. This report investigates some of the basic elementary steps for Fischer-Tropsch synthesis over ideal Pt, Ru and carbon-covered Pt and Ru metal surfaces by using ab initio density functional theoretical calculations. We examine in detail the adsorption sites as well as the binding energies for C, CH, CH{sub 2}, CH3 and CH4 on Pt(111), Ru(0001), 2x2-C-Pt(111) and 2x2-C-Ru(0001). The results indicate that the binding energies increase with decreasing the hydrogen in the fragment molecule, i.e. CH{sub 4} < CH{sub 3} < CH{sub 2} < CH < C. More specifically the work analyzes the elementary steps involved in the activation of methane. This is simply the reverse set of steps necessary for the hydrogenation of C to CH{sub 4}. The results indicate that these hydrocarbon intermediates bind more strongly to Ru than Pt. The introduction of co-adsorbed carbon atoms onto both Ru(0001) as well as Pt(111) significantly increased the overall energies as well as the activation barriers for C-H bond activation. The results suggest that Ru may be so active that it initially can initially activate CH4 into CH or C but ultimately it dies because the CH and C intermediates poison the surface and thus kill its activity. Methane can dissociate on Pt but subsequent hydrocarbon coupling reactions act to remove the surface carbon.

  15. Titania-supported bimetallic catalysts combined with HZSM-5 for Fischer-Tropsch synthesis

    SciTech Connect

    Jothimurugesan, K.; Gangwal, S.K.

    1998-04-01

    The Fischer-Tropsch synthesis (FTS) can convert coal or natural gas derived synthesis gas (CO + H{sub 2}) to liquid fuels and high-value chemicals. Fischer-Tropsch synthesis was studied in a fixed-bed reactor over single-metal and bimetallic alloy catalysts, selected from Co, Ni, and Fe, supported on TiO{sub 2} at a total metal loading of 10 wt%. The catalysts, prepared by incipient wetness impregnation using nitrate precursors, were tested as is and in combination with a HZSM-5 zeolite. The test conditions were 1 MPa, 250 C, H{sub 2}/CO = 1, and weight hourly space velocity (WHSV) = 0.77 h{sup {minus}1}. Alloying of metals resulted in a significant enhancement in CO conversion without an increase in methane selectivity. A 50:50 weight ratio Co-Ni catalyst physically mixed with HZSM-5 (5% Co-5% Ni/TiO{sub 2} + HZSM-5) gave the highest CO conversion (45.2%) at the conditions tested. This compares to conversion of 8.9% and 10.5% with Co-only and Ni-only catalysts, respectively. Mixing the Co-Ni catalyst with HZSM-5 resulted in a significant reduction in methane selectivity and a significant increase in C{sub 4}{sup +} selectivity. The aromatic fraction increased from 1.5 to 8.1 wt%, the C{sub 2}{sup +} olefins were nearly eliminated, and i-C{sub 4}H{sub 10} increased from 2.3 to 58.5 wt % in the C{sub 4} fraction.

  16. Techno-economic assessment of integrating methanol or Fischer-Tropsch synthesis in a South African sugar mill.

    PubMed

    Petersen, Abdul M; Farzad, Somayeh; Görgens, Johann F

    2015-05-01

    This study considered an average-sized sugar mill in South Africa that crushes 300 wet tonnes per hour of cane, as a host for integrating methanol and Fischer-Tropsch synthesis, through gasification of a combined flow of sugarcane trash and bagasse. Initially, it was shown that the conversion of biomass to syngas is preferably done by catalytic allothermal gasification instead of catalytic autothermal gasification. Thereafter, conventional and advanced synthesis routes for both Methanol and Fischer-Tropsch products were simulated with Aspen Plus® software and compared by technical and economic feasibility. Advanced FT synthesis satisfied the overall energy demands, but was not economically viable for a private investment. Advanced methanol synthesis is also not viable for private investment since the internal rate of return was 21.1%, because it could not provide the steam that the sugar mill required. The conventional synthesis routes had less viability than the corresponding advanced synthesis routes.

  17. Elementary steps in Fischer-Tropsch synthesis: CO bond scission, CO oxidation and surface carbiding on Co(0001)

    NASA Astrophysics Data System (ADS)

    Weststrate, C. J.; van Helden, P.; van de Loosdrecht, J.; Niemantsverdriet, J. W.

    2016-06-01

    Dissociation of CO on a Co(0001) surface is explored in the context of Fischer-Tropsch synthesis on cobalt catalysts. Experiments show that CO dissociation can occur on defect sites around 330 K, with an estimated barrier between 90 and 104 kJ mol- 1. Despite the ease of CO dissociation on defect sites, extensive carbon deposition onto the cobalt surface up to 0.33 ML requires a combination of high surface temperature and a relatively high CO pressure. Experimental data on the CO oxidation reaction indicate a high reaction barrier for the CO + O reaction, and it is argued that, due to the rather strong Co-O bond, (i) oxygen removal is the rate-limiting step during surface carbidization and (ii) in the context of Fischer-Tropsch synthesis, removal of surface oxygen rather than CO bond scission might be limiting the overall reaction rate.

  18. Metal-carbon nanosystem IR-PVA/Fe-Co for catalysis in the Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Vasilev, A. A.; Dzidziguri, E. L.; Ivantsov, M. I.; Efimov, M. N.

    2016-08-01

    Metal-carbon nanosystems consisting of nanodimensional bimetallic particles of Fe- Co dispersed in a carbon matrix for the Fischer-Tropsch synthesis were studied. Prepared metal-carbon nanopowders samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It was shown formation of FeCo nanoparticles with body-centered cubic structures started at 400 °C. FeCo nanoparticles have spherical form, the mean size is 7 - 12 nm and uniform distribution in a carbon matrix. The metal-carbon nanosystem demonstrates a catalytic activity in the Fischer- Tropsch synthesis. The maximum yield of liquid hydrocabons C5+ was 92 g/m3 while the selectivity for the target product - 35%.

  19. Gasoline range ether synthesis from light naphtha products of fluid catalytic cracking of Fischer-Tropsch wax

    SciTech Connect

    Reagan, W.J.

    1994-12-31

    The Fluid Catalytic Cracking of Fischer-Tropsch wax (C{sub 20}{sup +} paraffins) produces two to four time the concentration of reactive iso-olefins (isobutylene, isoamylenes, isohexenes) than observed from conventional gas oil feedstocks. Methanol reacts with these olefins to form the corresponding tertiary alkyl ethyl ethers: MTBE, TAME and MTHE`s. These etherification reactions are mildly exothermic and equilibrium limited. The reaction temperature and the olefin molecular structure are important variables for maximum ether yields. The base naphtha research octane number increases by 2-4 numbers after the etherification reaction. The presence of hydrogen has a detrimental affect on ether yields because of hydrogenation of reactive olefins to paraffins. The catalytic cracking of Fischer-Tropsch wax provides a non-conventional source of olefins for ether synthesis that can supplement existing and dwindling petroleum supplies.

  20. Techno-economic assessment of integrating methanol or Fischer-Tropsch synthesis in a South African sugar mill.

    PubMed

    Petersen, Abdul M; Farzad, Somayeh; Görgens, Johann F

    2015-05-01

    This study considered an average-sized sugar mill in South Africa that crushes 300 wet tonnes per hour of cane, as a host for integrating methanol and Fischer-Tropsch synthesis, through gasification of a combined flow of sugarcane trash and bagasse. Initially, it was shown that the conversion of biomass to syngas is preferably done by catalytic allothermal gasification instead of catalytic autothermal gasification. Thereafter, conventional and advanced synthesis routes for both Methanol and Fischer-Tropsch products were simulated with Aspen Plus® software and compared by technical and economic feasibility. Advanced FT synthesis satisfied the overall energy demands, but was not economically viable for a private investment. Advanced methanol synthesis is also not viable for private investment since the internal rate of return was 21.1%, because it could not provide the steam that the sugar mill required. The conventional synthesis routes had less viability than the corresponding advanced synthesis routes. PMID:25727762

  1. Fischer-Tropsch-Type Production of Organic Materials in the Solar Nebula: Studies Using Graphite Catalysts and Measuring the Trapping of Noble Gases

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Ferguson, Frank T.; Lucas, Christopher; Kimura, Yuki; Hohenberg, Charles

    2009-01-01

    The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.

  2. Mechanistic role of water on the rate and selectivity of Fischer-Tropsch synthesis on ruthenium catalysts.

    PubMed

    Hibbitts, David D; Loveless, Brett T; Neurock, Matthew; Iglesia, Enrique

    2013-11-18

    Water increases Fischer-Tropsch synthesis (FTS) rates on Ru through H-shuttling processes. Chemisorbed hydrogen (H*) transfers its electron to the metal and protonates the O-atom of CO* to form COH*, which subsequently hydrogenates to *HCOH* in the kinetically relevant step. H2 O also increases the chain length of FTS products by mediating the H-transfer steps during reactions of alkyl groups with CO* to form longer-chain alkylidynes and OH*.

  3. Fischer-tropsch synthesis in supercritical fluids. Quarterly technical progress report, October 1, 1994--December 21, 1994

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1995-01-31

    Progress reports are presented for the following two tasks: (1) diffusion coefficients of F-T products in supercritical fluids; and (2) Fischer-Tropsch reaction related studies. The objectives for this quarter for task 1 were to measure molecular diffusion coefficients and effective diffusivities at the same conditions. The objectives for task 2 were to conduct two additional tests with the Ruhrchemie catalyst and a catalyst synthesized in our laboratory under supercritical conditions.

  4. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Dennis Sparks; Khalid Azzam; Janet Chakkamadathil Mohandas; Wilson Shafer; Venkat Ramana Rao Pendyala

    2011-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H

  5. Fischer-Tropsch synthesis in supercritical phase carbon dioxide: Recycle rates

    NASA Astrophysics Data System (ADS)

    Soti, Madhav

    With increasing oil prices and attention towards the reduction of anthropogenic CO2, the use of supercritical carbon dioxide for Fischer Tropsch Synthesis (FTS) is showing promise in fulfilling the demand of clean liquid fuels. The evidence of consumption of carbon dioxide means that it need not to be removed from the syngas feed to the Fischer Tropsch reactor after the gasification process. Over the last five years, research at SIUC have shown that FTS in supercritical CO2reduces the selectivities for methane, enhances conversion, reduces the net CO2produces in the coal to liquid fuels process and increase the life of the catalyst. The research has already evaluated the impact of various operating and feed conditions on the FTS for the once through process. We believe that the integration of unreacted feed recycle would enhance conversion, increase the yield and throughput of liquid fuels for the same reactor size. The proposed research aims at evaluating the impact of recycle of the unreacted feed gas along with associated product gases on the performance of supercritical CO2FTS. The previously identified conditions will be utilized and various recycle ratios will be evaluated in this research once the recycle pump and associated fittings have been integrated to the supercritical CO2FTS. In this research two different catalysts (Fe-Zn-K, Fe-Co-Zn-K) were analyzed under SC-FTS in different recycle rate at 350oC and 1200 psi. The use of recycle was found to improve conversion from 80% to close to 100% with both catalysts. The experiment recycle rate at 4.32 and 4.91 was clearly surpassing theoretical recycle curve. The steady state reaction rate constant was increased to 0.65 and 0.8 min-1 for recycle rate of 4.32 and 4.91 respectively. Carbon dioxide selectivity was decreased for both catalyst as it was converting to carbon monoxide. Carbon dioxide consumption was increased from 0.014 to 0.034 mole fraction. This concluded that CO2is being used in the system and

  6. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2006-09-11

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various energy sources which will likely include fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch (FT) synthesis involves the adsorption and the activation of CO and H{sub 2}, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. The current commercial catalysts are supported Co and Co-alloys particles. This project set out with the following objectives in mind: (1) understand the reaction mechanisms that control FT kinetics, (2) predict how the intrinsic metal-adsorbate bond affects the sequence of elementary steps in FT, (3) establish the effects of the reaction environment on catalytic activity and selectivity, (4) construct a first-principles based algorithm that can incorporate the detailed atomic surface structure and simulate the kinetics for the myriad of elementary pathways that make up FT chemistry, and (5) suggest a set of optimal features such as alloy composition and spatial configuration, oxide support, distribution of defect sites. As part of this effort we devoted a significant portion of time to develop an ab initio based kinetic Monte Carlo simulation which can be used to follow FT surface chemistry over different transition metal and alloy surfaces defined by the user. Over the life of this program, we have used theory and have developed and applied stochastic Monte Carlo simulations in order to establish the fundamental

  7. In situ observation of self-assembled hydrocarbon Fischer-Tropsch products on a cobalt catalyst

    NASA Astrophysics Data System (ADS)

    Navarro, Violeta; van Spronsen, Matthijs A.; Frenken, Joost W. M.

    2016-10-01

    Fischer-Tropsch synthesis is a heterogeneous catalytic reaction that creates approximately 2% of the world's fuel. It involves the synthesis of linear hydrocarbon molecules from a gaseous mixture of carbon monoxide and hydrogen at high pressures (from a few to tens of bars) and high temperatures (200-350 °C). To gain further insight into the fundamental mechanisms of this industrial process, we have used a purpose-built scanning tunnelling microscope to monitor a cobalt model catalyst under reaction conditions. We show that, after 30 minutes of reaction, the terraces of the cobalt catalyst are covered by parallel arrays of stripes. We propose that the stripes are formed by the self-assembly of linear hydrocarbon product molecules. Surprisingly, the width of the stripes corresponds to molecules that are 14 or 15 carbon atoms long. We introduce a simple model that explains the accumulation of such long molecules by describing their monomer-by-monomer synthesis and explicitly accounting for their thermal desorption.

  8. ULTRA-CLEAN FISCHER-TROPSCH FUELS PRODUCTION AND DEMONSTRATION PROJECT

    SciTech Connect

    Steve Bergin

    2003-10-17

    The Syntroleum plant is mechanically complete and currently undergoing start-up. The fuel production and demonstration plan is near completion. The study on the impact of small footprint plant (SFP) fuel on engine performance is about half-completed. Cold start testing has been completed. Preparations have been completed for testing the fuel in diesel electric generators in Alaska. Preparations are in progress for testing the fuel in bus fleets at Denali National Park and the Washington Metropolitan Transit Authority. The experiments and analyses conducted during this project show that Fischer-Tropsch (FT) gas-to-liquid diesel fuel can easily be used in a diesel engine with little to no modifications. Additionally, based on the results and discussion presented, further improvements in performance and emissions can be realized by configuring the engine to take advantage of FT diesel fuel's properties. The FT fuel also shows excellent cold start properties and enabled the engine tested to start at more the ten degrees than traditional fuels would allow. This plant produced through this project will produce large amounts of FT fuel. This will allow the fuel to be tested extensively, in current, prototype, and advanced diesel engines. The fuel may also contribute to the nation's energy security. The military has expressed interest in testing the fuel in aircraft and ground vehicles.

  9. Small-Scale Coal-Biomass to Liquids Production Using Highly Selective Fischer-Tropsch Synthesis

    SciTech Connect

    Gangwal, Santosh K.; McCabe, Kevin

    2015-04-30

    The research project advanced coal-to-liquids (CTL) and coal-biomass to liquids (CBTL) processes by testing and validating Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to convert gasifier syngas predominantly to gasoline, jet fuel and diesel range hydrocarbon liquids, thereby eliminating expensive wax upgrading operations The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream testing/demonstration. Southern Research designed, installed and commissioned a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport integrated gasifier (TRIGTM). The test-rig was designed to receive up to 5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of 2 to 4 L/day. It employed a 2-inch diameter boiling water jacketed fixed-bed heat-exchange FT reactor incorporating Chevron’s catalyst in Intramicron’s high thermal conductivity micro-fibrous entrapped catalyst (MFEC) packing to efficiently remove heat produced by the highly exothermic FT reaction.

  10. Thermal Stability Results of a Fischer-Tropsch Fuel With Various Blends of Aromatic Solution

    NASA Technical Reports Server (NTRS)

    Lindsey, Jennifer; Klettlinger, Suder

    2013-01-01

    Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. F-T fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal paraffins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline commercial grade F-T jet fuel, and various blends of this F-T fuel with an aromatic solution. The goal of this research is to determine the effect of aromatic content on the thermal stability of F-T fuel. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonic Fixed Wing Project. Two different aromatic content fuels from Rentech, as well as these fuels with added aromatic blend were analyzed for thermal stability using the JFTOT method. Preliminary results indicate a reduction in thermal stability occurs upon increasing the aromatic content to 10% by adding an aromatic blend to the neat fuel. These results do not specify a failure based on pressure drop, but only on tube color. It is unclear whether tube color correlates to more deposition on the tube surface or not. Further research is necessary in order to determine if these failures are true failures based on tube color. Research using ellipsometry to determine tube deposit thickness rather than color will be continued in follow-up of this study.

  11. Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2015-01-01

    Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

  12. Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

    2016-01-01

    Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

  13. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    Patrick C. Joyce; Mark C. Thies

    1999-03-31

    The objective of this research project was to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, is to be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Aspen Plus{trademark} was used to perform process simulation studies on the proposed extraction process, with Redlich-Kwong-Soave (RKS) being used for the thermodynamic property model. In summary, we have made comprehensive VLE measurements for short alkane + long alkane systems over a wide range of pressures and temperatures, dramatically increasing the amount of high-quality data available for these simple, yet highly relevant systems. In addition, our work has demonstrated that, surprisingly, no current thermodynamic model can adequately predict VLE behavior for these systems. Thus, process simulations (such as those for our proposed SCF extraction process) that incorporate these systems can currently only give results that are qualitative at best. Although significant progress has been made in the past decade, more experimental and theoretical work remain to be done before the phase equilibria of asymmetric alkane mixtures can be predicted with confidence.

  14. Meteorites, Organics and Fischer-Tropsch Type Reaction: Production and Destruction

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M.; Burton, A. S.; Nurth, J. A., III

    2011-01-01

    There has been an ongoing debate about the relative importance about the various chemical reactions that fonned organics in the early solar system. One proposed method that has long been recognized as a potential source of organics is Fischer-Tropsch type (FTT) synthesis. This process is commonly used in industry to produce fuels (i.e., complex hydrocarbons) by catalytic hydrogenation of carbon monoxide. Hill and Nuth were the first to publish results of FTT experiments that also included Haber-Bosch (HB) processes (hydrogenation of nitrogen. Their findings included the production of nitrilebearing compounds as well as trace amounts of methyl amine. Previous experience with these reactions revealed that the organic coating deposited on the grains is also an efficient catalyst and that the coating is composed of insoluble organic matter (10M) and could be reminiscent of the organic matrix found in some meteorites. This current set of FTT-styled experiments tracks the evolution of a set of organics, amino acids, in detail.

  15. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst

    SciTech Connect

    Abrevaya, H.

    1991-01-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors. An experimental cobalt catalyst 585R2723 was tested three times in the fixed-bed reactor. The objective of the tests was to identify suitable testing conditions for screening catalyst. The {alpha}-alumina was determined to be a suitable diluent medium for controlling the catalyst bed temperature close to the inlet temperature. With 13 g of catalyst and 155 g of diluent, the catalyst maximum temperature were within 2{degree}C from the inlet temperatures. As a result of this work, 210{degree}C and 21 atm were shown to result in low methane selectivity and were used as initial conditions in the catalyst screening test. Ethane, which along with methane is undesirable, is typically produced with low selectivity and follows the same trend as methane. Other work reported here indicated that methane selectivity increases with increasing temperature but is not excessively high at 230{degree}C. Consequently, the catalyst screening test should include an evaluation of the catalyst performance at 230{degree}C. During Run 67, the increase in temperature from 210{degree}C to 230{degree}C was initiated at 30 hours on-stream.

  16. Incorporation of catalytic dehydrogenation into Fischer-Tropsch synthesis to lower carbon dioxide emissions

    DOEpatents

    Huffman, Gerald P

    2012-09-18

    A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbon monoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

  17. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    MARK C. THIES; PATRICK C. JOYCE

    1998-10-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished at conditions that do not entrain the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds. That is, a constant carbon-number distribution in the wax slurry must be maintained at steady-state column operation. Three major tasks are being undertaken to evaluate our proposed SCF extraction process. Task 1: Equilibrium solubility measurements for model F-T wax components in supercritical fluids at conditions representative of those in a SBC reactor. Task 2: Thermodynamic modeling of the measured VLE data for extending our results to real wax systems. Task 3: Process design studies of our proposed process. Additional details of the task structure are given.

  18. Low-pressure hydrocracking of coal-derived Fischer-Tropsch waxes to diesel

    SciTech Connect

    Dieter Leckel

    2007-06-15

    Coal-derived low-temperature Fischer-Tropsch (LTFT) wax was hydrocracked at pressures of 3.5-7.0 MPa using silica-alumina-supported sulfided NiW/NiMo and an unsulfided noble metal catalyst, modified with MoO{sub 3}. A low-pressure operation at 3.5 MPa produced a highly isomerized diesel, having low cloud points (from -12 to -28{sup o}C) combined with high cetane numbers (69-73). These properties together with the extremely low sulfur ({lt}5 ppm) and aromatic ({lt}0.5%) contents place coal/liquid (CTL) derived distillates as highly valuable blending components to achieve Eurograde diesel specifications. The upgrading of coal-based LTFT waxes through hydrocracking to high-quality diesel fuel blend components in combination with commercial-feasible coal-integrated gasification combined cycle (coal-IGCC) CO{sub 2} capture and storage schemes should make CTL technology more attractive. 28 refs., 7 figs., 8 tabs.

  19. SEPARATION OF FISCHER-TROPSCH WAX FROM CATALYST BY SUPERCRITICAL EXTRACTION

    SciTech Connect

    MARK C. THIES; PATRICK C. JOYCE

    1998-07-31

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for the recovery and fractionation of the wax product from the slurry bubble column (SBC) reactor of the Fischer-Tropsch (F-T) process. The wax, comprised mostly of branched and linear alkanes with a broad molecular weight distribution up to C{sub 100}, will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300 C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished at conditions that do not entrain the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds. That is, a constant carbon-number distribution in the wax slurry must be maintained at steady-state column operation. Three major tasks are being undertaken to evaluate our proposed SCF extraction process. Task 1: Equilibrium solubility measurements for model F-T wax components in supercritical fluids at conditions representative of those in a SBC reactor. Task 2: Thermodynamic modeling of the measured VLE data for extending our results to real wax systems. Task 3: Process design studies of our proposed process. Additional details of the task structure are given.

  20. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, October 1, 1993--December 31, 1993

    SciTech Connect

    Subramaniam, B.; Bochniak, D.; Snavely, K.

    1994-01-01

    Construction of the automated high pressure reactor unit was completed. Testing of the reactor and trial runs are currently in progress. An HP 5890 GC/FID system interfaced with an BP 3365 Chemstation is now in place for analysis of F-T synthesis products. Calibration methods are currently under development. The pressure transducers were successfully calibrated using high precision Heise gauges. Figure 1 shows the linearity of the transducer response. The HPLC pump, used for pumping n-hexane was also tested and calibrated. The agitated sand bath surrounding the reactor (meant for absorbing the high heat of reaction produced in Fischer-Tropsch synthesis) was assembled in place and successfully tested. The entire system was tested to withstand the operating pressures and to be free of leaks. A cold wax trap was fabricated and added to the existing setup. This is similar in nature to the hot wax trap and will serve to collect condensables from the product stream not collected in the hot wax trap and from the GC exhaust stream. Pressure control (using the stepping-motor-driven micrometering valve) and temperature control tests are currently in progress aimed at establishing the control parameters. Thereafter, the experimental investigations consisting of the blank runs and sub-, near-, and supercritical experiments will be commenced. Progress was made in the development of both on-line and off-line analyses. Off-line analysis determines retention times (compound identification) and response factors (quantitative analysis).

  1. Separation of fischer-Tropsch Wax from Catalyst by Supercritical Extraction.

    SciTech Connect

    Joyce, P.C.; Thies, M.C.; Sherrard, D.; Biales, J.; Kilpatrick, P.; Roberts, G.

    1997-07-31

    Although alkanes are the major constituent of a Fischer-Tropsch wax, significant quantities (e.g., up to 30 wt %) of long-chain alcohol and alkene compounds can also be found in a F-T wax. With the lack of experimental data, the effect that the hydroxy and double-bond functional groups have on the phase behavior of systems containing long- chain hydrocarbons is unknown. Therefore, the phase behavior of the system n-hexane/1-hexadecanol was measured for comparison with the previously measured system n-hexane/hexadecane. Vapor and liquid equilibrium compositions and mixture critical points were measured at 198.9, 251.3, 299.2, and 349.9 {degrees}C at pressures ranging from 6.2 to 46.4 bar. Temperature and pressure measurements for all isotherms are believed to be accurate to better than plus or minus 3 and 4 percent, respectively. Results indicate that the addition of the alcohol group to a C 16 hydrocarbon chain significantly affects the phase behavior with hexane, with the two-phase region extending to significantly higher (i.e., up to about 10 bar higher) pressures. The presence of an alcohol group was also found to be an impediment to obtaining a good fit of the experimental data with the Peng-Robinson equation.

  2. In situ observation of self-assembled hydrocarbon Fischer-Tropsch products on a cobalt catalyst.

    PubMed

    Navarro, Violeta; van Spronsen, Matthijs A; Frenken, Joost W M

    2016-10-01

    Fischer-Tropsch synthesis is a heterogeneous catalytic reaction that creates approximately 2% of the world's fuel. It involves the synthesis of linear hydrocarbon molecules from a gaseous mixture of carbon monoxide and hydrogen at high pressures (from a few to tens of bars) and high temperatures (200-350 °C). To gain further insight into the fundamental mechanisms of this industrial process, we have used a purpose-built scanning tunnelling microscope to monitor a cobalt model catalyst under reaction conditions. We show that, after 30 minutes of reaction, the terraces of the cobalt catalyst are covered by parallel arrays of stripes. We propose that the stripes are formed by the self-assembly of linear hydrocarbon product molecules. Surprisingly, the width of the stripes corresponds to molecules that are 14 or 15 carbon atoms long. We introduce a simple model that explains the accumulation of such long molecules by describing their monomer-by-monomer synthesis and explicitly accounting for their thermal desorption. PMID:27657868

  3. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, April--June 1992

    SciTech Connect

    Not Available

    1992-10-01

    Effective September 26, 1991, Bechtel, with Amoco as the main subcontractor, initiated a study to develop a computer model and baseline design for advanced Fischer-Tropsch (F-T) technology for the US Department of Energy`s Pittsburgh Energy Technology Center (PETC). The objectives of the study are to: Develop a baseline design for indirect liquefaction using advanced F-T technology; prepare the capital and operating costs for the baseline design; and develop a process flow sheet simulation (PI-S) model. The baseline design, the economic analysis, and the computer model win be the major research planning tools that PETC will use to plan, guide, and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction. for the manufacture of synthetic liquid fuels from coal. This report is Bechtel`s third quarterly technical progress report covering the period from March 16, 1992 through June 21, 1992. This report consists of seven sections: Section 1 - introduction; Section 2 - summary; Section 3 - carbon dioxide removal tradeoff study; Section 4 - preliminary plant designs for coal preparation; Section 5 - preliminary design for syngas production; Section 6 - Task 3 - engineering design criteria; and Section 7 - project management.

  4. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, October--December 1992

    SciTech Connect

    Not Available

    1992-12-31

    Bechtel, with Amoco as the main subcontractor, initiated a study on September 26, 1991, for the US Department of Energy`s (DOE`s) Pittsburgh Energy Technology Center (PETC) to develop a computer model and baseline design for advanced Fischer-Tropsch (F-T) technology. This 24-month study, with an approved budget of $2.3 million, is being performed under DOE Contract Number AC22-91PC90027. (1) Develop a baseline design and two alternative designs for indirect liquefaction using advanced F-T technology. The baseline design uses Illinois No. 6 Eastern Coal and conventional refining. There is an alternative refining case using ZSM-5 treatment of the vapor stream from the slurry F-T reactor and an alternative coal case using Western coal from the Powder River Basin. (2) Prepare the capital and operating costs for the baseline design and the alternatives. Individual plant costs for the alternative cases will be prorated on capacity, wherever possible, from the baseline case. (3) Develop a process flowsheet simulation (PFS) model. The baseline design, the economic analysis and computer model will be major research planning tools that PETC will use to plan, guide and evaluate its ongoing and future research and commercialization programs relating to indirect coal liquefaction for the manufacture of synthetic liquid fuels from coal.

  5. Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Ritter, G.; Simoneit, B. R.

    1999-01-01

    Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

  6. Microreactor and electron spectroscopy studies of Fischer-Tropsch synthesis on magnetite

    SciTech Connect

    Krebs, H.J.; Bonzel, H.P.; Schwarting, W.; Gafner, G.

    1981-12-01

    The Fischer-Tropsch synthesis from CO and H/sub 2/ (1:3 mixture) at 1 bar total pressure and 570 K has been studied in a differential microreactor system on reduced and unreduced Fe/sub 3/O/sub 4/ (magnetite). The catalytic reactivity data were complemented by surface analytical measurements using Auger electron and x-ray photoelectron spectroscopy (XPS, ESCA). XPS measurements showed evidence of carbon deposition, mostly in the form of graphite on all samples. The rate of methanation on reduced magnetite was characterized by a maximum and subsequent decrease. Both features were dependent on the reduction history of the sample. All samples gave rise to the production of higher-molecular-weight species. The selectivity of reduced magnetite tended towards the formation of saturated hydrocarbons while that of the unreduced magnetite favoured the formation of alkenes. It was concluded that the reduction of magnetite led to a considerable increase in surface area and porosity and that secondary reactions of the alkenes caused the primary product spectrum to shift from alkenes to alkanes. Accordingly the polymerisation probability increased from 0.3 for unreduced magnetite (also for clean foil) to greater than or equal to 0.42 for reduced magnetite.

  7. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, July 10, 1992--September 30, 1992

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260{degrees}C). The SCF medium to be employed is n-Hexane (P{sub c} = 29.7 bar; {Tc} = 233.7{degrees}C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H{sub 2}/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  8. Potential for Coal-to-Liquids Conversion in the United States-Fischer-Tropsch Synthesis

    SciTech Connect

    Patzek, Tad W. Croft, Gregory D.

    2009-09-15

    The United States has the world's largest coal reserves and Montana the highest potential for mega-mine development. Consequently, a large-scale effort to convert coal to liquids (CTL) has been proposed to create a major source of domestic transportation fuels from coal, and some prominent Montanans want to be at the center of that effort. We calculate that the energy efficiency of the best existing Fischer-Tropsch (FT) process applied to average coal in Montana is less than 1/2 of the corresponding efficiency of an average crude oil refining process. The resulting CO{sub 2} emissions are 20 times (2000%) higher for CTL than for conventional petroleum products. One barrel of the FT fuel requires roughly 800 kg of coal and 800 kg of water. The minimum energy cost of subsurface CO{sub 2} sequestration would be at least 40% of the FT fuel energy, essentially halving energy efficiency of the process. We argue therefore that CTL conversion is not the most valuable use for the coal, nor will it ever be, as long as it is economical to use natural gas for electric power generation. This finding results from the low efficiency inherent in FT synthesis, and is independent of the monumental FT plant construction costs, mine construction costs, acute lack of water, and the associated environmental impacts for Montana.

  9. Separation of Fischer-Tropsch catalyst/wax mixtures using dense gas extraction

    SciTech Connect

    Eyring, M.W.; Rohar, P.C.; Hickey, R.F.

    1995-12-01

    The separation of a Fischer-Tropsch catalyst from wax products is an important issue when the synthesis is conducted in a slurry bubble column reactor. This paper describes a new technique based on dense gas extraction of the soluble hydrocarbon components from the insoluble catalyst particles using light hydrocarbons as propane, butane, and pentane as the solvent. The extractions were conducted in a continuous unit operated near the critical point of the extraction gas on a catalyst/wax mixture containing about 4.91 wt% catalyst. The catalyst-free wax was collected in the second stage collector while the catalyst and some insoluble wax components were collected in the first stage collector. The yield of catalyst-free wax was about 60 wt% of the feed mixture. The catalyst content of the catalyst/wax mixture in the first stage was about 14.8 wt%. The catalyst content in the second stage collector was less than 1 part in 100,000.

  10. Separation of Fischer-Tropsch catalyst/wax mixtures using dense gas extraction

    SciTech Connect

    Eyring, M.W.; Rohar, P.C.; Hickey, R.F.; White, C.M.; Quiring, M.S.

    1995-12-31

    The separation of a Fischer-Tropsch catalyst from wax products is an important issue when the synthesis is conducted in a slurry bubble column reactor. This paper describes a new technique based on dense gas extraction of the soluble hydrocarbon components from the insoluble catalyst particles using light hydrocarbons as propane, butane, and pentane an the solvent. The extractions were conducted in a continuous unit operated near the critical point of the extraction gas on a catalyst/wax mixture containing about 4.91 wt% catalyst. The catalyst-free wax was collected in the second stage collector while the catalyst and some insoluble wax components were collected in the first stage collector. The yield of catalyst-free wax was about 60 wt% of the food mixture. The catalyst content of the catalyst/wax mixture in the first stage was about 14.8 wt%. The catalyst content in the second stage collector was less than 1 part in 100,000.

  11. Aspen Process Flowsheet Simulation Model of a Battelle Biomass-Based Gasification, Fischer-Tropsch Liquefaction and Combined-Cycle Power Plant

    SciTech Connect

    1998-10-30

    This study was done to support the research and development program of the National Renewable Energy Laboratory (NREL) in the thermochemical conversion of biomass to liquid transportation fuels using current state-of-the-art technology. The Mitretek study investigated the use of two biomass gasifiers; the RENUGAS gasifier being developed by the Institute of Gas Technology, and the indirectly heated gasifier being developed by Battelle Columbus. The Battelle Memorial Institute of Columbus, Ohio indirectly heated biomass gasifier was selected for this model development because the syngas produced by it is better suited for Fischer-Tropsch synthesis with an iron-based catalyst for which a large amount of experimental data are available. Bechtel with Amoco as a subcontractor developed a conceptual baseline design and several alternative designs for indirect coal liquefaction facilities. In addition, ASPEN Plus process flowsheet simulation models were developed for each of designs. These models were used to perform several parametric studies to investigate various alternatives for improving the economics of indirect coal liquefaction.

  12. Structural Sensitivity of Carbon Monoxide Hydrogenation by Nano-Structured Iron Catalyst.

    PubMed

    Pour, Ali Nakhaei; Chekreh, Soheila; Housaindokht, Mohammad Reza; Eftekhari, Ali

    2016-06-01

    A new size dependence kinetic equation for chain growth factor in Fischer-Tropsch synthesis (FTS) was developed using a thermodynamic analysis method. For evaluation of structural sensitivity of FTS reaction, a series of iron oxide nanoparticles were prepared as a catalyst via precipitation by microemulsion method. The experimental results indicated that the difference between activation energies for propagation and termination reactions (Et-Ep) decreased with decreasing the catalyst particle size. Calculated size dependent model parameters were employed for evaluation of surface tension energy (σ) and size-independent activation energy for chain growth probabilities. PMID:27427644

  13. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Janet ChakkamadathilMohandas; Wilson Shafer

    2009-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.

  14. Synthesis of octane enhancers during slurry-phase Fischer-Tropsch. Quarterly technical progress report No. 3, April 1, 1991--June 30, 1991

    SciTech Connect

    Marcelin, G.

    1991-10-15

    The objective of this project is to investigate three possible routes to the formation of ethers, in particular methyl tert-butytl ether (MTBE), during slurry phase Fischer-Tropsch reaction. The three reaction schemes to be investigated are: (1) Addition of isobutylene during the formation of methanol and/or higher alcohols directly from CO and H{sub 2} during slurry-phase Fischer-Tropsch; (2) addition of isobutylene to FT liquid products including alcohols in a slurry-phase reactor containing an MTBE or other acid catalyst; and, (3) addition of methanol to slurry phase FT synthesis making iso-olefins.

  15. Separation of Fischer-Tropsch wax from catalyst by supercritical fluid extraction. Technical progress report, January--March 1995

    SciTech Connect

    Thies, M.C.

    1995-08-01

    Objective is to evaluate the potential of supercritical fluid extraction for separating the catalyst slurry of a Fischer-Tropsch (F- T) slurry bubble column reactor into a wax and a concentrated catalyst slurry that is ready for recycle/regeneration. The automated apparatus was evaluated using a toluene-petroleum pitch system. The Statistical Associating Fluid Theory (SAFT) equation will be used to fit the VLE and LLE data for F-T wax-solvent systems; this equation was successful in predicting both phase compositions and average molecular weight distributions.

  16. Mechanism and kinetics of Fischer-Tropsch synthesis over supported ruthenium catalysts

    SciTech Connect

    Kellner, C.S.

    1981-06-01

    A detailed study of the kinetics of the Fischer-Tropsch synthesis of hydrocarbons, methanol, and acetaldehyde, over alumina- and silica-supported ruthenium catalysts has been carried out over a broad range of reaction conditions. Based on these results and information taken from the literature, mechanisms for the formation of normal paraffins, ..cap alpha..-olefins, methanol, and acetaldehyde have been proposed. Rate data were obtained between 448 and 548K, 1 and 10 atm, and H/sub 2//CO ratios between 1 and 3, utilizing a micro flow reactor operated at very low conversions. In addition to the studies performed with H/sub 2//CO mixtures, a series of experiments were carried out utilizing D/sub 2//CO mixtures. These studies were used to help identify rate limited steps and steps that were at equilibrium. A complementary investigation, carried out by in situ infrared spectroscopy, was performed using a Fourier Transform spectrometer. The spectra obtained were used to identify the modes of CO adsorption, the CO coverage, and the relative reactivity of different forms of adsorbed CO. It was established that CO adsorbs on alumina-supported Ru in, at least, two forms: (i) Ru-CO and (ii) OC-Ru-CO. Only the first of these forms participates in CO hydrogenation. The coverage of this species is described by a simple Langmuir isotherm. A reaction mechanism is presented for interpreting the kinetics of hydrocarbon synthesis, the olefin to paraffin ratio for each product, and the probability of chain propagation. Rate expressions based on this mechanism are reasonably consistent with the experimental data. Acetaldehyde, obtained mainly over silica-supported Ru, appears to be formed by a mechanism related to that for hydroformulation of olefins. The effect of the dispersion of Ru/Al/sub 2/O/sub 3/ catalysts on their specific activity and selectivity was also investigated. The specific activity for all products decreased rapidly with increasing dispersions.

  17. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio; Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2006-09-30

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for feedstocks consisting of synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based FT catalysts with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. More specifically, we were focused on the roles of hydrogen-assisted and alkali-assisted dissociation of CO in determining rates and CO{sub 2} selectivities. During this sixth reporting period, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that

  18. Effect of the porous structure of the support on hydrocarbon distribution in the Fischer-Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Bartolini, Monica; Molina, Jhoanna; Alvarez, Juan; Goldwasser, Mireya; Pereira Almao, Pedro; Zurita, M. Josefina Pérez

    2015-07-01

    Emissions standards are increasingly stringent due mainly to its impact on the environment. Although the diesel engine is an attractive solution for carbon dioxide reduction, a challenge remains to simultaneously control nitrogen oxides and matter particulate emissions to accepted levels. On engine tests, it has been observed that Fischer-Tropsch diesel significantly reduces CO, HC, PAHs and particulate emissions compared to oil derived diesel. However, selectivity control in Fischer Tropsch Synthesis is still a key challenge due the Anderson-Schultz-Flory polymerization mechanism followed by hydrocarbon distribution. In this work we are presenting the first steps towards a new strategy that can tune, in one step, the selectivity to desired products by taking advantage of the shape selectivity properties of SBA-15 mesoporous silica used as support. Co-SBA-15 (30%wt) catalysts with different pore size were prepared by excess solution impregnation. Our results show that pore diameter not only affects the size and reducibility of Co particles but it also significantly influence the liquid products distribution, with the high molecular weight hydrocarbon fraction increasing on large pores, attributed to the existence of a shape selectivity effect induced by the textural properties of the catalyst namely its pore size and pore volume.

  19. Effect of 1-olefin addition on supercritical phase Fischer-Tropsch synthesis over Co/SiO{sub 2} catalyst

    SciTech Connect

    Yan, S.R.; Zhang, Z.X.; Zhou, J.L.; Fan, L.; Fujimoto, Kaoru

    1997-12-31

    Hydrocarbon wax produced by Fischer-Tropsch Synthesis (FTS) has been used in many fields for its high quality, such as high melting point, high hardness value, low viscosity, being nitrogen sulfur and aromatics-free. Selective synthesis of FT wax has generated great interest, especially in the case of lower oil-prices. As a polymerization process, however, in conventional gas phase FTS, selectivity of wax is constrained by the Anderson-Schultz-Flory (ASF) kinetics. Supercritical phase Fischer-Tropsch synthesis co-fed with 1-tetradecene over Co/SiO{sub 2} catalysts has been carried out. It was found that added 1-tetradecene could reach the surface of the catalyst by the aid of a supercritical fluid, and participate in the chain growth process there, which was indistinguishable from the original chain propagation. Consequently, the yield of hydrocarbons larger than C{sub 14} increased significantly, while the selectivity of C{sub 1}-C{sub 13} decreased correspondingly, which made the carbon number distribution deviate from ASF kinetics drastically. In addition, the analytical results of wax showed that average molecular weight and degree of saturation of the wax increased, while the content of oxygenates in the wax decreased due to the addition of 1-tetradecene.

  20. Effect of preparation methods on the catalytic properties of zeolite-supported ruthenium in the Fischer-Tropsch synthesis

    SciTech Connect

    Chen, Y.W.; Wang, H.T.; Goodwin, J.G. Jr.

    1983-10-01

    Three preparation techniques (incipient wetness using a solution of ruthenium chloride (RuCl/sub 3/), vapor impregnation by the ruthenium carbonyl (Ru/sub 3/(CO)/sub 12/), and ion exchange with Ru(NH/sub 3/)/sub 6/Cl/sub 3/) have been used to prepare sodium (Na)Y zeolite-supported ruthenium catalysts. The effect of these preparation methods on the activity and product selectivity of the Ru catalysts in the Fischer-Tropsch synthesis was examined at temperatures in the range of 220 to 320/sup 0/C, a pressure of 1 atm, a CO/H/sub 2/ ratio of 1, and flow rates in the range GHSV = 1800 to 3600 h/sup -1/. It was found that there is a good inverse correlation of turnover numbers for CO conversion to the CO/H adsorption ratio, suggesting that the relative availability of adsorbed H/sub 2/ and CO determines catalyst activity during reaction. Selectivity in the Fischer-Tropsch synthesis was greatly influenced by the preparation method and metal loading. Catalysts prepared by incipient wetness produced mainly methane. Catalysts prepared by vapor impregnation had the best selectivities for higher hydrocarbons and olefins even though they had the smallest average Ru particle sizes. The observed changes in adsorption, activity, and selectivity with preparation method appear to result from differences produced in metal location in/on the zeolite, metal particle size, and zeolite-metal interactions. 12 figures, 2 tables.

  1. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 14, January 1, 1993--March 31, 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-05-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors.

  2. PROGRESS TOWARDS MODELING OF FISCHER TROPSCH SYNTHESIS IN A SLURRY BUBBLE COLUMN REACTOR

    SciTech Connect

    Donna Post Guillen; Tami Grimmett; Anastasia M. Gandrik; Steven P. Antal

    2010-11-01

    The Hybrid Energy Systems Testing (HYTEST) Laboratory is being established at the Idaho National Laboratory to develop and test hybrid energy systems with the principal objective to safeguard U.S. Energy Security by reducing dependence on foreign petroleum. A central component of the HYTEST is the slurry bubble column reactor (SBCR) in which the gas-to-liquid reactions will be performed to synthesize transportation fuels using the Fischer Tropsch (FT) process. SBCRs are cylindrical vessels in which gaseous reactants (for example, synthesis gas or syngas) is sparged into a slurry of liquid reaction products and finely dispersed catalyst particles. The catalyst particles are suspended in the slurry by the rising gas bubbles and serve to promote the chemical reaction that converts syngas to a spectrum of longer chain hydrocarbon products, which can be upgraded to gasoline, diesel or jet fuel. These SBCRs operate in the churn-turbulent flow regime which is characterized by complex hydrodynamics, coupled with reacting flow chemistry and heat transfer, that effect reactor performance. The purpose of this work is to develop a computational multiphase fluid dynamic (CMFD) model to aid in understanding the physico-chemical processes occurring in the SBCR. Our team is developing a robust methodology to couple reaction kinetics and mass transfer into a four-field model (consisting of the bulk liquid, small bubbles, large bubbles and solid catalyst particles) that includes twelve species: (1) CO reactant, (2) H2 reactant, (3) hydrocarbon product, and (4) H2O product in small bubbles, large bubbles, and the bulk fluid. Properties of the hydrocarbon product were specified by vapor liquid equilibrium calculations. The absorption and kinetic models, specifically changes in species concentrations, have been incorporated into the mass continuity equation. The reaction rate is determined based on the macrokinetic model for a cobalt catalyst developed by Yates and Satterfield [1]. The

  3. Heat transfer and bubble dynamics in slurry bubble columns for Fischer-Tropsch clean alternative energy

    NASA Astrophysics Data System (ADS)

    Wu, Chengtian

    With the increasing demand for alternative energy resources, the Fischer-Tropsch (FT) process that converts synthesis gas into clean liquid fuels has attracted more interest from the industry. Slurry bubble columns are the most promising reactors for FT synthesis due to their advantages over other reactors. Successful operation, design, and scale-up of such reactors require detailed knowledge of hydrodynamics, bubble dynamics, and transport characteristics. However, most previous studies have been conducted at ambient pressure or covered only low superficial gas velocities. The objectives of this study were to experimentally investigate the heat transfer coefficient and bubble dynamics in slurry bubble columns at conditions that can mimic FT conditions. The air-C9C 11-FT catalysts/glass beads systems were selected to mimic the physical properties of the gas, liquid, and solid phases at commercial FT operating conditions. A heat transfer coefficient measurement technique was developed, and for the first time, this technique was applied in a pilot scale (6-inch diameter) high pressure slurry bubble column. The effects of superficial gas velocity, pressure, solids loading, and liquid properties on the heat transfer coefficients were investigated. Since the heat transfer coefficient can be affected by the bubble properties (Kumar et al., 1992), in this work bubble dynamics (local gas holdup, bubble chord length, apparent bubble frequency, specific interfacial area, and bubble velocity) were studied using the improved four-point optical probe technique (Xue et al., 2003; Xue, 2004). Because the four-point optical technique had only been successfully applied in a churn turbulent flow bubble column (Xue, 2004), this technique was first assessed in a small scale slurry bubble column in this study. Then the bubble dynamics were studied at the same conditions as the heat transfer coefficient investigation in the same pilot scale column. The results from four-point probe

  4. Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

    NASA Technical Reports Server (NTRS)

    Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

    2014-01-01

    Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

  5. A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer-Tropsch synthesis.

    PubMed

    Sun, Zhenkun; Sun, Bo; Qiao, Minghua; Wei, Jing; Yue, Qin; Wang, Chun; Deng, Yonghui; Kaliaguine, Serge; Zhao, Dongyuan

    2012-10-24

    The organization of different nano objects with tunable sizes, morphologies, and functions into integrated nanostructures is critical to the development of novel nanosystems that display high performances in sensing, catalysis, and so on. Herein, using acetylacetone as a chelating agent, phenolic resol as a carbon source, metal nitrates as metal sources, and amphiphilic copolymers as a template, we demonstrate a chelate-assisted multicomponent coassembly method to synthesize ordered mesoporous carbon with uniform metal-containing nanoparticles. The obtained nanocomposites have a 2-D hexagonally arranged pore structure, uniform pore size (~4.0 nm), high surface area (~500 m(2)/g), moderate pore volume (~0.30 cm(3)/g), uniform and highly dispersed Fe(2)O(3) nanoparticles, and constant Fe(2)O(3) contents around 10 wt %. By adjusting acetylacetone amount, the size of Fe(2)O(3) nanoparticles is readily tunable from 8.3 to 22.1 nm. More importantly, it is found that the metal-containing nanoparticles are partially embedded in the carbon framework with the remaining part exposed in the mesopore channels. This unique semiexposure structure not only provides an excellent confinement effect and exposed surface for catalysis but also helps to tightly trap the nanoparticles and prevent aggregating during catalysis. Fischer-Tropsch synthesis results show that as the size of iron nanoparticles decreases, the mesoporous Fe-carbon nanocomposites exhibit significantly improved catalytic performances with C(5+) selectivity up to 68%, much better than any reported promoter-free Fe-based catalysts due to the unique semiexposure morphology of metal-containing nanoparticles confined in the mesoporous carbon matrix.

  6. Selective synthesis and chain growth of linear hydrocarbons in the Fischer-Tropsch synthesis over zeolite-entrapped cobalt catalysts

    SciTech Connect

    Koh, D.J.; Chung, J.S.; Kim, Y.G.

    1995-06-01

    The impregnation of NaOH solution into the pores of cobalt-exchanged zeolite promoted the conventional reduction of cobalt ions with hydrogen gas. The method yielded catalysts that had high degrees of reduction and small cobalt clusters located inside zeolite pores. In the Fischer-Tropsch synthesis these catalysts showed a chain-extension effect, producing hydrocarbons higher than C{sub 10} in appreciable amounts, and an enhanced production of linear hydrocarbons such as 1-olefins and n-paraffins. The formation of long-chain hydrocarbons is attributed to an increased chance of the chain growth owing to a hold-up effect of reaction intermediates, especially 1-olefins, which are accumulated inside zeolite pores during the reaction. Hydrocarbon isomers are produced over acidic sites of zeolite by secondary reactions (isomerization and cracking), which result in a chain shortening of the long-chain hydrocarbons.

  7. Effect of Surface Modification by Chelating Agents on Fischer- Tropsch Performance of Co/SiO{sub 2} Catalysts

    SciTech Connect

    Bambal, Ashish S.; Kugler, Edwin L.; Gardner, Todd H.; Dadyburjor, Dady B.

    2013-11-14

    The silica support of a Co-based catalyst for Fischer-Tropsch (FT) synthesis was modified by the chelating agents (CAs) nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA). After the modification, characterization of the fresh and spent catalysts show reduced crystallite sizes, a better-dispersed Co₃O₄ phase on the calcined samples, and increased metal dispersions for the reduced samples. The CA-modified catalysts display higher CO conversions, product yields, reaction rates and rate constants. The improved FT performance of CA-modified catalysts is attributed to the formation of stable complexes with Co. The superior performance of the EDTA-modified catalyst in comparison to the NTA-modified catalyst is due to the higher affinity of the former for complex formation with Co ions.

  8. Studies on the Role of Nitrogen in the Feed for Fischer-Tropsch Synthesis Under Fixed-Bed Reactor System.

    PubMed

    Hong, Gi Hoon; Jung, Jae-Sun; Kim, Na-Young; Lee, Sang Yong; Moon, Dong Ju

    2016-02-01

    In this study, Co/Al203 catalyst for Fischer-Tropsch synthesis was prepared via slurry impregnation method and the catalyst was characterized by various techniques such as TPR, XRD, TGA and N2 physisorption. To dissolve the wax, after-reaction catalyst was dewaxed using n-Hexane at 60 *C. The experiments were performed in a bench-scale fixed-bed reactor, under the reaction condition of 230 degrees C, 20 bar and feed volume ratio of H2:CO:N2 = 2:1:0.5-1.5. The methane selectivity and the ratio of olefin to paraffin among C2-C4 hydrocarbons were increased with higher contents of nitrogen in feed gas which result in higher partial pressure ratio of H2 to CO, and also affect methane selectivity which has a significant role in increased CO conversion. PMID:27433695

  9. Reductions in aircraft particulate emissions due to the use of Fischer-Tropsch fuels

    NASA Astrophysics Data System (ADS)

    Beyersdorf, A. J.; Timko, M. T.; Ziemba, L. D.; Bulzan, D.; Corporan, E.; Herndon, S. C.; Howard, R.; Miake-Lye, R.; Thornhill, K. L.; Winstead, E.; Wey, C.; Yu, Z.; Anderson, B. E.

    2013-06-01

    The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January-February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer-Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions of 84% averaged over all powers) and blended fuels (64%) relative to the JP-8 baseline with the largest reductions at idle conditions. The alternative fuels also produced smaller soot (e.g. at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the feedstock. As the plume cools downwind of the engine, nucleation-mode aerosols form. For the pure FT fuels, reductions (94% averaged over all powers) in downwind particle number emissions were similar to those measured at the exhaust plane (84

  10. Ultra-clean Fischer-Tropsch (F-T) Fuels Production and Demonstration Project

    SciTech Connect

    Stephen P. Bergin

    2006-06-30

    The objective of the DOE-NETL Fischer-Tropsch (F-T) Production and Demonstration Program was to produce and evaluate F-T fuel derived from domestic natural gas. The project had two primary phases: (1) fuel production of ultra-clean diesel transportation fuels from domestic fossil resources; and (2) demonstration and performance testing of these fuels in engines. The project also included a well-to-wheels economic analysis and a feasibility study of small-footprint F-T plants (SFPs) for remote locations such as rural Alaska. During the fuel production phase, ICRC partnered and cost-shared with Syntroleum Corporation to complete the mechanical design, construction, and operation of a modular SFP that converts natural gas, via F-T and hydro-processing reactions, into hydrogensaturated diesel fuel. Construction of the Tulsa, Oklahoma plant started in August 2002 and culminated in the production of over 100,000 gallons of F-T diesel fuel (S-2) through 2004, specifically for this project. That fuel formed the basis of extensive demonstrations and evaluations that followed. The ultra-clean F-T fuels produced had virtually no sulfur (less than 1 ppm) and were of the highest quality in terms of ignition quality, saturation content, backend volatility, etc. Lubricity concerns were investigated to verify that commercially available lubricity additive treatment would be adequate to protect fuel injection system components. In the fuel demonstration and testing phase, two separate bus fleets were utilized. The Washington DC Metropolitan Area Transit Authority (WMATA) and Denali National Park bus fleets were used because they represented nearly opposite ends of several spectra, including: climate, topography, engine load factor, mean distance between stops, and composition of normally used conventional diesel fuel. Fuel evaluations in addition to bus fleet demonstrations included: bus fleet emission measurements; F-T fuel cold weather performance; controlled engine dynamometer

  11. Predicting the performance of system for the co-production of Fischer-Tropsch synthetic liquid and power from coal

    SciTech Connect

    Wang, X.; Xiao, Y.; Xu, S.; Guo, Z.

    2008-01-15

    A co-production system based on Fischer-Tropsch (FT) synthesis reactor and gas turbine was simulated and analyzed. Syngas from entrained bed coal gasification was used as feedstock of the low-temperature slurry phase Fischer-Tropsch reactor. Raw synthetic liquid produced was fractioned and upgraded to diesel, gasoline, and liquid petrol gas (LPG). Tail gas composed of unconverted syngas and FT light components was fed to the gas turbine. Supplemental fuel (NG, or refinery mine gas) might be necessary, which was dependent on gas turbine capacity expander through flow capacity, etc. FT yield information was important to the simulation of this co-production system. A correlation model based on Mobil's two step pilot plant was applied. User models that can predict product yields and cooperate with other units were embedded into Aspen plus simulation. Performance prediction of syngas fired gas turbine was the other key of this system. The increase in mass flow through the turbine affects the match between compressor and turbine operating conditions. The calculation was carried out by GS software developed by Politecnico Di Milano and Princeton University. Various cases were investigated to match the FT synthesis island, power island, and gasification island in co-production systems. Effects of CO{sub 2} removal/LPG recovery, co-firing, and CH{sub 4} content variation were studied. Simulation results indicated that more than 50% of input energy was converted to electricity and FT products. Total yield of gasoline, diesel, and LPG was 136-155 g/N m{sup 3} (CO+H{sub 2}). At coal feed of 21.9 kg/s, net electricity exported to the grid was higher than 100 MW. Total production of diesel and gasoline (and LPG) was 118,000 t (134,000 t)/year. Under the economic analysis conditions assumed in this paper the co-production system was economically feasible.

  12. Shape-selective catalysts for Fischer-Tropsch chemistry. Final report : January 1, 2001 - December 31, 2008.

    SciTech Connect

    Cronauer, D. C.

    2011-04-11

    Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for

  13. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1989--December 31, 1989

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-12-31

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240{degrees}C, 0.5 to 1.5 MPa, H{sub 2}/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R{sub H{sub 2+Co}} = (a P{sub CO}P{sub H{sub 2}})/(1 + b P{sub CO}){sup 2}. The apparent activation energy was 93 to 95 kJ/mol. Data from previous studies on cobalt-based Fischer-Tropsch catalysts are also well correlated with this rate expression.

  14. Reductions in aircraft particulate emissions due to the use of Fischer-Tropsch fuels

    NASA Astrophysics Data System (ADS)

    Beyersdorf, A. J.; Timko, M. T.; Ziemba, L. D.; Bulzan, D.; Corporan, E.; Herndon, S. C.; Howard, R.; Miake-Lye, R.; Thornhill, K. L.; Winstead, E.; Wey, C.; Yu, Z.; Anderson, B. E.

    2014-01-01

    The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability, and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January-February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer-Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions in mass of 86% averaged over all powers) and blended fuels (66%) relative to the JP-8 baseline with the largest reductions at idle conditions. At 7% power, this corresponds to a reduction from 7.6 mg kg-1 for JP-8 to 1.2 mg kg-1 for the natural gas FT fuel. At full power, soot emissions were reduced from 103 to 24 mg kg-1 (JP-8 and natural gas FT, respectively). The alternative fuels also produced smaller soot (e.g., at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the natural gas FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the

  15. Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations.

    PubMed

    Klimkiewicz, Roman

    2014-01-01

    Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate. Graphical Abstract.

  16. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction.

  17. Comparison of PM emissions from a commercial jet engine burning conventional, biomass, and Fischer-Tropsch fuels.

    PubMed

    Lobo, Prem; Hagen, Donald E; Whitefield, Philip D

    2011-12-15

    Rising fuel costs, an increasing desire to enhance security of energy supply, and potential environmental benefits have driven research into alternative renewable fuels for commercial aviation applications. This paper reports the results of the first measurements of particulate matter (PM) emissions from a CFM56-7B commercial jet engine burning conventional and alternative biomass- and, Fischer-Tropsch (F-T)-based fuels. PM emissions reductions are observed with all fuels and blends when compared to the emissions from a reference conventional fuel, Jet A1, and are attributed to fuel properties associated with the fuels and blends studied. Although the alternative fuel candidates studied in this campaign offer the potential for large PM emissions reductions, with the exception of the 50% blend of F-T fuel, they do not meet current standards for aviation fuel and thus cannot be considered as certified replacement fuels. Over the ICAO Landing Takeoff Cycle, which is intended to simulate aircraft engine operations that affect local air quality, the overall PM number-based emissions for the 50% blend of F-T fuel were reduced by 34 ± 7%, and the mass-based emissions were reduced by 39 ± 7%.

  18. Performance characterization of CNTs and γ-Al2O3 supported cobalt catalysts in Fischer-Tropsch reaction

    NASA Astrophysics Data System (ADS)

    Ali, Sardar; Zabidi, Noor Asmawati Mohd; Subbarao, Duvvuri

    2014-10-01

    Catalysts were prepared via a wet impregnation method. Different physicochemical properties of the samples were revealed by transmission electron microscope (TEM), temperature programmed reduction (H2-TPR) and carbon dioxide desorption (CO2-desorption). Fischer-Tropsch reaction (FTS) was carried out in a fixed-bed microreactor at 220°C and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12L/g.h for 5 h. Various characterization techniques revealed that there was a stronger interaction between Co and Al2O3 support compared to that of CNTs support. CNTs support increased the reducibility and decreased Co particle size. A significant increase in % CO conversion and FTS reaction rate was observed over CNTs support compared to that of Co / Al2O3. Co/CNTs resulted in higher C5+ hydrocarbons selectivity compared to that of Co / Al2O3 catalyst. CNTs are a better support for Co compared to Al2O3.

  19. Separation of Fischer-Tropsch wax from catalyst by supercritical extraction. Quarterly report, July 1, 1996 - September 30, 1996

    SciTech Connect

    Joyce, P.C.; Thies, M.C.; Sherrard, D.; Biales, J.; Kilpatrick, P.; Roberts, G.

    1996-12-31

    The objective of this research projects is to evaluate the potential of SCF extraction for separating the catalyst slurry of a Fischer- Tropsch (F-T) slurry bubble column (SBC) reactor into two fractions: (1) a catalyst-free wax containing less than 10 ppm particulate matter and (2) a concentrated catalyst slurry that is ready for recycle or regeneration. The wax will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e. 200-300{degrees}C. Initial work is being performed using n-hexane as the solvent. The success of the projects depends on two major factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, the must be accomplished without entraining the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds, i.e., a constant carbon-number distribution of the alkanes in the wax slurry must be maintained at steady-state column operation. The project includes three tasks (1) equilibrium solubility measurements, (2) thermodynamic modeling, and (3) process design studies.

  20. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    PubMed

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction. PMID:27433672

  1. Organic Analysis of Catalytic Fischer-Tropsch Type Synthesis Products: Are they Similar to Organics in Chondritic Meteorites?

    NASA Technical Reports Server (NTRS)

    Yazzie, Cyriah A.; Locke, Darren R.; Johnson, Natasha M.

    2014-01-01

    Fischer-Tropsch Type (FTT) synthesis of organic compounds has been hypothesized to occur in the early solar nebula that formed our Solar System. FTT is a collection of abiotic chemical reactions that convert a mixture of carbon monoxide and hydrogen over nano-catalysts into hydrocarbons and other more complex aromatic compounds. We hypothesized that FTT can generate similar organic compounds as those seen in chondritic meteorites; fragments of asteroids that are characteristic of the early solar system. Specific goals for this project included: 1) determining the effects of different FTT catalyst, reaction temperature, and cycles on organic compounds produced, 2) imaging of organic coatings found on the catalyst, and 3) comparison of organic compounds produced experimentally by FTT synthesis and those found in the ordinary chondrite LL5 Chelyabinsk meteorite. We used Pyrolysis Gas Chromatography Mass Spectrometry (PY-GCMS) to release organic compounds present in experimental FTT and meteorite samples, and Scanning Electron Microscopy (SEM) to take images of organic films on catalyst grains.

  2. Incorporation of Reaction Kinetics into a Multiphase, Hydrodynamic Model of a Fischer Tropsch Slurry Bubble Column Reactor

    SciTech Connect

    Donna Guillen, PhD; Anastasia Gribik; Daniel Ginosar, PhD; Steven P. Antal, PhD

    2008-11-01

    This paper describes the development of a computational multiphase fluid dynamics (CMFD) model of the Fischer Tropsch (FT) process in a Slurry Bubble Column Reactor (SBCR). The CMFD model is fundamentally based which allows it to be applied to different industrial processes and reactor geometries. The NPHASE CMFD solver [1] is used as the robust computational platform. Results from the CMFD model include gas distribution, species concentration profiles, and local temperatures within the SBCR. This type of model can provide valuable information for process design, operations and troubleshooting of FT plants. An ensemble-averaged, turbulent, multi-fluid solution algorithm for the multiphase, reacting flow with heat transfer was employed. Mechanistic models applicable to churn turbulent flow have been developed to provide a fundamentally based closure set for the equations. In this four-field model formulation, two of the fields are used to track the gas phase (i.e., small spherical and large slug/cap bubbles), and the other two fields are used for the liquid and catalyst particles. Reaction kinetics for a cobalt catalyst is based upon values reported in the published literature. An initial, reaction kinetics model has been developed and exercised to demonstrate viability of the overall solution scheme. The model will continue to be developed with improved physics added in stages.

  3. Separation of Fischer-Tropsch wax from catalyst using supercritical fluid extraction. Quarterly technical progress report, July 1, 1995--September 31, 1995

    SciTech Connect

    Thies, M.C.; Joyce, P.C.

    1996-02-01

    Programming and testing of the highly complex Statistical Associating Fluid Theory (or SAFT) equation of state is essentially complete. As an accuracy check, results from our program were compared and found to be in excellent agreement with those of two other research groups (one in the US and two in Europe) for both a nonassociating (methane-hexadecane) and an associating (carbon dioxide-methanol) system. This equation is being used to model the solubility our model Fischer-Tropsch compounds in supercritical solvents such as hexane. SAFT has been chosen for this work because of its fundamental rigor. Therefore, extension of our model compound results to the poorly defined Fischer-Tropsch waxes should be more successful compared to more empirical equations such as Peng-Robinson. Computer-controlled automation of one of our dynamic supercritical fluid (SCF) extraction apparatus is complete. The apparatus collects samples automatically, dramatically reducing operator manpower and fatigue, and is also capable of controlling the operating pressure more precisely (i.e., within {plus_minus}2 psi). This apparatus (SFE I) will be used for future experiments with actual Fischer-Tropsch waxes. Modification/construction of another apparatus (SCF II) that will be used for our model component-SCF phase equilibria/solubility studies is nearly complete; it is currently being leak-tested. This apparatus was built to handle the low mass flow rates that will be required when measuring solubility data for the more expensive model compounds, such as n-C40. Anticipated results for the next quarter include VLE measurements for hexane-squalane at temperatures to 573 K.

  4. Abiogenic Fischer-Tropsch synthesis of methane at the Baogutu reduced porphyry copper deposit, western Junggar, NW-China

    NASA Astrophysics Data System (ADS)

    Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; Jin, LuYing

    2014-09-01

    Methane is widely developed in hydrothermal fluids from reduced porphyry copper deposits, but its origin remains enigmatic. The occurrence of methane in fluid inclusions at the Late Carboniferous Baogutu reduced porphyry copper deposit in western Junggar, Xinjiang, NW-China, presents an excellent opportunity to address this problem. A systematic study including fluid inclusion Laser-Raman and CO2-CH4 carbon isotope analyses, igneous and hydrothermal mineral H-O isotope analyses, and in situ major, trace element and Sr isotopic analyses of hydrothermal epidote was conducted to constrain the origin of CH4 and CH4-rich fluids. The δ2H and δ18O of water in equilibrium with igneous biotite ranges from -65.0‰ to -66.0‰ and +7.2‰ to +7.4‰, respectively, indicating notable degassing of probably supercritical fluids in the magma chamber. The wide range of δ2H (-58.0‰ to -107.0‰, n = 23) for water within quartz suggests the existence of significant hydrothermal fluid boiling. Water-rock interaction is the most likely mechanism leading to the wide range of δ18O values for water in vein quartz with water/rock ratios (wt.% in O) of 0.15 to 0.75 and 0.13 to 0.46 for a closed and open system, respectively. Detailed Laser-Raman analyses indicate CO2 in apatite included in granodiorite porphyry phenocrystic biotite that records the carbon species of the early stage magmatic stage, whereas later hydrothermal fluids containing CH4 with trace or without CO2 are found in inclusions of vein quartz. We propose that CH4 is probably transformed from CO2 by Fischer-Tropsch type reactions at 500 °C, assumed from CO2-CH4 C isotope equilibrium. The (87Sr/86Sr)i of hydrothermal epidote yields values of 0.70369-0.70404, consistent with that reported for the whole rocks. The δ13CCH4 (-28.6‰ to -22.6‰) and δ2HCH4 (-108.0‰ to -59.5‰) are characteristic of abiogenic methane. The measured δ13CCO2 shows a slightly depleted 13C (-13.5‰ to -7.2‰) relative to upper mantle

  5. Combinatorial computational chemistry approach for materials design: applications in deNOx catalysis, Fischer-Tropsch synthesis, lanthanoid complex, and lithium ion secondary battery.

    PubMed

    Koyama, Michihisa; Tsuboi, Hideyuki; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A; Miyamoto, Akira

    2007-02-01

    Computational chemistry can provide fundamental knowledge regarding various aspects of materials. While its impact in scientific research is greatly increasing, its contributions to industrially important issues are far from satisfactory. In order to realize industrial innovation by computational chemistry, a new concept "combinatorial computational chemistry" has been proposed by introducing the concept of combinatorial chemistry to computational chemistry. This combinatorial computational chemistry approach enables theoretical high-throughput screening for materials design. In this manuscript, we review the successful applications of combinatorial computational chemistry to deNO(x) catalysts, Fischer-Tropsch catalysts, lanthanoid complex catalysts, and cathodes of the lithium ion secondary battery.

  6. Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

    SciTech Connect

    Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.; Nilekar, Anand U.; Mavrikakis, Manos; Iglesia, Enrique

    2010-11-25

    H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes on both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.

  7. Fossil-fuel processing technical/professional services: comparison of Fischer-Tropsch reactor systems. Phase I, final report

    SciTech Connect

    Thompson, G.J.; Riekena, M.L.; Vickers, A.G.

    1981-09-01

    The Fischer-Tropsch reaction was commercialized in Germany and used to produce military fuels in fixed bed reactors. It was recognized from the start that this reactor system had severe operating and yield limitations and alternative reactor systems were sought. In 1955 the Sasol I complex, using an entrained bed (Synthol) reactor system, was started up in South Africa. Although this reactor was a definite improvement and is still operating, the literature is filled with proponents of other reactor systems, each claiming its own advantages. This report provides a summary of the results of a study to compare the development potential of three of these reactor systems with the commercially operating Synthol-entrained bed reactor system. The commercial Synthol reactor is used as a benchmark against which the development potential of the other three reactors can be compared. Most of the information on which this study is based was supplied by the M.W. Kellogg Co. No information beyond that in the literature on the operation of the Synthol reactor system was available for consideration in preparing this study, nor were any details of the changes made to the original Synthol system to overcome the operating problems reported in the literature. Because of conflicting claims and results found in the literature, it was decided to concentrate a large part of this study on a kinetic analysis of the reactor systems, in order to provide a theoretical analysis of intrinsic strengths and weaknesses of the reactors unclouded by different catalysts, operating conditions and feed compositions. The remainder of the study considers the physical attributes of the four reactor systems and compares their respective investment costs, yields, catalyst requirements and thermal efficiencies from simplified conceptual designs.

  8. Fischer-Tropsch fuel for use by the U.S. military as battlefield-use fuel of the future

    SciTech Connect

    Delanie Lamprecht

    2007-06-15

    The United States Department of Defense (DoD) has been interested in low-sulfur, environmentally cleaner Fischer-Tropsch (FT) fuels since 2001 because they want to be less dependent upon foreign crude oil and ensure the security of the supply. A three-phase Joint Battlefield-Use Fuel of the Future (BUFF) program was initiated to evaluate, demonstrate, certify, and implement turbine fuels produced from alternative energy resources for use in all of its gas turbine and diesel engine applications. Sasol Synfuels International (Pty) Ltd. and Sasol Chevron Holdings Ltd., among others, were invited to participate in the program with the objective to supply the DoD with a FT BUFF that conforms to Jet Propulsion 8 (JP-8) and JP-5 fuel volatility and low-temperature fluidity requirements. Although the DoD is more interested in coal-to-liquid (CTL) technology, the product from a gas-to-liquid (GTL) Products Work-Up Demonstration Unit in Sasolburg, South Africa, was used to evaluate (on a bench scale) the possibility of producing a BUFF fraction from the Sasol Slurry Phase Distillate (Sasol SPD) low-temperature FT (LTFT) process and Chevron Isocracking technology. It was concluded from the study that the production of a synthetic FT BUFF is feasible using the Sasol SPD LTFT technology together with the current Chevron isocracking technology. The product yield for a BUFF conforming to JP-8 requirements is 30 vol % of the fractionator feed, whereas the product yield for a BUFF conforming to the JP-5 volatility requirement is slightly less than 22 vol % of the fractionator feed. Also concluded from the study was that the end point of the Sasol SPD LTFT BUFF will be restricted by the freezing point requirement of the DoD and not the maximum viscosity requirement. One would therefore need to optimize the hydrocracking process conditions to increase the Sasol SPD LTFT BUFF product yield. 16 refs., 8 figs., 6 tabs.

  9. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    SciTech Connect

    Cronauer, D. C.

    2011-04-15

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first

  10. Effect of Thermal Treatment on Structure and Catalytic Activity of Supported Fischer-Tropsch Nano-Cobalt Catalysts for Clean Fuels

    NASA Astrophysics Data System (ADS)

    Chu, Wei; Hong, J. P.; Payen, E.; Dai, X. Y.

    2007-12-01

    A series of 15%Co/Al2O3 catalysts were prepared by incipient wetness impregnation under various calcination conditions (90-500°C), and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy experiments (XPS), temperature programmed reduction, and catalytic measurements of hydrogenation of carbon monoxide to long-chained hydrocarbons leading to clean fuels (Fischer-Tropsch synthesis). The results of XPS show the presence of incompletely decomposed cobalt nitrate for catalysts calcined at 90-200°C, and the presence of Co3O4 for catalysts calcined at 200-500°C. For the four alumina-supported nano-cobalt catalysts with different thermal treatment (200-500°C), XRD and XPS results illustrated that there were mainly nano Co3O4 crystalite phases of 9-10 nm and the size of cobalt nano-particles did almost not change with the different temperature of thermal treatment. This was different from that of silica-supported cobalt catalysts. The supported cobalt catalyst (CoAp340 sample) calcinated at 340°C presented a better activity for Fischer Tropsch synthesis to clean fuels, at mild conditions like atmospheric pressure (100 kPa), 1800 mL/g/h and 190°C rather than high pressure (2 MPa or more).

  11. The selective catalytic cracking of Fischer-Tropsch liquids to high value transportation fuels. Quarterly technical progress report No. 5, first quarter fiscal year 1993, October 1, 1992--December 31, 1992

    SciTech Connect

    Reagan, W.J.

    1995-01-01

    Amoco Oil Company, under a contract with the United States Department of Energy, is investigating a selective catalytic cracking process to convert the Fischer-Tropsch gasoline and wax fractions to high value transportation fuels. This report describes the work in the first quarter, fiscal year, 1993.

  12. Laboratory Studies of Fischer-Tropsch-Type Reactions and Their Implications for Organics in Asteroids and Comets

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph

    2011-01-01

    We have been studying Fischer-Tropsch type (FTT) reactions as a source for organic materials both in the gas phase of the solar nebula and incorporated into primitive comets and asteroids for almost 10 years, and over this time our concept has evolved greatly from the standard "catalytic" model to a much more robust chemical scenario. Our simulations have been conducted at temperatures that are much higher than we like, primarily for practical reasons such as the timescale of individual reactions, and we are just starting a series of measurements to allow us to measure reaction rates at temperatures from 873K down to as low as 373K. We have preliminary data on the carbon (d13C = -50) & nitrogen (d15N = +9.5) isotopic fractionation at 873K, but not on materials produced at lower temperature. Isotope values are on the VPDB scale for carbon and vs. Air for nitrogen. We have also investigated the noble gas trapping efficiency of the FTT process by adding a small amount of a noble gas mix to our standard synthesis mix. The noble gas ratio is 49:49:1:1::Ne:Ar:Kr:Xe. Xe and Kr are trapped at 873K and are more efficiently trapped at 673K with no isotopic fractionation at either temperature. Ar trapping is detected at 673K, but not at 873K. Ne has not yet been observed in our samples. The solar nebula was an extremely complex system, mixing materials from the innermost regions out to well into the zones where comets formed and thus mixing highly processed nebular materials with grains and coatings formed before the nebula began to collapse. Laboratory studies may provide the means to separate such diverse components based on carbon or nitrogen isotopic fractionation or the quantities of noble gases trapped in grain coatings and their thermal release patterns, among other observables. The ultimate goal of laboratory synthesis of nebular analogs is to provide the means to identifY the conditions under which natural samples were formed and the signatures of subsequent

  13. DEVELOPMENT OF A COMPUTATIONAL MULTIPHASE FLOW MODEL FOR FISCHER TROPSCH SYNTHESIS IN A SLURRY BUBBLE COLUMN REACTOR

    SciTech Connect

    Donna Post Guillen; Tami Grimmett; Anastasia M. Gribik; Steven P. Antal

    2010-09-01

    The Hybrid Energy Systems Testing (HYTEST) Laboratory is being established at the Idaho National Laboratory to develop and test hybrid energy systems with the principal objective to safeguard U.S. Energy Security by reducing dependence on foreign petroleum. A central component of the HYTEST is the slurry bubble column reactor (SBCR) in which the gas-to-liquid reactions will be performed to synthesize transportation fuels using the Fischer Tropsch (FT) process. SBCRs are cylindrical vessels in which gaseous reactants (for example, synthesis gas or syngas) is sparged into a slurry of liquid reaction products and finely dispersed catalyst particles. The catalyst particles are suspended in the slurry by the rising gas bubbles and serve to promote the chemical reaction that converts syngas to a spectrum of longer chain hydrocarbon products, which can be upgraded to gasoline, diesel or jet fuel. These SBCRs operate in the churn-turbulent flow regime which is characterized by complex hydrodynamics, coupled with reacting flow chemistry and heat transfer, that effect reactor performance. The purpose of this work is to develop a computational multiphase fluid dynamic (CMFD) model to aid in understanding the physico-chemical processes occurring in the SBCR. Our team is developing a robust methodology to couple reaction kinetics and mass transfer into a four-field model (consisting of the bulk liquid, small bubbles, large bubbles and solid catalyst particles) that includes twelve species: (1) CO reactant, (2) H2 reactant, (3) hydrocarbon product, and (4) H2O product in small bubbles, large bubbles, and the bulk fluid. Properties of the hydrocarbon product were specified by vapor liquid equilibrium calculations. The absorption and kinetic models, specifically changes in species concentrations, have been incorporated into the mass continuity equation. The reaction rate is determined based on the macrokinetic model for a cobalt catalyst developed by Yates and Satterfield [1]. The

  14. Mössbauer studies of ferrihydrite for Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Lim, Jung Tae; Kim, Chul Sung; Chun, Dong Hyun; Park, Ji Chan

    2016-01-01

    The 6-line ferrihydrite sample for Ficher-Tropsch catalysts was prepared by using a combination of a co-precipitation technique and a spraydrying method. The crystallographic and magnetic properties of 6-line ferrihydrite sample were investigated by using x-ray diffractometer (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrometer. The XRD patterns of the ferrihydrite sample, measured at 295 K, showed 6-lines peak and its structure was found to be a single-phased hexagonal with space group of P3m1 according to JCPDS card. The temperaturedependent magnetization curves were measured under 1000 Oe between 4.2 and 300 K, and showed blocking temperature ( T B ) around 110 K. Also, Mössbauer spectra of the 6-line ferrihydrite sample were taken at various temperatures ranging from 4.2 to 295 K. At temperature below T B , the obtained spectra were analyzed as two-sextets for Fe sites, while At temperature above T B , the obtained spectra showed a doublet due to relaxation, resulting from the spin dynamic effect.

  15. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2006-03-31

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rate, selectivity for feedstocks consisting of synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based FT catalysts with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During this fifth reporting period, we have studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influences the performance of these materials in the Fischer-Tropsch synthesis. The resulting procedures have been optimized to improve further upon the already unprecedented rates and C{sub 5+} selectivities of the Fe-based catalysts that we have developed as part of this project. During this fifth reporting period, we have also continued our studies of optimal activation procedures, involving reduction and carburization of oxide precursors during the early stages of contact with synthesis gas. We have completed the analysis of the evolution of oxide, carbide, and metal phases of the active iron components during initial contact with synthesis gas using advanced synchrotron techniques based on X-ray absorption spectroscopy. We have confirmed that the Cu or Ru compensates for inhibitory effects of Zn, a

  16. Performance of Cobalt-Based Fischer-Tropsch Synthesis Catalysts Using Dielectric-Barrier Discharge Plasma as an Alternative to Thermal Calcination

    NASA Astrophysics Data System (ADS)

    Bai, Suli; Huang, Chengdu; Lv, Jing; Li, Zhenhua

    2012-01-01

    Co-based catalysts were prepared by using dielectric-barrier discharge (DBD) plasma as an alternative method to conventional thermal calcination. The characterization results of N2-physisorption, temperature programmed reduction (TPR), transmission electron microscope (TEM), and X-ray diffraction (XRD) indicated that the catalysts prepared by DBD plasma had a higher specific surface area, lower reduction temperature, smaller particle size and higher cobalt dispersion as compared to calcined catalysts. The DBD plasma method can prevent the sintering and aggregation of active particles on the support due to the decreased treatment time (0.5 h) at lower temperature compared to the longer thermal calcination at higher temperature (at 500° C for 5 h). As a result, the catalytic performance of the Fischer-Tropsch synthesis on DBD plasma treated Co/SiO2 catalyst showed an enhanced activity, C5+ selectivity and catalytic stability as compared to the conventional thermal calcined Co/SiO2 catalyst.

  17. A Facile Synthesis of SiO2@Co/mSiO2 Egg-Shell Nanoreactors for Fischer-Tropsch Reaction.

    PubMed

    Kwon, Jae In; Kim, Tae Wan; Park, Ji Chan; Yang, Jung-Il; Lee, Kwan Young

    2016-02-01

    Recently, a convenient melt-infiltration method, using a hydrated metal salt with porous support, was developed to prepare various metal/metal-oxide nanocatalysts. Until now, millimeter-scale, bead-shaped, cobalt egg-shell catalysts have been used to enhance the rate of reactant diffusion and catalyst performance. In the present work, new SiO2@Co/mSiO2 egg-shell nanoreactors (~300 nm) were synthesized with controlled Co content of 10 and 20 wt%. This was accomplished using a selective melt-infiltration process with porous silica shells around solid-silica cores. The SiO2@Co(10 wt%)/mSiO2 egg-shell catalyst that bears small cobalt nanoparticles of -2 nm was successfully employed for the industrially valuable Fischer-Tropsch synthesis reaction, showing the high activity of -8.0 x 10(-5) mol(CO) x gCo(-1) x S(-1).

  18. Fischer-Tropsch Catalysts

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Taylor, Jesse W. (Inventor)

    2008-01-01

    Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

  19. Enhancing the properties of Fischer-Tropsch fuel produced from syngas over Co/SiO2 catalyst: Lubricity and Calorific Value

    NASA Astrophysics Data System (ADS)

    Doustdar, O.; Wyszynski, M. L.; Mahmoudi, H.; Tsolakis, A.

    2016-09-01

    Bio-fuel produced from renewable sources is considered the most viable alternatives for the replacement of mineral diesel fuel in compression ignition engines. There are several options for biomass derived fuels production involving chemical, biological and thermochemical processes. One of the best options is Fischer Tropsch Synthesis, which has an extensive history of gasoline and diesel production from coal and natural gas. FTS fuel could be one of the best solutions to the fuel emission due to its high quality. FTS experiments were carried out in 16 different operation conditions. Mini structured vertical downdraft fixed bed reactor was used for the FTS. Instead of Biomass gasification, a simulated N2 -rich syngas cylinder of, 33% H2 and 50% N2 was used. FT fuels products were analyzed in GCMS to find the hydrocarbon distributions of FT fuel. Calorific value and lubricity of liquid FT product were measured and compared with commercial diesel fuel. Lubricity has become an important quality, particularly for biodiesel, due to higher pressures in new diesel fuel injection (DFI) technology which demands better lubrication from the fuel and calorific value which is amount of energy released in combustion paly very important role in CI engines. Results show that prepared FT fuel has desirable properties and it complies with standard values. FT samples lubricities as measured by ASTM D6079 standard vary from 286μm (HFRR scar diameter) to 417μm which are less than limit of 520μm. Net Calorific value for FT fuels vary from 9.89 MJ/kg to 43.29 MJ/kg, with six of the samples less than EN 14213 limit of 35MJ/kg. Effect of reaction condition on FT fuel properties was investigated which illustrates that in higher pressure Fischer-Tropsch reaction condition liquid product has better properties.

  20. The selective catalytic cracking of Fischer-Tropsch liquids to high value transportation fuels. Quarterly technical status report for first quarter fiscal year, 1994 - report No. 41, October 1, 1993--December 31, 1993

    SciTech Connect

    Schwartz, M.M.

    1995-01-01

    Amoco Oil Company, under a contract with the United States Department of Energy, is investigating a selective catalytic cracking process to convert the Fischer-Tropsch gasoline and wax fractions to high value transportation fuels. Characterization of the IBP-430, 430-650, and 650+ {degrees}F fractions of the three pilot plant runs that were made in August, 1993 was completed. Sasol wax was the feedstock for those runs. The catalysts used were 10% steamed USY, 10% steamed Beta, and standard equilibrium USY. A comparison of the economics for using Fischer-Tropsch wax as feedstock for hydrocracking versus catalytic cracking processes was performed. Hydrocracker values are similar to FCC product values for a simple refinery configuration (no Ether Unit). Hydrocracker values are less than FCC product values for a complex refinery configuration (contains Ether Unit). The work in this area is now complete.

  1. Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

    NASA Technical Reports Server (NTRS)

    Klettlinger, Jennifer Lindsey Suder

    2012-01-01

    The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the

  2. Relating rheological measurements to primary and secondary skin feeling when mineral-based and Fischer-Tropsch wax-based cosmetic emulsions and jellies are applied to the skin.

    PubMed

    Bekker, M; Webber, G V; Louw, N R

    2013-08-01

    Rheology measurements were correlated to skin sensations occurring when cream and petroleum jelly cosmetic products containing different amounts of synthetic Fischer-Tropsch wax were applied to the skin. A panel of 15 people with a background in cosmetic product development were asked to rate skin feelings when a range of petroleum jelly and cream samples are applied to the skin. Primary skin feel, or the spreadability of a cosmetic product, was correlated to the product's flow onset and maximum viscosity as measured by a Anton Paar rheometer, whereas secondary skin feel or the sensation occurring at the end of application when the product was completely rubbed into the skin was correlated to the product's viscosity measured at high shear rates. The cream samples prepared with a petroleum jelly containing 10% and 20% Fischer-Tropsch wax fell within the boundary of good primary skin feeling of cream products. Predominantly, synthetic petroleum jellies were given the best assessments in terms of primary skin feeling and were used with mineral-based petroleum jellies to determine the boundary of good primary skin feeling for petroleum jelly products. The further away a product falls from this rheological boundary the poorer the skin feeling assessment appears to be by the panel. Products containing Fischer-Tropsch waxes were given the best assessment by the panel for secondary skin feeling. Comments from the panel include that these products feel silky and light on the skin. The higher the Fischer-Tropsch wax content, the lower viscosity was at high shear rate (ϒ = 500 s(-1) ) and the higher the assessment by the panel. Rheological measurements can be used to objectively determine skin sensation when products are applied to the skin; this may shorten research and development times. A rheology boundary of certain product viscosity and shear stress applied is associated with good primary skin feeling for lotions, creams and petroleum jellies. Lower product viscosity

  3. Relating rheological measurements to primary and secondary skin feeling when mineral-based and Fischer-Tropsch wax-based cosmetic emulsions and jellies are applied to the skin.

    PubMed

    Bekker, M; Webber, G V; Louw, N R

    2013-08-01

    Rheology measurements were correlated to skin sensations occurring when cream and petroleum jelly cosmetic products containing different amounts of synthetic Fischer-Tropsch wax were applied to the skin. A panel of 15 people with a background in cosmetic product development were asked to rate skin feelings when a range of petroleum jelly and cream samples are applied to the skin. Primary skin feel, or the spreadability of a cosmetic product, was correlated to the product's flow onset and maximum viscosity as measured by a Anton Paar rheometer, whereas secondary skin feel or the sensation occurring at the end of application when the product was completely rubbed into the skin was correlated to the product's viscosity measured at high shear rates. The cream samples prepared with a petroleum jelly containing 10% and 20% Fischer-Tropsch wax fell within the boundary of good primary skin feeling of cream products. Predominantly, synthetic petroleum jellies were given the best assessments in terms of primary skin feeling and were used with mineral-based petroleum jellies to determine the boundary of good primary skin feeling for petroleum jelly products. The further away a product falls from this rheological boundary the poorer the skin feeling assessment appears to be by the panel. Products containing Fischer-Tropsch waxes were given the best assessment by the panel for secondary skin feeling. Comments from the panel include that these products feel silky and light on the skin. The higher the Fischer-Tropsch wax content, the lower viscosity was at high shear rate (ϒ = 500 s(-1) ) and the higher the assessment by the panel. Rheological measurements can be used to objectively determine skin sensation when products are applied to the skin; this may shorten research and development times. A rheology boundary of certain product viscosity and shear stress applied is associated with good primary skin feeling for lotions, creams and petroleum jellies. Lower product viscosity

  4. Long-term operation of biomass-to-liquid systems coupled to gasification and Fischer-Tropsch processes for biofuel production.

    PubMed

    Kim, Kwangsu; Kim, Youngdoo; Yang, Changwon; Moon, Jihong; Kim, Beomjong; Lee, Jeongwoo; Lee, Uendo; Lee, Seehoon; Kim, Jaeho; Eom, Wonhyun; Lee, Sangbong; Kang, Myungjin; Lee, Yunje

    2013-01-01

    Long-term operation of the biomass-to-liquid (BTL) process was conducted with a focus on the production of bio-syngas that satisfies the purity standards for the Fischer-Tropsch (FT) process. The integrated BTL system consisted of a bubbling fluidized bed (BFB) gasifier (20 kW(th)), gas cleaning unit, syngas compression unit, acid gas removing unit, and an FT reactor. Since the raw syngas from the gasifier contains different types of contaminants, such as particulates, condensable tars, and acid gases, which can cause various mechanical problems or deactivate the FT catalyst, the syngas was purified by passing through cyclones, a gravitational dust collector, a two-stage wet scrubber (packing-type), and a methanol absorption tower. The integrated system was operated for 500 h over several runs, and stable operating conditions for each component were achieved. The cleaned syngas contained no sulfur compounds (under 1 ppmV) and satisfied the requirements for the FT process.

  5. Performance characterization of CNTs and γ-Al{sub 2}O{sub 3} supported cobalt catalysts in Fischer-Tropsch reaction

    SciTech Connect

    Ali, Sardar; Zabidi, Noor Asmawati Mohd; Subbarao, Duvvuri

    2014-10-24

    Catalysts were prepared via a wet impregnation method. Different physicochemical properties of the samples were revealed by transmission electron microscope (TEM), temperature programmed reduction (H{sub 2}-TPR) and carbon dioxide desorption (CO{sub 2}-desorption). Fischer-Tropsch reaction (FTS) was carried out in a fixed-bed microreactor at 220°C and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12L/g.h for 5 h. Various characterization techniques revealed that there was a stronger interaction between Co and Al{sub 2}O{sub 3} support compared to that of CNTs support. CNTs support increased the reducibility and decreased Co particle size. A significant increase in % CO conversion and FTS reaction rate was observed over CNTs support compared to that of Co/Al{sub 2}O{sub 3}. Co/CNTs resulted in higher C{sub 5+} hydrocarbons selectivity compared to that of Co/Al{sub 2}O{sub 3} catalyst. CNTs are a better support for Co compared to Al{sub 2}O{sub 3}.

  6. Comparing a Fischer-Tropsch Alternate Fuel to JP-8 and Their 50-50 Blend: Flow and Flame Visualization Results

    NASA Technical Reports Server (NTRS)

    Hicks, Yolanda R.; Tacina, M.

    2013-01-01

    Combustion performance of a Fischer-Tropsch (FT) jet fuel manufactured by Sasol was compared to JP-8 and a 50-50 blend of the two fuels, using the NASA/Woodward 9 point Lean Direct Injector (LDI) in its baseline configuration. The baseline LDI configuration uses 60deg axial air-swirlers, whose vanes generate clockwise swirl, in the streamwise sense. For all cases, the fuel-air equivalence ratio was 0.455, and the combustor inlet pressure and pressure drop were 10-bar and 4 percent. The three inlet temperatures used were 828, 728, and 617 K. The objectives of this experiment were to visually compare JP-8 flames with FT flames for gross features. Specifically, we sought to ascertain in a simple way visible luminosity, sooting, and primary flame length of the FT compared to a standard JP grade fuel. We used color video imaging and high-speed imaging to achieve these goals. The flame color provided a way to qualitatively compare soot formation. The length of the luminous signal measured using the high speed camera allowed an assessment of primary flame length. It was determined that the shortest flames resulted from the FT fuel.

  7. Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

    SciTech Connect

    Sartipi, Sina E-mail: J.Gascon@tudelft.nl; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge E-mail: J.Gascon@tudelft.nl; Kapteijn, Freek

    2013-12-15

    Design and operation of a “six-flow fixed-bed microreactor” setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.

  8. [Emission characteristics of a diesel car fueled with coal based Fischer-Tropsch (F-T) diesel and fossil diesel blends].

    PubMed

    Hu, Zhi-Yuan; Cheng, Liang; Tan, Pi-Qiang; Lou, Di-Ming

    2012-11-01

    According to the first type test cycle of China national standard GB 18352.3-2005, the CO, NO(x), HC, PM and CO2 emission characteristics of a PASSAT diesel car fueled with Shanghai local IV diesel, coal based Fischer-Tropsch (F-T) diesel, and the blends of coal based F-T diesel and Shanghai local IV diesel up to 10% and 50% by volume were analyzed respectively. And the environmental impacts such as decreased air quality, health impact, photochemical ozone, global warming, and acidification that could be caused by CO, NO(x), HC, PM and CO2 emission of the diesel car were also assessed. The results showed that under GB 18352.3-2005 No. 1 test driving cycle, which consisted of four urban driving cycles and one extra urban driving cycle, the CO, HC, PM and CO2 emissions were released mainly in the urban driving cycles whereas the NO(x) emissions occurred mainly in the extra urban driving cycle. Compared with Shanghai local IV diesel, all of the CO, NO(x), HC, PM and CO2 emissions of the diesel car decreased to different extents when fueled with coal based F-T diesel blends. Moreover, the aerosol generation potential, global warming potential and acidification potential of F-T diesel fueled diesel car were also reduced. To sum up, coal based F-T diesel would be one of the alternative fuels to diesel in China. PMID:23323400

  9. [Emission characteristics of a diesel car fueled with coal based Fischer-Tropsch (F-T) diesel and fossil diesel blends].

    PubMed

    Hu, Zhi-Yuan; Cheng, Liang; Tan, Pi-Qiang; Lou, Di-Ming

    2012-11-01

    According to the first type test cycle of China national standard GB 18352.3-2005, the CO, NO(x), HC, PM and CO2 emission characteristics of a PASSAT diesel car fueled with Shanghai local IV diesel, coal based Fischer-Tropsch (F-T) diesel, and the blends of coal based F-T diesel and Shanghai local IV diesel up to 10% and 50% by volume were analyzed respectively. And the environmental impacts such as decreased air quality, health impact, photochemical ozone, global warming, and acidification that could be caused by CO, NO(x), HC, PM and CO2 emission of the diesel car were also assessed. The results showed that under GB 18352.3-2005 No. 1 test driving cycle, which consisted of four urban driving cycles and one extra urban driving cycle, the CO, HC, PM and CO2 emissions were released mainly in the urban driving cycles whereas the NO(x) emissions occurred mainly in the extra urban driving cycle. Compared with Shanghai local IV diesel, all of the CO, NO(x), HC, PM and CO2 emissions of the diesel car decreased to different extents when fueled with coal based F-T diesel blends. Moreover, the aerosol generation potential, global warming potential and acidification potential of F-T diesel fueled diesel car were also reduced. To sum up, coal based F-T diesel would be one of the alternative fuels to diesel in China.

  10. Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

    SciTech Connect

    Alptekin, Gokhan

    2013-02-15

    Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H2S, NH3, HCN, AsH3, PH3, HCl, NaCl, KCl, AS3, NH4NO3, NH4OH, KNO3, HBr, HF, and HNO3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

  11. Influence of gas feed composition and pressure on the catalytic conversion of CO{sub 2} to hydrocarbons using a traditional cobalt-based Fischer-Tropsch catalyst

    SciTech Connect

    Robert W. Dorner; Dennis R. Hardy; Frederick W. Williams; Burtron H. Davis; Heather D. Willauer

    2009-08-15

    The hydrogenation of CO{sub 2} using a traditional Fischer-Tropsch Co-Pt/Al{sub 2}O{sub 3} catalyst for the production of valuable hydrocarbon materials is investigated. The ability to direct product distribution was measured as a function of different feed gas ratios of H{sub 2} and CO{sub 2} (3:1, 2:1, and 1:1) as well as operating pressures (ranging from 450 to 150 psig). As the feed gas ratio was changed from 3:1 to 2:1 and 1:1, the production distribution shifted from methane toward higher chain hydrocarbons. This change in feed gas ratio is believed to lower the methanation ability of Co in favor of chain growth, with possibly two different active sites for methane and C2-C4 products. Furthermore, with decreasing pressure, the methane conversion drops slightly in favor of C{sub 2}-C{sub 4} paraffins. Even though under certain reaction conditions product distribution can be shifted slightly away from the formation of methane, the catalyst studied behaves like a methanation catalyst in the hydrogenation of CO{sub 2}. 36 refs., 2 figs., 4 tabs.

  12. Assessment of fuel-cycle energy use and greenhouse gas emissions for Fischer-Tropsch diesel from coal and cellulosic biomass.

    SciTech Connect

    Xie, X.; Wang, M.; Han, J.

    2011-04-01

    This study expands and uses the GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation) model to assess the effects of carbon capture and storage (CCS) technology and cellulosic biomass and coal cofeeding in Fischer-Tropsch (FT) plants on energy use and greenhouse gas (GHG) emissions of FT diesel (FTD). To demonstrate the influence of the coproduct credit methods on FTD life-cycle analysis (LCA) results, two allocation methods based on the energy value and the market revenue of different products and a hybrid method are employed. With the energy-based allocation method, fossil energy use of FTD is less than that of petroleum diesel, and GHG emissions of FTD could be close to zero or even less than zero with CCS when forest residue accounts for 55% or more of the total dry mass input to FTD plants. Without CCS, GHG emissions are reduced to a level equivalent to that from petroleum diesel plants when forest residue accounts for 61% of the total dry mass input. Moreover, we show that coproduct method selection is crucial for LCA results of FTD when a large amount of coproducts is produced.

  13. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress reports No. 7 and 8, April 1, 1991--September 30, 1991

    SciTech Connect

    Abrevaya, H.

    1991-12-31

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors. An experimental cobalt catalyst 585R2723 was tested three times in the fixed-bed reactor. The objective of the tests was to identify suitable testing conditions for screening catalyst. The {alpha}-alumina was determined to be a suitable diluent medium for controlling the catalyst bed temperature close to the inlet temperature. With 13 g of catalyst and 155 g of diluent, the catalyst maximum temperature were within 2{degree}C from the inlet temperatures. As a result of this work, 210{degree}C and 21 atm were shown to result in low methane selectivity and were used as initial conditions in the catalyst screening test. Ethane, which along with methane is undesirable, is typically produced with low selectivity and follows the same trend as methane. Other work reported here indicated that methane selectivity increases with increasing temperature but is not excessively high at 230{degree}C. Consequently, the catalyst screening test should include an evaluation of the catalyst performance at 230{degree}C. During Run 67, the increase in temperature from 210{degree}C to 230{degree}C was initiated at 30 hours on-stream.

  14. Toward a more comprehensive greenhouse gas emissions assessment of biofuels: the case of forest-based fischer-tropsch diesel production in Finland.

    PubMed

    Soimakallio, Sampo

    2014-01-01

    Increasing the use of biofuels influences atmospheric greenhouse gas concentrations. Although widely recognized, uncertainties related to the particular impacts are typically ignored or only partly considered. In this paper, various sources of uncertainty related to the GHG emission savings of biofuels are considered comprehensively and transparently through scenario analysis and stochastic simulation. Technology and feedstock production chain-specific factors, market-mediated factors and climate policy time frame issues are reflected using as a case study Fischer-Tropsch diesel derived from boreal forest biomass in Finland. This case study shows that the GHG emission savings may be positive or negative in many of the cases studied, and are subject to significant uncertainties, which are mainly determined by market-mediated factors related to fossil diesel substitution. Regardless of the considerable uncertainties, some robust conclusions could be drawn; it was likely of achieving some sort of but unlikely of achieving significant savings in the GHG emissions within the 100 year time frame in many cases. Logging residues (branches) performed better than stumps and living stem wood in terms of the GHG emission savings, which could be increased mainly by blocking carbon leakage. Forest carbon stock changes also significantly contributed to the GHG emission savings. PMID:24528291

  15. Separation of Fischer-Tropsch wax from catalyst using supercritical fluid extraction. Quarterly technical progress report, April 1, 1996--June 30, 1996

    SciTech Connect

    Joyce, P.C.; Thies, M.C.

    1996-11-01

    The objective of this research project is to evaluate the potential of SCF extraction for separating the catalyst slurry of a Fischer- Tropsch (F-T) slurry bubble column (SBC) reactor into two fractions: (1) a catalyst-free wax containing less than 10 ppm particulate matter and (2) a concentrated catalyst slurry that is ready for recycle or regeneration. The wax will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300{degrees}C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two major factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished without entraining the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds, i.e., a constant carbon-number distribution of the alkanes in the wax slurry must be maintained at steady-state column operation. To implement our objectives, the following task structure is being implemented: Task 1 equilibrium solubility measurements; Task 2 thermodynamic modeling; and Task 3 process design studies. Progress reports are presented for each task.

  16. Separation of Fischer-Tropsch wax from catalyst using supercritical fluid extraction. Quarterly technical progress report, 1 January 1996--31 March 1996

    SciTech Connect

    Joyce, P.C.; Thies, M.C.

    1996-09-01

    The objective of this research project is to evaluate the potential of supercritical fluid extraction for separating the catalyst slurry of a Fischer-Tropsch (F-T) slurry bubble column (SBC) reactor into two fractions: (1) a catalyst-free wax containing less than 10 ppm particulate matter and (2) a concentrated catalyst slurry that is ready for recycle or regeneration. The wax will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200--300 {degrees}C. Initial work is being performed using n-hexane as the solvent. The success of the project depends on two major factors. First, the supercritical solvent must be able to dissolve the F-T wax; furthermore, this must be accomplished without entraining the solid catalyst. Second, the extraction must be controlled so as not to favor the removal of the low molecular weight wax compounds, i.e., a constant carbon-number distribution of the alkanes in the wax slurry must be maintained at steady-state column operation. During this quarter work focused on task 1b, experimental measurement of selected model systems. Vapor-liquid equilibrium experiments for the n- hexane/squalane system, which we initiated in the previous quarter, were continued and results are discussed in this report.

  17. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System.

    PubMed

    Ferguson, Frank T; Johnson, Natasha M; Nuth, Joseph A

    2015-10-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the High-Resolution Transmission Molecular Absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

  18. Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

    PubMed

    Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

    2014-07-15

    Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

  19. Toward a more comprehensive greenhouse gas emissions assessment of biofuels: the case of forest-based fischer-tropsch diesel production in Finland.

    PubMed

    Soimakallio, Sampo

    2014-01-01

    Increasing the use of biofuels influences atmospheric greenhouse gas concentrations. Although widely recognized, uncertainties related to the particular impacts are typically ignored or only partly considered. In this paper, various sources of uncertainty related to the GHG emission savings of biofuels are considered comprehensively and transparently through scenario analysis and stochastic simulation. Technology and feedstock production chain-specific factors, market-mediated factors and climate policy time frame issues are reflected using as a case study Fischer-Tropsch diesel derived from boreal forest biomass in Finland. This case study shows that the GHG emission savings may be positive or negative in many of the cases studied, and are subject to significant uncertainties, which are mainly determined by market-mediated factors related to fossil diesel substitution. Regardless of the considerable uncertainties, some robust conclusions could be drawn; it was likely of achieving some sort of but unlikely of achieving significant savings in the GHG emissions within the 100 year time frame in many cases. Logging residues (branches) performed better than stumps and living stem wood in terms of the GHG emission savings, which could be increased mainly by blocking carbon leakage. Forest carbon stock changes also significantly contributed to the GHG emission savings.

  20. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

    NASA Technical Reports Server (NTRS)

    Ferguson, Frank T.; Johnson, Natasha M.; Nuth, Joseph A., III

    2015-01-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

  1. A Facile Synthesis of SiO2@Co/mSiO2 Egg-Shell Nanoreactors for Fischer-Tropsch Reaction.

    PubMed

    Kwon, Jae In; Kim, Tae Wan; Park, Ji Chan; Yang, Jung-Il; Lee, Kwan Young

    2016-02-01

    Recently, a convenient melt-infiltration method, using a hydrated metal salt with porous support, was developed to prepare various metal/metal-oxide nanocatalysts. Until now, millimeter-scale, bead-shaped, cobalt egg-shell catalysts have been used to enhance the rate of reactant diffusion and catalyst performance. In the present work, new SiO2@Co/mSiO2 egg-shell nanoreactors (~300 nm) were synthesized with controlled Co content of 10 and 20 wt%. This was accomplished using a selective melt-infiltration process with porous silica shells around solid-silica cores. The SiO2@Co(10 wt%)/mSiO2 egg-shell catalyst that bears small cobalt nanoparticles of -2 nm was successfully employed for the industrially valuable Fischer-Tropsch synthesis reaction, showing the high activity of -8.0 x 10(-5) mol(CO) x gCo(-1) x S(-1). PMID:27433671

  2. Six-flow operations for catalyst development in Fischer-Tropsch synthesis: bridging the gap between high-throughput experimentation and extensive product evaluation.

    PubMed

    Sartipi, Sina; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge; Kapteijn, Freek

    2013-12-01

    Design and operation of a "six-flow fixed-bed microreactor" setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors. PMID:24387446

  3. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System.

    PubMed

    Ferguson, Frank T; Johnson, Natasha M; Nuth, Joseph A

    2015-10-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the High-Resolution Transmission Molecular Absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments. PMID:26449809

  4. SLURRY PHASE IRON CATALYSTS FOR INDIRECT COAL LIQUEFACTION

    SciTech Connect

    Abhaya K. Datye

    1998-11-19

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, they have studied the attrition behavior of iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for converting coal based syngas into liquid fuels.

  5. Slurry Phase Iron Catalysts for Indirect Coal Liquefaction

    SciTech Connect

    Abhaya K. Datye

    1998-09-10

    This report describes research conducted to support the DOE program in indirect coal liquefaction. Specifically, we have studied the attrition behavior of Iron Fischer-Tropsch catalysts, their interaction with the silica binder and the evolution of iron phases in a synthesis gas conversion process. The results provide significant insight into factors that should be considered in the design of catalysts for the conversion of coal-derived synthesis gas into liquid fuels.

  6. Gaseous product mixture from Fischer-Tropsch synthesis as an efficient carbon feedstock for low temperature CVD growth of carbon nanotube carpets

    NASA Astrophysics Data System (ADS)

    Almkhelfe, Haider; Carpena-Núñez, Jennifer; Back, Tyson C.; Amama, Placidus B.

    2016-07-01

    Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst pretreatment and/or preheating of the carbon feedstock. The efficiency of the process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe-Cu catalysts even at temperatures as low as 400 °C - a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The grown CNTs exhibit a straight morphology with hollow interior and parallel graphitic planes along the tube walls. The apparent activation energies for CNT carpet growth on Fe and Fe-Cu catalysts are 0.71 and 0.54 eV, respectively. The synergistic effect of Fe and Cu show a strong dependence on the growth temperature, with Cu being more influential at temperatures higher than 450 °C. The low activation energies and long catalyst lifetimes observed are rationalized based on the unique composition of FTS-GP and Gibbs free energies for the decomposition reactions of the hydrocarbon components. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability.Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst

  7. Gaseous product mixture from Fischer-Tropsch synthesis as an efficient carbon feedstock for low temperature CVD growth of carbon nanotube carpets.

    PubMed

    Almkhelfe, Haider; Carpena-Núñez, Jennifer; Back, Tyson C; Amama, Placidus B

    2016-07-21

    Low-temperature chemical vapor deposition (CVD) growth of carbon nanotube (CNT) carpets from Fe and Fe-Cu catalysts using a gaseous product mixture from Fischer-Tropsch synthesis (FTS-GP) as a superior carbon feedstock is demonstrated. This growth approach addresses a persistent issue of obtaining thick CNT carpets on temperature-sensitive substrates at low temperatures using a non-plasma CVD approach without catalyst pretreatment and/or preheating of the carbon feedstock. The efficiency of the process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe-Cu catalysts even at temperatures as low as 400 °C - a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The grown CNTs exhibit a straight morphology with hollow interior and parallel graphitic planes along the tube walls. The apparent activation energies for CNT carpet growth on Fe and Fe-Cu catalysts are 0.71 and 0.54 eV, respectively. The synergistic effect of Fe and Cu show a strong dependence on the growth temperature, with Cu being more influential at temperatures higher than 450 °C. The low activation energies and long catalyst lifetimes observed are rationalized based on the unique composition of FTS-GP and Gibbs free energies for the decomposition reactions of the hydrocarbon components. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability.

  8. Quantification of trace O-containing compounds in GTL process samples via Fischer-Tropsch reaction by comprehensive two-dimensional gas chromatography/mass spectrometry.

    PubMed

    Fernandes, Daniella R; Pereira, Vinícius B; Stelzer, Karen T; Gomes, Alexandre O; Neto, Francisco R Aquino; Azevedo, Débora A

    2015-11-01

    Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was successfully applied to eight real Brazilian Fischer-Tropsch (FT) product samples for the quantitative analysis of O-containing compounds. It not only allowed identifying and quantifying simultaneously a large number of O-containing compounds but also resolved many co-eluting components, such as carboxylic acids, which co-elute in one-dimensional gas chromatography. The homologous series of alcohols and carboxylic acids as trimethylsilyl derivatives were detected and identified at trace levels. The absolute quantification of each compound was accomplished with reliability using analytical curves. Linear alcohols (from C5 to C19), branched alcohols (C6-C13) and carboxylic acids (C4 to C12) were obtained in the range of 1.58 mg g(-1) to 14.75 mg g(-1), 0.51 mg g(-1) to 1.12 mg g(-1) and 0.21 mg g(-1) to 1.63 mg g(-1) of FT product samples, respectively. GC×GC-TOFMS provided a linear range (from 0.3 ng µL(-1) to 10 ng µL(-1)), good precision (<8%), and excellent accuracy (recovery range of 77% to 118%) for quantification of individual O-containing compounds in FT product samples. The results can benefit the development of gas-to-liquid technologies from natural gas and guide the choice of an FT conversion process that generates clean products with higher added value.

  9. Separation of Fischer-Tropsch wax from catalyst using supercritical fluid extraction. Quarterly technical progress report, 1 October 1995--31 December 1995

    SciTech Connect

    Thies, M.C.; Joyce, P.C.

    1996-06-01

    The objective of this research project is to evaluate the potential of supercritical fluid (SCF) extraction for separating the catalyst slurry of a Fischer-Tropsch slurry bubble column (SBC) reactor into two fractions: (1) a catalyst-free wax containing less than 10 ppm particulate matter and (2) a concentrated catalyst slurry that is ready for recycle or regeneration. The wax will be extracted with a hydrocarbon solvent that has a critical temperature near the operating temperature of the SBC reactor, i.e., 200-300{degrees}C. Initial work is being performed using n-hexane as the solvent. During the reporting period, work on the small-scale, continuous-flow apparatus continued. Initial experiments have been performed on a binary mixture of n-hexane (solvent) and squalane (model compound) at 200{degrees}C. A total of fifteen samples were collected at 135, 160, and 208 psig, with pressures being controlled to within {plus_minus}2 psi. Results indicate that the equilibrium phase compositions can in principle be measured to a reproducibility of {plus_minus}0.5% in the squalane-rich bottomphase and {plus_minus}2% in the hexane-rich top phase, with respect to the minor component. However, other data measured at these same conditions at another time exhibited scatter that was as much as 5 times greater. We believe that improvements in (1) the method of preheating the feed to the view cell/phase separator and to (2) the sample collection technique are required before data of high accuracy can consistently be generated. The apparatus modifications required to effect these improvements are currently underway and should be completed by the middle of February.

  10. Influence of pH of the impregnation solution on the catalytic properties of Co/{gamma}-alumina for Fischer-Tropsch synthesis

    SciTech Connect

    Jong Wook Bae; Yun-Jo Lee; Jo-Yong Park; Ki-Won Jun

    2008-09-15

    The Co/{gamma}-Al{sub 2}O{sub 3} catalysts were prepared by the slurry impregnation of an aqueous solution of cobalt(II) nitrate precursor. Nitric acid or ammonium hydroxide was added to the cobalt nitrate solution, during impregnation, to give an acidic or basic environment. The changes in the particle size of cobalt species were estimated by X-ray diffraction (XRD) and hydrogen chemisorption. The reduction degree of cobalt oxides was measured by temperature-programmed reduction (TPR). The catalysts prepared under acidic conditions showed a higher reduction degree compared to those prepared at higher pH because of the reduced salt-support interaction. During the Fischer-Tropsch synthesis at 220{sup o}C, employing the catalysts prepared at a different pH (0.80, 4.94, 9.96, and 11.12), a considerable difference in the initial activity was observed, depending upon the cobalt metal surface area. However, after stabilization, all of the catalysts attained a similar level of conversion, possibly because of the active-site rearrangement, deactivation, and wax formation on the catalyst surface. At a higher reaction temperature of 240{sup o}C, the catalysts prepared at lower solution pH exhibited higher conversion than those prepared at higher solution pH. The cobalt species on the catalysts prepared under acidic conditions had a heterogeneous particle size distribution, showing higher steady-state activity, because of the reduced interaction with the support. The product distribution revealed a higher selectivity to C{sub 1} and C{sub 8+} on the catalyst prepared with a higher solution pH. 44 refs., 6 figs., 3 tabs.

  11. Fischer-Tropsch synthesis of hydrocarbons during sub-solidus alteration of the Strange Lake peralkaline granite, Quebec/Labrador, Canada

    SciTech Connect

    Salvi, S.; Williams-Jones, A.E.

    1997-01-01

    The composition of the carbonic phase(s) of fluid inclusions in pegmatite quartz from the Strange Lake peralkaline complex has been analysed by gas chromatography using online extraction of inclusion contents and a PoraPLOT{reg_sign} Q capillary column. The measured gas species are, in order of abundance, CH{sub 4} H{sub 2}, C{sub 2}H{sub 6}, CO{sub 2}, N{sub 2}, C{sub 3}H{sub 8}, n-C{sub 4}H{sub 10}, n-C{sub 5}H{sub 12}, C{sub 2}H{sub 2}-i-C{sub 4}H{sub 10}, and C{sub 2}H{sub 4}. Minor amounts of i-C{sub 5}H{sub 12}, n-C{sub 6}H{sub 14}, i-C{sub 6}H{sub 14}, and neo-C{sub 6}H{sub 14}, were also detected (but not quantified) in some samples. A suite of quartz samples from Ca-metasomatised pegmatites contains fluid inclusions with a similar distribution of hydrocarbons but much higher proportions of CO{sub 2}. The carbonic fluid coexisted immiscibly with a brine, which on the basis of field and petrographic evidence, was interpreted to have originated from the magma. However, thermodynamic calculations indicate that the above gas species, specifically the hydrocarbons, could not have coexisted at equilibrium in the proportions measured, at any geologically reasonable conditions either prior to or post entrapment. We propose, instead, that the gas compositions measured in the Strange Lake inclusions, and in inclusions from other alkalic complexes, resulted from the production of H{sub 2} during the alteration of arfvedsonite to aegirine, and the subsequent reaction of this H{sub 2} with orthomagmatic CO{sub 2} and CO to form hydrocarbons in a magnetite-catalysed Fischer-Tropsch synthesis. Locally, influx of an oxidised calcic brine, derived externally from the pluton, altered the original composition of the fluid by converting hydrocarbons to CO{sub 2}. 70 refs., 7 figs., 5 tabs.

  12. Poisoning of a silica supported cobalt catalyst due to the presence of sulfur impurities in syngas during Fischer-Tropsch synthesis: Effect of chelating agent

    SciTech Connect

    Bambal, A.S.; Gardner, T.H.; Kugler, E.L.; Dadyburjor, D.B.

    2012-01-01

    Sulfur compounds that are generally found in syngas derived from coal and biomass are a poison to Fischer-Tropsch (FT) catalysts. The presence of sulfur impurities in the ppm range can limit the life of a FT catalyst to a few hours or a few days. In this study, FT synthesis was carried out in a fixed-bed reactor at 230 °C, 20 bar, and 13,500 Ncm3/h/gcat for 72 h using syngas with H2/CO = 2.0. Cobalt-based catalysts were subjected to poisoning by 10 and 50 ppm sulfur in the syngas. The performance of FT catalyst was compared in context of syngas conversion, product selectivities and yields, during the poisoning as well as post-poisoning stages. At both the impurity concentrations, the sulfur was noted to cause permanent loss in the activity, possibly by adsorbing irreversibly on the surface. The sulfur poison affects the hydrogenation and the chain-propagation ability of the catalysts, and shifts the product selectivity towards short-chain hydrocarbons with higher percentages of olefins. Additional diffusion limitations caused due to sulfur poisoning are thought to alter the product selectivity. The shifts in product selectivities suggest that the sulfur decreases the ability of the catalyst to form C-C bonds to produce longer-chain hydrocarbons. The selective blocking of sulfur is thought to affect the hydrogenation ability on the catalyst, resulting in more olefins in the product after sulfur poisoning. The sulfur poisoning on the cobalt catalyst is expected to cause an increase in the number of sites responsible for WGS or to influence the Boudouard reaction, resulting in a higher CO2 selectivity. Both the sites responsible for CO adsorptions as well as the sites for chain growth are poisoned during the poisoning. Additionally, the performance of a base-case cobalt catalyst is compared with that of catalysts modified by chelating agents (CAs). The superior performance of CA-modified catalysts during sulfur poisoning is attributed to the presence of smaller

  13. Determination of the Effect of Coal/Biomass-Derived Syngas Contaminants on the Performance of Fischer-Tropsch and Water-Gas-Shift Catalysts

    SciTech Connect

    Trembly, Jason; Cooper, Matthew; Farmer, Justin; Turk, Brian; Gupta, Raghubir

    2010-12-31

    Today, nearly all liquid fuels and commodity chemicals are produced from non-renewable resources such as crude oil and natural gas. Because of increasing scrutiny of carbon dioxide (CO{sub 2}) emissions produced using traditional fossil-fuel resources, the utilization of alternative feedstocks for the production of power, hydrogen, value-added chemicals, and high-quality hydrocarbon fuels such as diesel and substitute natural gas (SNG) is critical to meeting the rapidly growing energy needs of modern society. Coal and biomass are particularly attractive as alternative feedstocks because of the abundant reserves of these resources worldwide. The strategy of co-gasification of coal/biomass (CB) mixtures to produce syngas for synthesis of Fischer-Tropsch (FT) fuels offers distinct advantages over gasification of either coal or biomass alone. Co-feeding coal with biomass offers the opportunity to exploit economies of scale that are difficult to achieve in biomass gasification, while the addition of biomass to the coal gasifier feed leverages proven coal gasification technology and allows CO{sub 2} credit benefits. Syngas generated from CB mixtures will have a unique contaminant composition because coal and biomass possess different concentrations and types of contaminants, and the final syngas composition is also strongly influenced by the gasification technology used. Syngas cleanup for gasification of CB mixtures will need to address this unique contaminant composition to support downstream processing and equipment. To investigate the impact of CB gasification on the production of transportation fuels by FT synthesis, RTI International conducted thermodynamic studies to identify trace contaminants that will react with water-gas-shift and FT catalysts and built several automated microreactor systems to investigate the effect of single components and the synergistic effects of multiple contaminants on water-gas-shift and FT catalyst performance. The contaminants

  14. Abiogenic Fischer-Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

    NASA Astrophysics Data System (ADS)

    Potter, Joanna; Rankin, Andrew H.; Treloar, Peter J.

    2004-08-01

    the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer-Tropsch type reactions involving an early CO 2-rich fluid and H 2 derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilı´maussaq, at temperatures between 400 and 500 °C.

  15. Fischer-Tropsch slurry phase process variations to understand wax formations: Quarterly report, July 1, 1987-September 30, 1987

    SciTech Connect

    Satterfield, C.N.

    1987-01-01

    The performance of a sample of Ruhrchemie catalyst is compared in an approximate fashion to that of a PETC precipitated Fe catalyst, Mobil low wax and high wax catalysts, Sasol fixed bed catalyst and C-73 fused magnetite catalyst. Results indicate that the Ruhrchemie catalyst has about one-third the activity of the other catalysts, and is much less active for the water gas shift. It shows a double ..cap alpha.. distribution, breaking at about C/sub 7/, ..cap alpha../sub 1/ = 0.68 and ..cap alpha../sub 2/ = 0.85. C/sub 12+/ formation was comparable to that from the PETC catalyst and the Mobil low wax catalyst, higher than that from C-73 and lower than that produced by Mobil high wax catalyst and in the Sasol fixed bed reactors. The effect of adding CO/sub 2/ during synthesis on a C-73 magnetite catalyst has been studied. CO/sub 2/ forms H/sub 2/O by the reverse water gas shift and the kinetics observed can be attributed to the H/sub 2/O formation. The effects on product selectivity also seem to be mostly attributable to the H/sub 2/O formed. 6 figs., 3 tabs.

  16. KINETIC MODELING OF A FISCHER-TROPSCH REACTION OVER A COBALT CATALYST IN A SLURRY BUBBLE COLUMN REACTOR FOR INCORPORATION INTO A COMPUTATIONAL MULTIPHASE FLUID DYNAMICS MODEL

    SciTech Connect

    Anastasia Gribik; Doona Guillen, PhD; Daniel Ginosar, PhD

    2008-09-01

    Currently multi-tubular fixed bed reactors, fluidized bed reactors, and slurry bubble column reactors (SBCRs) are used in commercial Fischer Tropsch (FT) synthesis. There are a number of advantages of the SBCR compared to fixed and fluidized bed reactors. The main advantage of the SBCR is that temperature control and heat recovery are more easily achieved. The SBCR is a multiphase chemical reactor where a synthesis gas, comprised mainly of H2 and CO, is bubbled through a liquid hydrocarbon wax containing solid catalyst particles to produce specialty chemicals, lubricants, or fuels. The FT synthesis reaction is the polymerization of methylene groups [-(CH2)-] forming mainly linear alkanes and alkenes, ranging from methane to high molecular weight waxes. The Idaho National Laboratory is developing a computational multiphase fluid dynamics (CMFD) model of the FT process in a SBCR. This paper discusses the incorporation of absorption and reaction kinetics into the current hydrodynamic model. A phased approach for incorporation of the reaction kinetics into a CMFD model is presented here. Initially, a simple kinetic model is coupled to the hydrodynamic model, with increasing levels of complexity added in stages. The first phase of the model includes incorporation of the absorption of gas species from both large and small bubbles into the bulk liquid phase. The driving force for the gas across the gas liquid interface into the bulk liquid is dependent upon the interfacial gas concentration in both small and large bubbles. However, because it is difficult to measure the concentration at the gas-liquid interface, coefficients for convective mass transfer have been developed for the overall driving force between the bulk concentrations in the gas and liquid phases. It is assumed that there are no temperature effects from mass transfer of the gas phases to the bulk liquid phase, since there are only small amounts of dissolved gas in the liquid phase. The product from the

  17. Precipitation of iron in multicrystalline silicon during annealing

    NASA Astrophysics Data System (ADS)

    Liu, A. Y.; Macdonald, Daniel

    2014-03-01

    In this paper, the precipitation kinetics of iron in multicrystalline silicon during moderate temperature annealing are systematically studied with respect to annealing time, temperature, iron super-saturation level, and different types and densities of precipitation sites. The quantitative analysis is based on examining the changes in the concentrations and distributions of interstitial iron in multicrystalline silicon wafers after annealing at 400-700 °C. This is achieved by using the photoluminescence imaging technique to produce high-resolution spatially resolved images of the interstitial iron concentrations. The concentrations of interstitial iron are found to decrease exponentially with the annealing time. Comparison of the precipitation time constants of wafers annealed at different temperatures and of different initial interstitial iron concentrations indicates that higher levels of iron super-saturation result in faster precipitation processes. The impact of iron super-saturation on the precipitation kinetics becomes increasingly important at low levels of super-saturation, while its impact saturates at very high levels of super-saturation (above 1000). Some grain boundaries are shown to act as effective precipitation sites for iron during annealing, and the reduction in the interstitial iron concentrations in the intra-grain regions is found to be mainly due to precipitation at dislocations. Some important differences between the iron precipitation behaviour at the grain boundaries and at the intra-grain dislocations are discussed. The effect of hydrogenation of the multicrystalline silicon wafers on the apparent iron precipitation rate is also presented and discussed.

  18. DESIGN, SYNTHESIS, AND MECHANISTIC EVALUATION OF IRON-BASED CATALYSIS FOR SYNTHESIS GAS CONVERSION TO FUELS AND CHEMICALS

    SciTech Connect

    Jian Xu; Enrique Iglesia

    2004-03-31

    This project explores the extension of previously discovered Fe-based catalysts with unprecedented Fischer-Tropsch synthesis rate, selectivity, and ability to convert hydrogen-poor synthesis gas streams typical of those produced from coal and biomass sources. Contract negotiations between the U.S. Department of Energy and the University of California were completed on December 9, 2004. During this first reporting period, we have modified and certified a previously decommissioned microreactor, ordered and installed a budgeted gas chromatograph, developed and reviewed safe operating procedures and data analysis methods, and reproduced successfully previous synthetic protocols and catalytic performance of catalytic materials based on Fe-Zn-Cu-K oxide precursors synthesized using precipitation methods, drying using surface-active agents, and activated in synthesis gas within Fischer-Tropsch synthesis tubular reactors.

  19. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed Central

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  20. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed

    Sainna, Mala A; de Visser, Sam P

    2015-09-28

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)₂(μ²-H) (μ²-NHCH₃)(μ³-C)PtCH₃(P(CH₃)₃)₂](CO)n⁺ with n=0, 2 and Cp=η⁵-C₅(CH₃)₅, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes.

  1. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed

    Sainna, Mala A; de Visser, Sam P

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)₂(μ²-H) (μ²-NHCH₃)(μ³-C)PtCH₃(P(CH₃)₃)₂](CO)n⁺ with n=0, 2 and Cp=η⁵-C₅(CH₃)₅, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  2. Precipitated iron: A limit on gettering efficacy in multicrystalline silicon

    NASA Astrophysics Data System (ADS)

    Fenning, D. P.; Hofstetter, J.; Bertoni, M. I.; Coletti, G.; Lai, B.; del Cañizo, C.; Buonassisi, T.

    2013-01-01

    A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

  3. Technology development for iron Fischer-Tropsch catalysts, September 30, 1991. Technical progress report for quarterly period ending September 30, 1991

    SciTech Connect

    Davis, B.H.

    1991-12-31

    Although the oxidation process of Fe(OH){sub 2} and the mechanism of formation of {gamma}-FeOOH have been studied by several groups, many questions still need to be answered. In addition, the procedure for the synthesis of pure {gamma}-FeOOH has not been well defined. This study is to an attempt to define better the chemistry associated with oxidizing Fe{sup 2+} to {gamma}-FeOOH, and to provide a rationale for scaling this method up to produce kg/hr amounts of {gamma}-FeOOH.

  4. Promotion and nucleation of carbonate precipitation during microbial iron reduction.

    PubMed

    Zeng, Z; Tice, M M

    2014-07-01

    Iron-bearing early diagenetic carbonate cements are common in sedimentary rocks, where they are thought to be associated with microbial iron reduction. However, little is yet known about how local environments around actively iron-reducing cells affect carbonate mineral precipitation rates and compositions. Precipitation experiments with the iron-reducing bacterium Shewanella oneidensis MR-1 were conducted to examine the potential role of cells in promoting precipitation and to explore the possible range of precipitate compositions generated in varying fluid compositions. Actively iron-reducing cells induced increased carbonate mineral saturation and nucleated precipitation on their poles. However, precipitation only occurred when calcium was present in solution, suggesting that cell surfaces lowered local ferrous iron concentrations by adsorption or intracellular iron oxide precipitation even as they locally raised pH. Resultant precipitates were a range of thermodynamically unstable calcium-rich siderites that would likely act as precursors to siderite, calcite, or even dolomite in nature. By modifying local pH, providing nucleation sites, and altering metal ion concentrations around cell surfaces, iron-reducing micro-organisms could produce a wide range of carbonate cements in natural sediments. PMID:24862734

  5. Promotion and nucleation of carbonate precipitation during microbial iron reduction.

    PubMed

    Zeng, Z; Tice, M M

    2014-07-01

    Iron-bearing early diagenetic carbonate cements are common in sedimentary rocks, where they are thought to be associated with microbial iron reduction. However, little is yet known about how local environments around actively iron-reducing cells affect carbonate mineral precipitation rates and compositions. Precipitation experiments with the iron-reducing bacterium Shewanella oneidensis MR-1 were conducted to examine the potential role of cells in promoting precipitation and to explore the possible range of precipitate compositions generated in varying fluid compositions. Actively iron-reducing cells induced increased carbonate mineral saturation and nucleated precipitation on their poles. However, precipitation only occurred when calcium was present in solution, suggesting that cell surfaces lowered local ferrous iron concentrations by adsorption or intracellular iron oxide precipitation even as they locally raised pH. Resultant precipitates were a range of thermodynamically unstable calcium-rich siderites that would likely act as precursors to siderite, calcite, or even dolomite in nature. By modifying local pH, providing nucleation sites, and altering metal ion concentrations around cell surfaces, iron-reducing micro-organisms could produce a wide range of carbonate cements in natural sediments.

  6. Analysis of iron oxide precipitates in constructed mine wastewater treatments

    SciTech Connect

    Partezana, J.M.

    1996-10-01

    The purpose or this research project is to characterize iron oxide precipitates collected from abandoned mine drainage (AMD) treatment facilities in order to determine whether these precipitates have possible commercial value. The treatment facilities use constructed wetlands to raise pH levels to near neutral levels and to remove iron and other heavy metals from AMD polluted water. The main commercial value of interest is in the use of pigments in products such as paints, clay and brick. The precipitates arc characterized for composition and quality against natural and synthetic commercial pigment products. Various processing techniques were developed for sample preparation. Analysis tests include: general pigment tests, heavy metals, anions, particle size, and particle composition. Results show that the iron oxide precipitates are chemically similar to the commercial iron oxide but will require additional processing to meet pigment qualifications.

  7. Precipitation of iron minerals by a natural microbial consortium

    SciTech Connect

    Brown, D.A.; Sherriff, B.L.; Sparling, R.; Sawicki, J.A.

    1999-08-01

    A microbial biofilm consortium enriched from Shield surface water is able to mediate geochemical cycling of iron within a biofilm. Iron can be leached from Fe(II) containing minerals such as magnetite, biotite and ilmenite to generate a colloidal Fe(III) suspension. The Fe(III) can then be reduced back to Fe(II) by iron-reducing bacteria that utilize it as an electron acceptor. On precipitation, different iron compounds are formed depending on the ratio of iron to carbon in the media and upon the local environment. Moessbauer and X-ray diffraction spectroscopy show these compounds to include ferrous hydroxide, vivianite, ferrihydrite and hematite. These minerals may then become incorporated into stratifer iron deposits such as Banded Iron Formations.

  8. Precipitation Of Iron Minerals In Porous Media

    NASA Astrophysics Data System (ADS)

    Grover, D.; Baham, J. E.; Dragila, M. I.

    2007-12-01

    Formation of soil redoximorphic features, such as mottles, concretions and placic horizons is governed by Fe (II) and oxygen transport in porous media. We have conducted column experiments with four grades of silica sand that were placed vertically in the reduced saturated soil. Two sets of iron bands appeared within one week. Red oxidized bands (ferrihydrite and/or possibly lepidocrocite) were formed at the upper extent of the capillary fringe. Whereas, black bands (magnetite and/or green rust) were formed below the oxidized iron bands. These bands were transformed to the red bands as the experiment progressed. We propose a conceptual mechanistic framework for abiotic band formation and have developed a numerical model that incorporates the relevant factors contributing to the abiotic genesis of iron bands. This study reveals that abiotic iron oxide formation in unsaturated media is mainly a diffusion controlled process. The position of iron oxide bands is regulated by the diffusion rates of Fe (II) (aq) and Oxygen (g); thus elucidating the role of air-water and water-mineral interfacial properties, and diffusion gradients on iron transformations in natural systems. Our results suggest that the formation of Fe (III) oxide cemented bands in unsaturated hydrological systems is a rapid process occurring on a time scale relevant to human activity.

  9. Extracellular iron-sulfur precipitates from growth of Desulfovibrio desulfuricans

    SciTech Connect

    Antonio, M. R.; Tischler, M. L.; Witzcak, D.

    1999-12-20

    The authors have examined extracellular iron-bearing precipitates resulting from the growth of Desulfovibrio desulfuricans in a basal medium with lactate as the carbon source and ferrous sulfate. Black precipitates were obtained when D. desulfuricans was grown with an excess of FeSO{sub 4}. When D. desulfuricans was grown under conditions with low amounts of FeSO{sub 4}, brown precipitates were obtained. The precipitates were characterized by iron K-edge XAFS (X-ray absorption fine structure), {sup 57}Fe Moessbauer-effect spectroscopy, and powder X-ray diffraction. Both were noncrystalline and nonmagnetic (at room temperature) solids containing high-spin Fe(III). The spectroscopic data for the black precipitates indicate the formation of an iron-sulfur phase with 6 nearest S neighbors about Fe at an average distance of 2.24(1) {angstrom}, whereas the brown precipitates are an iron-oxygen-sulfur phase with 6 nearest O neighbors about Fe at an average distance of 1.95(1) {angstrom}.

  10. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Enrique Iglesia; Akio Ishikawa; Manual Ojeda; Nan Yao

    2007-09-30

    ) structural evolution of Fe-Zn oxide promoted with K and Cu, and (ii) evaluation of hydrocarbon and CH{sub 4} formation rates during activation procedures at various temperature and H{sub 2}/CO ratios. On the basis of the obtained results, we suggest that lower reactor temperature can be sufficient to activate catalysts and lead to the high FTS performance. In this project, we have also carried out a detailed kinetic and mechanistic study of the Fischer-Tropsch Synthesis with Fe-based catalysts. We have proposed a reaction mechanism with two CO activation pathways: unassisted and H-assisted. Both routes lead to the formation of the same surface monomers (CH{sub 2}). However, the oxygen removal mechanism is different. In the H-assisted route, oxygen is removed exclusively as water, while oxygen is rejected as carbon dioxide in the unassisted CO dissociation. The validity of the mechanism here proposed has been found to be in agreement with the experimental observation and with theoretical calculations over a Fe(110) surface. Also, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that the use of D{sub 2} instead of H{sub 2} leads to higher hydrocarbons formation rates (inverse kinetic isotopic effect). On the contrary, primary carbon dioxide formation is not influenced. These experimental observations can be explained by two CO activation pathways. We have also explored the catalytic performance of Co-based catalysts prepared by using inverse micelles techniques. We have studied several methods in order to terminate the silanol groups on SiO{sub 2} support including impregnation, urea homogeneous deposition-precipitation, or zirconium (IV) ethoxide titration. Although hydroxyl groups on the SiO{sub 2} surface are difficult to be stoichiometrically titrated by ZrO{sub 2}, a requirement to

  11. Fischer-Tropsch Slurry Reactor modeling

    SciTech Connect

    Soong, Y.; Gamwo, I.K.; Harke, F.W.

    1995-12-31

    This paper reports experimental and theoretical results on hydrodynamic studies. The experiments were conducted in a hot-pressurized Slurry-Bubble Column Reactor (SBCR). It includes experimental results of Drakeol-10 oil/nitrogen/glass beads hydrodynamic study and the development of an ultrasonic technique for measuring solids concentration. A model to describe the flow behavior in reactors was developed. The hydrodynamic properties in a 10.16 cm diameter bubble column with a perforated-plate gas distributor were studied at pressures ranging from 0.1 to 1.36 MPa, and at temperatures from 20 to 200{degrees}C, using a dual hot-wire probe with nitrogen, glass beads, and Drakeol-10 oil as the gas, solid, and liquid phase, respectively. It was found that the addition of 20 oil wt% glass beads in the system has a slight effect on the average gas holdup and bubble size. A well-posed three-dimensional model for bed dynamics was developed from an ill-posed model. The new model has computed solid holdup distributions consistent with experimental observations with no artificial {open_quotes}fountain{close_quotes} as predicted by the earlier model. The model can be applied to a variety of multiphase flows of practical interest. An ultrasonic technique is being developed to measure solids concentration in a three-phase slurry reactor. Preliminary measurements have been made on slurries consisting of molten paraffin wax, glass beads, and nitrogen bubbles at 180 {degrees}C and 0.1 MPa. The data show that both the sound speed and attenuation are well-defined functions of both the solid and gas concentrations in the slurries. The results suggest possibilities to directly measure solids concentration during the operation of an autoclave reactor containing molten wax.

  12. Improved Fischer-Tropsch Slurry Reactors

    SciTech Connect

    Andrew Lucero

    2009-03-20

    The conversion of synthesis gas to hydrocarbons or alcohols involves highly exothermic reactions. Temperature control is a critical issue in these reactors for a number of reasons. Runaway reactions can be a serious safety issue, even raising the possibility of an explosion. Catalyst deactivation rates tend to increase with temperature, particularly of there are hot spots in the reactor. For alcohol synthesis, temperature control is essential because it has a large effect on the selectivity of the catalysts toward desired products. For example, for molybdenum disulfide catalysts unwanted side products such as methane, ethane, and propane are produced in much greater quantities if the temperature increases outside an ideal range. Slurry reactors are widely regarded as an efficient design for these reactions. In a slurry reactor a solid catalyst is suspended in an inert hydrocarbon liquid, synthesis gas is sparged into the bottom of the reactor, un-reacted synthesis gas and light boiling range products are removed as a gas stream, and heavy boiling range products are removed as a liquid stream. This configuration has several positive effects for synthesis gas reactions including: essentially isothermal operation, small catalyst particles to reduce heat and mass transfer effects, capability to remove heat rapidly through liquid vaporization, and improved flexibility on catalyst design through physical mixtures in addition to use of compositions that cannot be pelletized. Disadvantages include additional mass transfer resistance, potential for significant back-mixing on both the liquid and gas phases, and bubble coalescence. In 2001 a multiyear project was proposed to develop improved FT slurry reactors. The planned focus of the work was to improve the reactors by improving mass transfer while considering heat transfer issues. During the first year of the project the work was started and several concepts were developed to prepare for bench-scale testing. PowerEnerCat was unable to raise their cash contribution for the project, and the work was stopped. This report summarizes some of the progress of the project and the concepts that were intended for experimental tests.

  13. Moderated ruthenium Fischer-Tropsch synthesis catalyst

    SciTech Connect

    Abrevaya, H.

    1991-10-22

    This patent describes a catalyst useful for producing C{sub 3}-hydrocarbons from hydrogen and carbon monoxide. It comprises an inorganic oxide support; about 0.3-6.0 wt. percent ruthenium present as particles of about 40-60 Angstroms and about 0.1-5.0 wt. % of a modifier component chosen from the group consisting of aluminum, silicon, lead, arsenic, and bismuth.

  14. Precipitation-strengthening effects in iron-aluminides

    SciTech Connect

    Maziasz, P.J.; McKamey, C.G.; Goodwin, G.M.

    1995-05-01

    The purpose of this work is to produce precipitation to improve both high-temperature strength and room-temperature ductibility in FeAl-type(B2 phase) iron-aluminides. Previous work has focused on primarily wrought products, but stable precipitates can also refine the grain size and affect the properties of as-cast and/or welded material as well. New work began in FY 1994 on the properties of these weldable, strong FeAl alloys in the as-cast condition. Because the end product of this project is components for industry testing, simpler and better (cheaper, near-net-shape) processing methods must be developed for industrial applications of FeAl alloys.

  15. Interactions of hydrogen with the iron and iron carbide interfaces: a ReaxFF molecular dynamics study.

    PubMed

    Islam, Md Mahbubul; Zou, Chenyu; van Duin, Adri C T; Raman, Sumathy

    2016-01-14

    Hydrogen embrittlement (HE) is a well-known material phenomenon that causes significant loss in the mechanical strength of structural iron and often leads to catastrophic failures. In order to provide a detailed atomistic description of HE we have used a reactive bond order potential to adequately describe the diffusion of hydrogen as well as its chemical interaction with other hydrogen atoms, defects, and the host metal. The currently published ReaxFF force field for Fe/C/H systems was originally developed to describe Fischer-Tropsch (FT) catalysis [C. Zou, A. C. T. van Duin and D. C. Sorescu, Top. Catal., 2012, 55, 391-401], and especially had been trained for surface formation energies, binding energies of small hydrocarbon radicals on different surfaces of iron and the barrier heights of surface reactions. We merged this force field with the latest ReaxFF carbon parameters [S. Goverapet Srinivasan, A. C. T. van Duin and P. Ganesh, J. Phys. Chem. A, 2015, 119, 1089-5639] and used the same training data set to refit the Fe/C interaction parameters. The present work is focused on evaluating the applicability of this reactive force field to describe material characteristics and study the role of defects and impurities in the bulk and at the precipitator interfaces. We study the interactions of hydrogen with pure and defective α-iron (ferrite), Fe3C (cementite), and ferrite-cementite interfaces with a vacancy cluster. We also investigate the growth of nanovoids in α-iron using a grand canonical Monte Carlo (GCMC) scheme. The calculated hydrogen diffusion coefficients for both ferrite and cementite phases predict a decrease in the work of separation with increasing hydrogen concentration at the ferrite-cementite interface, suggesting a hydrogen-induced decohesion behavior. Hydrogen accumulation at the interface was observed during molecular dynamics (MD) simulations, which is consistent with experimental findings. These results demonstrate the ability of the Reax

  16. DESIGN, SYNTHESIS, AND MECHANISTIC EVALUATION OF IRON-BASED CATALYSIS FOR SYNTHESIS GAS CONVERSION TO FUELS AND CHEMICALS

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Enrique Iglesia

    2005-03-31

    This project explores the extension of previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have previously shown unprecedented Fischer-Tropsch synthesis rate, selectivity with synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic performance previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During this third reporting period, we have prepared a large number of Fe-based catalyst compositions using precipitation and impregnations methods with both supercritical and subcritical drying and with the systematic use of surface active agents to prevent pore collapse during drying steps required in synthetic protocols. These samples were characterized during this period using X-ray diffraction, surface area, and temperature-programmed reduction measurements. These studies have shown that these synthesis methods lead to even higher surface areas than in our previous studies and confirm the crystalline structures of these materials and their reactivity in both oxide-carbide interconversions and in Fischer-Tropsch synthesis catalysis. Fischer-Tropsch synthesis reaction rates and selectivities with low H{sub 2}/CO ratio feeds (H{sub 2}/CO = 1) were the highest reported in the literature at the low-temperature and relatively low pressure in our measurements. Current studies are exploring the optimization of the sequence of impregnation of Cu, K, and Ru promoters, of the activation and reaction conditions, and of the co-addition of light hydrocarbons to increase diffusion rates of primary olefin products so as to increase the selectivity to unsaturated products. Finally, we are also addressing

  17. Slurry Phase Iron Catalysts for Indirect Coal LIquefaction.

    SciTech Connect

    Datye, A.K.

    1997-08-08

    This report covers the fourth six month period of this three year grant under the University Coal Research program. During this period, we have begun the synthesis of precipitated catalysts using a bench-top spray dryer. The influence of binders on particle strength was also studied using the ultrasonic fragmentation approach to derive particle breaking stress. A similar approach was used to derive particle strength of catalysts obtained from Mr. Robert Gormley at FETC. Over the next six month period, this work will be continued while the catalysts prepared here will be examined by TPR to determine reducibility and the extent of adverse iron-silica interactions. A fundamental study of Fe/silica interactions has been performed using temperature programmed reaction and TEM to provide understanding of how the silica binders influence the activity of Fe catalysts. To understand differences in the reducibility of the iron phase caused by silica, we have set up a temperature programmed reduction facility. TPR in H, as well as in CO was performed of Fe/ SiO, catalysts prepared by impregnation as well as by precipitation. What is unique about these studies is that high resolution TEM was performed on samples removed from the reactor at various stages of reduction. This helps provide direct evidence for the phase changes that are detected by TPR. We have continued the analysis of catalysts received from slurry reactor runs at Texas A&M university (TAMU) and the University of Kentucky Center for Applied Energy Research (CAER) by x-ray diffraction. The purpose of the XRD analysis was to determine the phase composition of catalysts derived from a slurry reaction run using Fe Fischer-Tropsch catalysts. We had previously described how catalyst removed in the hot wax may oxidize to magnetite if the wax is air-exposed. We have now received catalysts from CAER that were removed under a protective inert blanket, and we are in the process of analyzing them, but preliminary work

  18. Diffusion and precipitation processes in iron-based silica gardens.

    PubMed

    Glaab, F; Rieder, J; García-Ruiz, J M; Kunz, W; Kellermeier, M

    2016-09-28

    Silica gardens are tubular structures that form along the interface of multivalent metal salts and alkaline solutions of sodium silicate, driven by a complex interplay of osmotic and buoyant forces together with chemical reaction. They display peculiar plant-like morphologies and thus can be considered as one of the few examples for the spontaneous biomimetic self-ordering of purely inorganic materials. Recently, we could show that silica gardens moreover are highly dynamic systems that remain far from equilibrium for considerable periods of time long after macroscopic growth is completed. Due to initial compartmentalisation, drastic concentration gradients were found to exist across the tube walls, which give rise to noticeable electrochemical potential differences and decay only slowly in a series of coupled diffusion and precipitation processes. In the present work, we extend these studies and investigate the effect of the nature of the used metal cations on the dynamic behaviour of the system. To that end, we have grown single macroscopic silica garden tubes by controlled addition of sodium silicate sol to pellets of iron(ii) and iron(iii) chloride. In the following, the concentrations of ionic species were measured as a function of time on both sides of the formed membranes, while electrochemical potentials and pH were monitored online by immersing the corresponding sensors into the two separated solution reservoirs. At the end of the experiments, the solid tube material was furthermore characterised with respect to composition and microstructure by a combination of ex situ techniques. The collected data are compared to the previously reported case of cobalt-based silica gardens and used to shed light on ion diffusion through the inorganic membranes as well as progressive mineralisation at both surfaces of the tube walls. Our results reveal important differences in the dynamics of the three studied systems, which can be explained based on the acidity of the

  19. Diffusion and precipitation processes in iron-based silica gardens.

    PubMed

    Glaab, F; Rieder, J; García-Ruiz, J M; Kunz, W; Kellermeier, M

    2016-09-28

    Silica gardens are tubular structures that form along the interface of multivalent metal salts and alkaline solutions of sodium silicate, driven by a complex interplay of osmotic and buoyant forces together with chemical reaction. They display peculiar plant-like morphologies and thus can be considered as one of the few examples for the spontaneous biomimetic self-ordering of purely inorganic materials. Recently, we could show that silica gardens moreover are highly dynamic systems that remain far from equilibrium for considerable periods of time long after macroscopic growth is completed. Due to initial compartmentalisation, drastic concentration gradients were found to exist across the tube walls, which give rise to noticeable electrochemical potential differences and decay only slowly in a series of coupled diffusion and precipitation processes. In the present work, we extend these studies and investigate the effect of the nature of the used metal cations on the dynamic behaviour of the system. To that end, we have grown single macroscopic silica garden tubes by controlled addition of sodium silicate sol to pellets of iron(ii) and iron(iii) chloride. In the following, the concentrations of ionic species were measured as a function of time on both sides of the formed membranes, while electrochemical potentials and pH were monitored online by immersing the corresponding sensors into the two separated solution reservoirs. At the end of the experiments, the solid tube material was furthermore characterised with respect to composition and microstructure by a combination of ex situ techniques. The collected data are compared to the previously reported case of cobalt-based silica gardens and used to shed light on ion diffusion through the inorganic membranes as well as progressive mineralisation at both surfaces of the tube walls. Our results reveal important differences in the dynamics of the three studied systems, which can be explained based on the acidity of the

  20. Design, Synthesis and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Nan Yao; Enrique Iglesia

    2007-03-31

    This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based materials with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth and sixth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials during the sixth reporting period. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. Finally, we also started a study of the use of colloidal precipitation methods for the synthesis small Co clusters using recently developed methods to explore possible further improvements in FTS rates and selectivities. We found that colloidal synthesis makes possible the preparation of small cobalt particles, although large amount of cobalt silicate species, which are difficult to reduce, were formed. During this

  1. Iron isotope fractionation by microbial iron reduction in modern chemically precipitated sediments

    NASA Astrophysics Data System (ADS)

    Roden, E. E.; Tangalos, G. E.; Beard, B. L.; Johnson, C. M.; Alpers, C. N.; Shelobolina, E. S.; Xu, H.; Konishi, H.

    2008-12-01

    Laboratory experiments have demonstrated that dissimilatory microbial iron oxide reduction (DIR) can produce Fe(II) phases that have low 56Fe/54Fe ratios similar to those found in Neoarchean and Paleoproterozoic banded iron formations (BIFs) and shales. Direct application of these experiments to BIF formation has been hindered by the lack of Fe isotope data from modern environments that are analogous to BIFs. Here we report Fe inventories and isotopic compositions for chemically precipitated sediments in the Spring Creek Arm of Keswick Reservoir (SCAKR) downstream of the Iron Mountain acid mine drainage site in northern California, USA. The high concentration of reactive Fe(III) (ca. 50-100 mmol of amorphous Fe(III) oxyhydroxides per liter of bulk sediment) allows dissimilatory iron-reducing bacteria (DIRB) to predominate over dissimilatory sulfate-reducing bacteria in sediment carbon metabolism, making the SCAKR a better analog for BIFs compared to modern marine environments. DIR has generated millimolar concentrations of aqueous Fe(II) (Fe(II)aq) in SCAKR sediments. The Fe(II)aq has lower 56Fe/54Fe values than bulk HCl-extractable Fe; δ56Fe values for bulk HCl-extractable Fe fall within the range previously defined for mafic- to intermediate-composition terrestrial igneous rocks, modern marine sediments, suspended river sediments, Proterozoic-Phanerozoic shales, loess, aerosols, and soils. After removal of pore fluid, sediment was reacted for 1 hr with 0.1M HCl to isolate solid-phase Fe(II) (Fe(II)s), which was likely a mixture of sorbed Fe(II) and amorphous surface-precipitated Fe(II) hydroxide. Subsequent 24-hr extraction with 0.5M HCl recovered amorphous Fe(III) oxide (Fe(III)am). Sediment incubation experiments with SCAKR sediment produced trends in in Fe isotopic fractionations between Fe(II)aq, Fe(II)s, and Fe(III)am analogous to those observed in situ. Collectively the data suggest an equilibrium 56Fe/54Fe isotope fractionation between Fe(II)aq and Fe

  2. Field tests indicate tubing is main source of iron precipitation in the wellbore

    SciTech Connect

    Coulter, A.W.; Gougler, P.D.

    1984-09-03

    Among the many problems that arise in a producing well is the production decline from impairment of near-wellbore permeability. This can result from a number of causes, including particle migration, water saturation, or precipitation of a mineral scale in the flow channels. Efforts to overcome the decline normally utilize acid. Acid introduces another possible problem, the precipitation of dissolved iron near the wellbore. Although many investigators have considered the danger of iron precipitation near the wellbore, very few have considered rust and debris from the tubing as the primary source of the problem.

  3. Morphological and chemical evidence of stromatolitic deposits in the 2.75 Ga Carajás banded iron formation, Brazil

    NASA Astrophysics Data System (ADS)

    Ribeiro da Luz, Beatriz; Crowley, James K.

    2012-11-01

    We describe evidence of biogenicity in the morphology and carbon content of well-preserved, Neoarchean samples of banded iron formation (BIF) from Carajás, Brazil. Silica-rich BIF layers contain translucent ellipsoidal or trapezoidal structures (˜5-10 μm diameter) composed of silica, hematite, and kerogen, which are arranged in larger ring-like forms (rosettes). Stable carbon isotope analysis yields a δ13C value of -24.5‰ indicating that the contained carbon is likely biogenic. Raman and SEM analyses, as well as wavelength-dispersive X-ray elemental maps, show kerogen inside the rosette forms. Within the iron-rich BIF layers, tubular structures (0.5-5 μm) were observed between hematite granules and blades. Kerogen and kaolinite are present in these structures. Both the rosettes and the tubular structures resemble morphologies that are characteristic of some bacterial species. We hypothesize that the Carajás BIFs originated as biomats formed by one or more species that over time produced large stromatolitic structures. The rosettes and the tubular structures, associated with chert-rich and iron-rich BIF layers, respectively, may represent two different species, or perhaps, two phases of a bacterium life cycle. For example, some modern myxobacteria exhibit similar morphologies in their resting and vegetative stages. Fe(III) precipitation may have occurred by contact of Fe(II) with bacterial slime, leading to oxidation by chemical reactions with exposed polysaccharide hydroxyl and carboxyl groups. The Fe(III) would then have been available for use as a source of energy in a dissimilatory iron reduction type of metabolism. Organic carbon input presumably came from primary producers (not necessarily aerobic) within the local water column, perhaps in shallow-water communities. Alternatively, the carbon may have originated by Fischer-Tropsch synthesis at ocean hydrothermal vents. The observed lateral continuity of BIF layers may perhaps be explained by chemical

  4. Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous FeII solutions.

    PubMed

    Boparai, Hardiljeet K; Comfort, Steve D; Satapanajaru, Tunlawit; Szecsody, Jim E; Grossl, Paul R; Shea, Patrick J

    2010-05-01

    Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron Fe(II)/Fe(III) minerals. This was accomplished by quantifying the effects of initial Fe(II) concentration, pH, and the presence of aquifer solids (Fe(III) phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing Fe(II) concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous Fe(II) during HE treatment under anaerobic conditions. Geochemical modeling also predicted Fe(II) activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated Fe(II)/Fe(III) minerals in aqueous Fe(II) solutions play in the transformation of high explosives. PMID:20226494

  5. Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous FeII solutions.

    PubMed

    Boparai, Hardiljeet K; Comfort, Steve D; Satapanajaru, Tunlawit; Szecsody, Jim E; Grossl, Paul R; Shea, Patrick J

    2010-05-01

    Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron Fe(II)/Fe(III) minerals. This was accomplished by quantifying the effects of initial Fe(II) concentration, pH, and the presence of aquifer solids (Fe(III) phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing Fe(II) concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous Fe(II) during HE treatment under anaerobic conditions. Geochemical modeling also predicted Fe(II) activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated Fe(II)/Fe(III) minerals in aqueous Fe(II) solutions play in the transformation of high explosives.

  6. Supported iron nanoparticles as catalysts for sustainable production of lower olefins.

    PubMed

    Torres Galvis, Hirsa M; Bitter, Johannes H; Khare, Chaitanya B; Ruitenbeek, Matthijs; Dugulan, A Iulian; de Jong, Krijn P

    2012-02-17

    Lower olefins are key building blocks for the manufacture of plastics, cosmetics, and drugs. Traditionally, olefins with two to four carbons are produced by steam cracking of crude oil-derived naphtha, but there is a pressing need for alternative feedstocks and processes in view of supply limitations and of environmental issues. Although the Fischer-Tropsch synthesis has long offered a means to convert coal, biomass, and natural gas into hydrocarbon derivatives through the intermediacy of synthesis gas (a mixture of molecular hydrogen and carbon monoxide), selectivity toward lower olefins tends to be low. We report on the conversion of synthesis gas to C(2) through C(4) olefins with selectivity up to 60 weight percent, using catalysts that constitute iron nanoparticles (promoted by sulfur plus sodium) homogeneously dispersed on weakly interactive α-alumina or carbon nanofiber supports. PMID:22344440

  7. Characterization by thermoelectric power of a commercial aluminum-iron-silicon alloy (8011) during isothermal precipitation

    SciTech Connect

    Luiggi A., N.J.

    1998-11-01

    The author has characterized a commercial 8011 (Al-Fe-Si) alloy by studying samples under different initial states of strain hardening and iron and silicon supersaturation using thermoelectric power as a measurement technique. Isothermal kinetics of precipitation are obtained in the temperature range between 225 C and 600 C. He has determined the atom fraction precipitated for each microstructural condition, identifying the dominant alloying additions and evaluating the typical parameters of the precipitated phases, such as, for example, the apparent activation energy. Finally, he determined the time-temperature-transformation (TTT) diagrams. These results prove that iron is the alloying addition that controls the precipitation kinetics of the 8011 alloy in the temperature range studied.

  8. Iron oxide and hydroxide precipitation from ferrous solutions and its relevance to Martian surface mineralogy

    NASA Technical Reports Server (NTRS)

    Posey-Dowty, J.; Moskowitz, B.; Crerar, D.; Hargraves, R.; Tanenbaum, L.

    1986-01-01

    Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished.

  9. Synthesis of hydrocarbons from CO and H/sub 2/ in the presence of catalysts based on mononuclear iron complexes

    SciTech Connect

    Lapidus, A.L.; Savel'ev, M.M.; Tsapkina, M.V.; Solodov, S.N.; Sominskii, S.D.

    1985-01-01

    Iron catalysts for Fischer-Tropsch synthesis, activated by alkaline additives are active in the synthesis of hydrocarbons from CO and H/sub 2/. It is well known that catalysts obtained by applying K/sub 2/(Fe/sub 3/(CO)/sub 11/) complexes on ..gamma..-Al/sub 2/O/sub 3/ have increased selectivity in the formation of lower olefins from CO and H/sub 2/. IR spectroscopy using catalysts based on K/sub 2/(Fe/sub 3/(CO)/sub 11/) showed that during heat treatment in vacuum, CO, H/sub 2/, CO + H/sub 2/ atmosphere a transition is observed of polynuclear complexes found on a carrier surface, to a (Fe(CO)/sub 5/, Fe(acac)/sub 3/ and Fe(C/sub 5/H/sub 5/)/sub 2/, in Fischer-Tropsch synthesis. A study was made in this paper of the effect of the type of initial Fe-complex: iron pentacarbonyl Fe(CO)/sub 5/-I, iron acetylacetonate Fe(acac)/sub 3/-II, ferrocene Fe(C/sub 5/H/sub 5/)/sub 2/-III, on the activity and selectivity of Fe-K catalysts in the synthesis of lower olefins from CO and H/sub 2/. In these complexes Fe is oxidized from Fe/sup 0/ to Fe/sup 3 +/ (3). In order to prepare catalysts by the same method, Fe(acac)/sub 3/ was selected as Fe/sup 3 +/ compound, which is soluble in alkaline methanol solution.

  10. A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns

    NASA Astrophysics Data System (ADS)

    Wu, Yuxin; Slater, Lee; Versteeg, Roelof; LaBrecque, Douglas

    2008-01-01

    Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe 0 columns using (a) Na 2SO 4, and (b) NaHCO 3 plus CaCl 2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ.

  11. Interstitial-phase precipitation in iron-base alloys: a comparative study

    SciTech Connect

    Pelton, A.R.

    1982-06-01

    Recent developments have elucidated the atomistic mechanisms of precipitation of interstitial elements in simple alloy systems. However, in the more technologically important iron base alloys, interstitial phase precipitation is generally not well understood. The present experimental study was therefore designed to test the applicability of these concepts to more complex ferrous alloys. Hence, a comparative study was made of interstitial phase precipitation in ferritic Fe-Si-C and in austenitic phosphorus-containing Fe-Cr-Ni steels. These systems were subjected to a variety of quench-age thermal treatments, and the microstructural development was subsequently characterized by transmission electron microscopy.

  12. Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

    SciTech Connect

    Wu, Yuxin; Versteeg, R.; Slater, L.; LaBrecque, D.

    2009-06-01

    Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO{sub 3} and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO{sub 3} as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO{sub 3} dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO{sub 3} forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO{sub 3} precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

  13. A model for the biological precipitation of Precambrian iron-formation

    NASA Technical Reports Server (NTRS)

    Laberge, G. L.

    1986-01-01

    A biological model for the precipitation of Precambrian iron formations is presented. Assuming an oxygen deficient atmosphere and water column to allow sufficient Fe solubility, it is proposed that local oxidizing environments, produced biologically, led to precipitation of iron formations. It is further suggested that spheroidal structures about 30 mm in diameter, which are widespread in low grade cherty rion formations, are relict forms of the organic walled microfossil Eosphaera tylerii. The presence of these structures suggests that the organism may have had a siliceous test, which allowed sufficient rigidity for accumulation and preservation. The model involves precipitation of ferric hydrates by oxidation of iron in the photic zone by a variety of photosynthetic organisms. Silica may have formed in the frustules of silica secreting organisms, including Eosphaera tylerii. Iron formates formed, therefore, by a sediment rain of biologically produced ferric hydrates and silica and other organic material. Siderite and hematite formed diagenetically on basin floors, and subsequent metamorphism produced magnetite and iron silicates.

  14. A model for the biological precipitation of Precambrian iron-formation

    NASA Astrophysics Data System (ADS)

    Laberge, G. L.

    A biological model for the precipitation of Precambrian iron formations is presented. Assuming an oxygen deficient atmosphere and water column to allow sufficient Fe solubility, it is proposed that local oxidizing environments, produced biologically, led to precipitation of iron formations. It is further suggested that spheroidal structures about 30 mm in diameter, which are widespread in low grade cherty rion formations, are relict forms of the organic walled microfossil Eosphaera tylerii. The presence of these structures suggests that the organism may have had a siliceous test, which allowed sufficient rigidity for accumulation and preservation. The model involves precipitation of ferric hydrates by oxidation of iron in the photic zone by a variety of photosynthetic organisms. Silica may have formed in the frustules of silica secreting organisms, including Eosphaera tylerii. Iron formates formed, therefore, by a sediment rain of biologically produced ferric hydrates and silica and other organic material. Siderite and hematite formed diagenetically on basin floors, and subsequent metamorphism produced magnetite and iron silicates.

  15. In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation

    SciTech Connect

    Ghosh, R.S.; Dzombak, D.A.; Luthy, R.G.; Smith, J.R.

    1999-10-01

    Groundwater contamination with cyanide is common at many former or active industrial sites. Metal-cyanide complexes typically dominate aqueous speciation of cyanide in groundwater systems, with iron-cyanide complexes often most abundant. Typically, metal-cyanide complexes behave as nonadsorbing solutes in sand-gravel aquifer systems in the neutral pH range, rendering cyanide relatively mobile in groundwater systems. Groundwater pump-and-treat systems have often been used to manage cyanide contamination in groundwater. This study examined the feasibility of using in situ precipitation of iron cyanide in a reactive barrier to attenuate the movement of cyanide in groundwater. Laboratory column experiments were performed in which cyanide solutions were passed through mixtures of sand and elemental iron filings. Removal of dissolved cyanide was evaluated in a variety of cyanide-containing influents under various flow rates and sand-to-iron weight ratios. Long-term column tests performed with various cyanide-containing influents under both oxic and anoxic conditions, at neutral pH and at flow rates typical of sand-gravel porous media, yielded effluent concentrations of total cyanide as low as 0.5 mg/L. Effluent cyanide concentrations achieved were close to the solubilities of Turnbull's blue-hydrous ferric oxide solid solutions, indicating co-precipitation of the two solids. Maximum cyanide removal efficiency was achieved with approximately 10% by weight of iron in the sand-iron mixtures; higher iron contents did not increase removal efficiency significantly. Results obtained indicate that in situ precipitation is a promising passive treatment approach for cyanide in groundwater.

  16. Mineral Precipitation Upgradient from a Zero-Valent Iron Permeable Reactive Barrier

    SciTech Connect

    Johnson, R. L.; Thoms, R. B.; Johnson, R. O.; Nurmi, J. T.; Tratnyek, Paul G.

    2008-07-01

    Core samples taken from a zero-valent iron permeable reactive barrier (ZVI PRB) at Cornhusker Army Ammunition Plant, Nebraska, were analyzed for physical and chemical characteristics. Precipitates containing iron and sulfide were present at much higher concentrations in native aquifer materials just upgradient of the PRB than in the PRB itself. Sulfur mass balance on core solids coupled with trends in ground water sulfate concentrations indicates that the average ground water flow after 20 months of PRB operation was approximately twenty fold less than the regional ground water velocity. Transport and reaction modeling of the aquifer PRB interface suggests that, at the calculated velocity, both iron and hydrogen could diffuse upgradient against ground water flow and thereby contribute to precipitation in the native aquifer materials. The initial hydraulic conductivity (K) of the native materials is less than that of the PRB and, given the observed precipitation in the upgradient native materials, it is likely that K reduction occurred upgradient to rather than within the PRB. Although not directly implicated, guar gum used during installation of the PRB is believed to have played a role in the precipitation and flow reduction processes by enhancing microbial activity.

  17. Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

    USGS Publications Warehouse

    Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

    2006-01-01

    Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments

  18. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Akio Ishikawa; Manuel Ojeda; Enrique Iglesia

    2005-09-30

    during the reduction-carburization processes. In this reporting period, we have measured the evolution of oxide, carbide, and metal phases of the active iron components using advanced synchrotron techniques based on X-ray absorption spectroscopy. These studies have revealed that Zn inhibits the isothermal reduction and carburization of iron oxide precursors. The concurrent presence of Cu or Ru compensates for these inhibitory effects and lead to the formation of active carbide phases at the low temperatures required to avoid deactivation via carbon deposition or sintering. Finally, we have also examined the kinetic behavior of these materials, specifically the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch synthesis reactions. This has led to a rigorous rate expressions that allows the incorporation of these novel materials into larger scale reactors and to predictions of performance based on the coupling of hydrodynamic and kinetic effects ubiquitous in such reactors.

  19. In situ precipitation: a novel approach for preparation of iron-oxide magnetoliposomes

    PubMed Central

    Xia, Shudong; Li, Peng; Chen, Qiang; Armah, Malik; Ying, Xiaoying; Wu, Jian; Lai, Jiangtao

    2014-01-01

    Background Conventional methods of preparing magnetoliposomes are complicated and inefficient. A novel approach for magnetoliposomes preparation was investigated in the study reported here. Methods FeCl3/FeCl2 solutions were hydrated with lipid films to obtain liposome-encapsulated iron ions by ultrasonic dispersion. Non-encapsulated iron ions were removed by dialysis. NH3 · H2O was added to the system to adjust the pH to a critical value. Four different systems were prepared. Each was incubated at a different temperature for a different length of time to facilitate the permeation of NH3 · H2O into the inner phase of the liposomes and the in situ formation of magnetic iron-oxide cores in the liposomes. Single-factor analysis and orthogonal-design experiments were applied to determinate the effects of alkalization pH, temperature, duration, and initial Fe concentration on encapsulation efficiency and drug loading. Results The magnetoliposomes prepared by in situ precipitation had an average particle size of 168±14 nm, zeta potential of −26.2±1.9 mV and polydispersity index of 0.23±0.06. The iron-oxide cores were confirmed as Fe3O4 by X-ray diffraction and demonstrated a superparamagnetic response. Encapsulation efficiency ranged from 3% to 22%, while drug loading ranged from 0.2 to 1.58 mol Fe/mol lipid. The optimal conditions for in situ precipitation were found to be an alkalization pH of 12, temperature of 60°C, time of 60 minutes, and initial Fe concentration of 100 mM Fe3+ + 50 mM Fe2+. Conclusion In situ precipitation could be a simple and efficient approach for the preparation of iron-oxide magnetoliposomes. PMID:24920898

  20. Cobalt-ruthenium catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Iglesia, E.; Soled, S.L.; Fiato, R.A.

    1989-04-18

    A hydrocarbon synthesis process is described which comprises reacting hydrogen and carbon monoxide in the presence of a catalyst comprised of cobalt and ruthenium on titania, at reaction conditions suitable for the formation of higher hydrocarbons. The catalyst is prepared by impregnating titania with solutions of cobalt and ruthenium salts, drying the impregnated support, reducing the cobalt and ruthenium, treating the reduced metals with an oxygen containing stream at conditions sufficient to form oxides of cobalt and oxides of ruthenium and reducing the cobalt and ruthenium oxides.

  1. Fischer-Tropsch synthesis on functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Pokhrel, Sewa

    The aim of this research was to investigate the role of chemical functionalization on carbon nanotubes surfaces and its effect on FT catalysis. Multi walled carbon nanotubes (MWNT) were first treated with acid (HCl) to remove the residual metal particles and were then functionalized using H2O2 and HNO3 to introduce oxygen-containing groups to the MWNT surface. These treatments also add defects on MWNT surface. Morphological analyses were performed on the MWNT samples with TEM and it was found that the peroxide and acid treated MWNTs showed an increase oxygen functional groups and created additional surface defects on the MWNTs. Results of FT experiments showed enhanced CO conversion, FT activity and product selectivity towards liquid hydrocarbons due to functionalization. The liquid selectivity was found to be significantly high for H2O 2 treated catalyst. HNO3 treated catalyst had highest activity although selectivity to methane and CO2 was found higher than the H2O2 treated catalyst. It was observed that the chemical treatments increase the carbon chain length of the produced hydrocarbons. While comparing hydrocarbon distribution of as-produced and H2O2 treated MWNT, it was found that carbon-chain length increases for peroxide treated catalyst. Along with as-produced and functionalized nanotube, FT experiments were also conducted using B-doped sponge, un-doped sponge and N-doped CNT catalyst. B-doped sponge showed enhanced CO conversion and FT activity as compared to un-doped sponge. Conversion and product selectivity were found to be affected by temperature when test was conducted with N-CNT. Operating conditions like temperature, syngas feed flow rate and syngas ratio were also to impact the FT performance.

  2. Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

    SciTech Connect

    Adeyiga, Adeyinka

    2010-02-05

    Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditions as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).

  3. Synthesis gas solubility in Fischer-Tropsch slurry

    SciTech Connect

    Huang, S.H.

    1987-01-01

    A semi-flow apparatus is designed and constructed for the measurements of gas solubilities in molten waxes. Test data of CO/sub 2//toluene mixture show excellent agreement with literature data from a static apparatus. Five gases are studied: hydrogen, carbon monoxide, methane, ethane, and carbon dioxide. Data measurements are completed for each gas in n-eicosane (C/sub 20/), n-octacosane (C/sub 28/), and in n-hexatriacontane (C/sub 36/) as well as in an industrial wax over 100 to 300/sup 0/C and 10 to 50 atm. Solubilities of gas mixtures of H/sub 2/ + CO in n-C/sub 28/ are also measured at several equilibrium gas compositions. The gas K-value, defined as the ratio of the composition in the vapor phase to that in the liquid phase, is found independent as gas compositions within experimental errors. The Krichevski-Kasarnovsky equation represents well the data of binary systems. Henry's constants and partial molar volumes of gases at infinite dilution are determined from the equation. The Redlich-Kwong-Soave equation of state is modified to describe the vapor pressures of n-paraffins up to n-C/sub 100/. The modified equation is combined with a new mixing rule, whose derivation is based on a polymer solution theory, to correlate the data, and the results are satisfactory. Furthermore, the adjustable parameter can be correlated as an asymptotical function of the solvent molecular weight except for H/sub 2/ and CO at the lowest temperature. The modified equation with correlated parameter can predict the gas mixture solubilities in n-C/sub 28/. Also, gas solubilities in a wax mixture can be predicted if the wax is treated as a pure n-paraffin with the same number average molecular weight.

  4. VLE MEASUREMENTS FOR ASYMMETRIC MIXTURES OF FISCHER-TROPSCH HYDROCARBONS

    SciTech Connect

    Mark C. Thies

    2004-01-12

    The ability to model the thermodynamic phase behavior of long-chain and short-chain alkane mixtures is of considerable industrial and theoretical interest. However, attempts to accurately describe the phase behavior of what we call asymmetric mixtures of hydrocarbons (AMoHs) have met with only limited success. Vapor-liquid equilibrium (VLE) data are surprisingly scarce, and the limited data that are available suggest that cubic equations of state may not be capable of fitting (much less predicting) the phase behavior of AMoHs. The following tasks, which address the problems described above, were accomplished during the one-year period of this Phase I UCR grant: (1) A continuous-flow apparatus was modified for the measurement of AMoHs and used to measure VLE for propane + hexadecane mixtures at temperatures from 473 to 626 K and pressures up to the mixture critical pressures of about 100 bar. (2) The extent to which cubic vs. modern, statistical mechanics-based equations of state (EoS) are applicable to AMoHs was evaluated. Peng-Robinson (PR) was found to be a surprisingly accurate equation for fitting AMoHs, but only if its pure component parameters were regressed to liquid densities and vapor pressures. However, even this form of PR was still not a predictive equation, as there was a significant variation of kij with temperature. In spite of its deficiencies in terms of vapor-phase predictions and modeling of the critical region, PC-SAFT was found to be the most appropriate EoS for truly predicting the phase behavior of highly asymmetric mixtures of alkanes. (3) Finally, a dense-gas extraction (DGE) apparatus was designed and constructed for the fractionation of F-T waxes into cuts of pure oligomers. Such oligomers are needed in g-sized quantities to perform VLE measurements with long-chain alkanes with carbon numbers greater than 40. The dense gas and the solute mixture to be extracted are contacted in a packed column that has a separation power significantly greater than what can be achieved in one equilibrium stage. Thus, wax oligomer purities are expected to be much better than what can be obtained by conventional supercritical extraction processes.

  5. Fischer-Tropsch Synthesis on Ceramic Monolith-Structured Catalysts

    SciTech Connect

    Wang, Yong; Liu, Wei

    2009-04-19

    This paper reports recent research results about impact of different catalyst bed configurations on FT reaction product distribution. A CoRe/γ-alumina catalyst is prepared in bulk particle form and tested in the packed bed reactor at a size of 60 to 100 mesh. The same catalyst is ball milled and coated on a ceramic monolith support structure of channel size about 1mm. The monolith catalyst module is tested in two different ways, as a whole piece and as well-defined channels. Steady-state reaction conversion is measured at various temperatures under constant H2/CO feed ratio of 2 and reactor pressure of 25 bar. Detailed product analysis is performed. Significant formation of wax is evident with the packed particle bed and with the monolith catalyst that is improperly packed. By contrast, the wax formation is not detected in the liquid product by confining the reactions inside the monolith channel. This study presents an important finding about the structured catalyst/reactor system that the product distribution highly depends on the way how the structured reactor is set up. Even if the same catalyst and same reaction conditions (T, P, H2/oil ratio) are used, hydrodynamics (or flow conditions) inside a structured channel can have a significant impact on the product distribution.

  6. Attrition resistant Fischer-Tropsch catalyst and support

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2004-05-25

    A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

  7. Analysis of Valence Electron Structure on Fe3AlCx Precipitated from C-Alloyed Iron Aluminides

    NASA Astrophysics Data System (ADS)

    Tian, Xiao-Feng; Zhang, Wei-Ke; Qi, Yu

    2013-12-01

    Carbides of Fe3AlCx precipitated from iron aluminides can strengthen the matrix; the empirical electron theory (EET) was applied to analyze the attribute of carbides in the paper, giving theoretical explanation on the matrix and precipitation. Valence electron structure (VES) of Fe3AlCx was studied in detail, comparison with the iron aluminides matrix, the hard and brittle phase of Fe3AlCx can be interpreted form the viewpoint of valence electron structure.

  8. Dispersion-precipitation synthesis of nanosized magnetic iron oxide for efficient removal of arsenite in water.

    PubMed

    Cheng, Wei; Xu, Jing; Wang, Yajie; Wu, Feng; Xu, Xiuyan; Li, Jinjun

    2015-05-01

    Nanosized magnetic iron oxide was facilely synthesized by a dispersion-precipitation method, which involved acetone-promoted precipitation of colloidal hydrous iron oxide nanoparticles and subsequent calcination of the precipitate at 250°C. Characterization by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, nitrogen sorption, and vibrating-sample magnetometry revealed that the material was a composite of α-Fe2O3 and γ-Fe2O3 with primary particle size of 15-25 nm and specific surface area of 121 m(2)/g, as well as superparamagnetic property. The material was used as adsorbent for the removal of arsenite in water. Batch experiments showed that the adsorption isotherms at pH 3.0-11.0 fit the Langmuir equation and the adsorption obeys pseudo-second-order kinetics. Its maximum sorption capability for arsenite is 46.5 mg/g at pH 7.0. Coexisting nitrate, carbonate, sulfate, chloride, and fluoride have no significant effect on the removal efficiency of arsenite, while phosphate and silicate reduce the removal efficiency to some extent. The As(III) removal mechanism is chemisorption through forming inner-sphere surface complexes. The efficiency of arsenic removal is still maintained after five cycles of regeneration-reuse. PMID:25612934

  9. Analysis of flow decay potential on Galileo. [oxidizer flow rate reduction by iron nitrate precipitates

    NASA Technical Reports Server (NTRS)

    Cole, T. W.; Frisbee, R. H.; Yavrouian, A. H.

    1987-01-01

    The risks posed to the NASA's Galileo spacecraft by the oxidizer flow decay during its extended mission to Jupiter is discussed. The Galileo spacecraft will use nitrogen tetroxide (NTO)/monomethyl hydrazine bipropellant system with one large engine thrust-rated at a nominal 400 N, and 12 smaller engines each thrust-rated at a nominal 10 N. These smaller thrusters, because of their small valve inlet filters and small injector ports, are especially vulnerable to clogging by iron nitrate precipitates formed by NTO-wetted stainless steel components. To quantify the corrosion rates and solubility levels which will be seen during the Galileo mission, corrosion and solubility testing experiments were performed with simulated Galileo materials, propellants, and environments. The results show the potential benefits of propellant sieving in terms of iron and water impurity reduction.

  10. Ultrastructural Study of Iron Oxide Precipitates: Implications for the Search for Biosignatures in the Meridiani Hematite Concretions, Mars

    NASA Astrophysics Data System (ADS)

    Souza-Egipsy, Virginia; Ormö, Jens; Bowen, Brenda Beitler; Chan, Marjorie A.; Komatsu, Goro

    2006-08-01

    Two terrestrial environments that have been proposed as analogs for the iron oxide precipitation in the Meridiani Planum region of Mars include the Rio Tinto precipitates and southern Utah marble concretions. Samples of two typical Utah iron oxide concretions and iron oxide precipitates in contact with biofilms from Rio Tinto have been studied to determine whether evidence could be found for biomediation in the precipitation process and to identify likely locations for fossil microorganisms. Scanning electron microscopy, energy dispersive X-ray, and gas chromatography-mass spectrometry (GC-MS) were used to search for biosignatures in the Utah marbles. The precipitation of iron oxides resembles known biosignatures, though organic compounds could not be confirmed with GC-MS analysis. In contrast, textural variations induced by biological activity are abundant in the modern Rio Tinto samples. Although no compelling evidence of direct or indirect biomediation was found in the Utah marbles, the ultrastructure of the iron oxide cement in the concretion suggests an inward growth during concretion precipitation from an initially spherical redox front. No indication for growth from a physical nucleus was found.

  11. A detailed study on the transition from the blocked to the superparamagnetic state of reduction-precipitated iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Witte, K.; Bodnar, W.; Mix, T.; Schell, N.; Fulda, G.; Woodcock, T. G.; Burkel, E.

    2016-04-01

    Magnetic iron oxide nanoparticles were prepared by salt-assisted solid-state chemical precipitation method with alternating fractions of the ferric iron content. The physical properties of the precipitated nanoparticles mainly consisting of magnetite were investigated by means of transmission electron microscopy, high energy X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopy. With particle sizes ranging from 16.3 nm to 2.1 nm, a gradual transition from the blocked state to the superparamagnetic state was observed. The transition was described as a dependence of the ferric iron content used during the precipitation. Composition, mean particle size, coercivity, saturation polarisation, as well as hyperfine interaction parameters and their evolution were studied systematically over the whole series of iron oxide nanoparticles.

  12. Deactivation by carbon of iron catalysts for indirect liquefaction

    SciTech Connect

    Bartholomew, C.H.

    1991-01-10

    Although promoted cobalt and iron catalysts for Fischer-Tropsch (FT) synthesis of gasoline feedstock were first developed more than three decades ago, a major technical problem still limiting the commercial use of these catalysts today is carbon deactivation. This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for FT synthesis, the objectives of which are to: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; and model the rates of deactivation of the same catalysts in fixed-bed reactors. To accomplish the above objectives, the project is divided into the following tasks: (1) determine the kinetics of reaction and of carbon deactivation during CO hydrogenation on Fe and Fe/K catalysts coated on monolith bodies. (2) Determine the reactivities and types of carbon deposited during reaction on the same catalysts from temperature-programmed-surface-reaction spectroscopy (TPSR) and transmission electron microscopy (TEM). Determine the types of iron carbides formed at various temperatures and H{sub 2}/CO ratios using x-ray diffraction and Moessbauer spectroscopy. (3) Develop mathematical deactivation models which include heat and mass transport contributions for FT synthesis is packed-bed reactors. Progress to date is described. 48 refs., 3 figs., 1 tab.

  13. Pyrophosphate synthesis in iron mineral films and membranes simulating prebiotic submarine hydrothermal precipitates

    NASA Astrophysics Data System (ADS)

    Barge, Laura M.; Doloboff, Ivria J.; Russell, Michael J.; VanderVelde, David; White, Lauren M.; Stucky, Galen D.; Baum, Marc M.; Zeytounian, John; Kidd, Richard; Kanik, Isik

    2014-03-01

    Cells use three main ways of generating energy currency to drive metabolism: (i) conversion of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) by the proton motive force through the rotor-stator ATP synthase; (ii) the synthesis of inorganic phosphate˜phosphate bonds via proton (or sodium) pyrophosphate synthase; or (iii) substrate-level phosphorylation through the direct donation from an active phosphoryl donor. A mechanism to produce a pyrophosphate bond as “energy currency” in prebiotic systems is one of the most important considerations for origin of life research. Baltscheffsky (1996) suggests that inorganic pyrophosphate (PO74-; PPi) may have preceded ATP/ADP as an energy storage molecule in earliest life, produced by an H+ pyrophosphatase. Here we test the hypothesis that PPi could be synthesized in inorganic precipitates simulating hydrothermal chimney structures transected by thermal and/or ionic gradients. Appreciable yields of PPi were obtained via substrate phosphorylation by acetyl phosphate within the iron sulfide/silicate precipitates at temperatures expected for an alkaline hydrothermal system. The formation of PPi only occurred in the solid phase, i.e. when both Pi and the phosphoryl donor were precipitated with Fe-sulfides or Fe-silicates. The amount of Ac-Pi incorporated into the precipitate was a significant factor in the amount of PPi that could form, and phosphate species were more effectively incorporated into the precipitate at higher temperatures (⩾50 to >85 °C). Thus, we expect that the hydrothermal precipitate would be more enriched in phosphate (and especially, Ac-Pi) near the inner margins of a hydrothermal mound where PPi formation would be at a maximum. Iron sulfide and iron silicate precipitates effectively stabilized Ac-Pi and PPi against hydrolysis (relative to hydrolysis in aqueous solution). Thus it is plausible that PPi could accumulate as an energy currency up to useful concentrations for early life in a

  14. Iron Isotope Fractionation in Microbial and Non-Biological Precipitates, and the Human Body

    NASA Astrophysics Data System (ADS)

    von Blanckenburg, F.; Boettcher, M. E.; Hofmann, B.; Walczyk, T.

    2001-12-01

    We have investigated biotic and abiotic stable iron isotope fractionation pathways in experiments, the low-T natural environment, and the human body. Fe samples were analysed using a Nu Plasma Multicollector ICP-MS. All measured samples plot on the theoretically predicted exponential fractionation line in the Delta57Fe versus Delta56Fe space, demonstrating absence of ArN or ArO interferences. An experimental calibration of Fe isotope fractionation during abiotic formation of iron (III) oxyhydroxide and iron(II) minerals from aqueous solution resulted in significant differences: (a) During fast precipitation of FeOOH during alkalization of a Fe(III)Cl3 solution at room temperature the solid is only slightly enriched by about 0.1permil in 57Fe compared to the solution. (b) Slow precipitation of akaganeite (beta-FeOOH) from aqueous Fe(III)Cl3 solution leads to a depletion of 57Fe by about -2.2permil in the solid phase without a significant influence of temperature. (c) Precipitation of FeOOH during oxidation of aqueous Fe(II) solutions by oxygen yields an enrichment of up to 4.8permil in 57Fe in the solid phase. (d) Iron(II) carbonate precipitation between 20 and 60C leads to an almost negligible depletion in 57Fe compared to aqueous ferrous ions. Interpretation: Large enrichment of the heavy isotope is observed where Fe is oxidised, whereas small to interme-diate depletions of heavy Fe isotopes occur upon forma-tion of Fe-minerals without change in redox state. Addi-tionally, kinetic effects, the speciation of the aqueous solution, or the effect of crystal structures may have to be considered. Biotic isotope fractionation by microorganisms was investigated at two field sites. In a Fe mine (Gonzen, Switzerland), Fe-precipitating microbes (Gallionella ferrugina and Leptohrix ochtraceae) have formed Fe(III)-oxyhydroxides that are ca. 0.6permil heavier in Delta57Fe than the Fe-rich parent solutions. At Cady Mts, California, filamentous fabrics of goethite, thought to

  15. Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous Fe¹¹ solutions

    SciTech Connect

    Boparai, Hardiljeet K.; Comfort, Steve; Satapanajaru, Tunlawit; Szecsody, James E.; Grossl, Paul; Shea, Patrick

    2010-05-11

    Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated FeII phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron FeII/FeIII minerals. This was accomplished by quantifying the effects of initial FeII concentration, pH, and the presence of aquifer solids (FeIII phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing FeII concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous FeII during HE treatment under anaerobic conditions. Geochemical modeling also predicted FeII activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated FeII/FeIII minerals in aqueous FeII solutions play in the transformation of high explosives.

  16. Fischer–Tropsch Synthesis: Characterization Rb Promoted Iron Catalyst

    SciTech Connect

    Sarkar,A.; Jacobs, G.; Ji, Y.; Hamdeh, H.; Davis, B.

    2008-01-01

    Rubidium promoted iron Fischer-Tropsch synthesis (FTS) catalysts were prepared with two Rb/Fe atomic ratios (1.44/100 and 5/100) using rubidium nitrate and rubidium carbonate as rubidium precursors. Results of catalytic activity and deactivation studies in a CSTR revealed that rubidium promoted catalysts result in a steady conversion with a lower deactivation rate than that of the corresponding unpromoted catalyst although the initial activity of the promoted catalyst was almost half that of the unpromoted catalyst. Rubidium promotion results in lower methane production, and higher CO2, alkene and 1-alkene fraction in FTS products. M{umlt o}ssbauer spectroscopic measurements of CO activated and working catalyst samples indicated that the composition of the iron carbide phase formed after carbidization was -Fe5 C2 for both promoted and unpromoted catalysts. However, in the case of the rubidium promoted catalyst, '-Fe2.2C became the predominant carbidic phase as FTS continued and the overall catalyst composition remained carbidic in nature. In contrast, the carbide content of the unpromoted catalyst was found to decline very quickly as a function of synthesis time. Results of XANES and EXAFS measurements suggested that rubidium was present in the oxidized state and that the compound most prevalent in the active catalyst samples closely resembled that of rubidium carbonate.

  17. Iron Release and Precipitation in Fracture Fluid-Shale Fracturing Systems

    NASA Astrophysics Data System (ADS)

    Jew, A. D.; Joe-Wong, C. M.; Harrison, A. L.; Thomas, D.; Dustin, M. K.; Brown, G. E.; Maher, K.; Bargar, J.

    2015-12-01

    Hydraulic fracturing of unconventional hydrocarbon reservoirs is important to the United States energy portfolio. Hydrocarbon production from new wells generally declines rapidly over the initial months of production. One possible reason for the decrease is the mineralization and clogging of microfracture networks proximal to propped fractures. One important but relatively unexplored class of reactions is oxidation of Fe(II) derived from Fe(II)-bearing mineral dissolution (primarily pyrite and siderite) and subsequent precipitation of Fe(III)-(oxy)hydroxides. To explore this topic, we reacted fracture fluid with sand-sized and whole rock chips from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.) containing highly varied concentrations of clays, carbonates, and TOC. Additionally, kerogen was isolated from the Green River Fm. and reacted with fracture fluid. All the shale sands showed an initial release of Fe into solution during the first 96 hours of reaction followed by a plateau or significant drop in Fe indicating that mineral precipitation occurred. Conversely, the Fe concentrations in the kerogen reactors kept increasing throughout the 3-week experiments. The whole rock samples showed a steady increase then a plateau in Fe during the 3-weeks, indicating a slower Fe release and subsequently, slower Fe precipitation. Reactors with Marcellus Fm. Sands contained dilute HCl, water only, the fracture fluid with no headspace, and fracture fluid with no HCl. Results from these experiments show that HCl is the most important additive for the promotion of Fe release into solution. Iron oxidation is not promoted solely by O2 or organics but instead requires a combination of the two for precipitation in these systems. These results indicate that Fe redox cycling is an important and complex part of hydraulic fracturing that most likely results in production slowdown over the life of a well.

  18. Iron particle size effects for direct production of lower olefins from synthesis gas.

    PubMed

    Torres Galvis, Hirsa M; Bitter, Johannes H; Davidian, Thomas; Ruitenbeek, Matthijs; Dugulan, A Iulian; de Jong, Krijn P

    2012-10-01

    The Fischer-Tropsch synthesis of lower olefins (FTO) is an alternative process for the production of key chemical building blocks from non-petroleum-based sources such as natural gas, coal, or biomass. The influence of the iron carbide particle size of promoted and unpromoted carbon nanofiber supported catalysts on the conversion of synthesis gas has been investigated at 340-350 °C, H(2)/CO = 1, and pressures of 1 and 20 bar. The surface-specific activity (apparent TOF) based on the initial activity of unpromoted catalysts at 1 bar increased 6-8-fold when the average iron carbide size decreased from 7 to 2 nm, while methane and lower olefins selectivity were not affected. The same decrease in particle size for catalysts promoted by Na plus S resulted at 20 bar in a 2-fold increase of the apparent TOF based on initial activity which was mainly caused by a higher yield of methane for the smallest particles. Presumably, methane formation takes place at highly active low coordination sites residing at corners and edges, which are more abundant on small iron carbide particles. Lower olefins are produced at promoted (stepped) terrace sites that are available and active, quite independent of size. These results demonstrate that the iron carbide particle size plays a crucial role in the design of active and selective FTO catalysts. PMID:22953753

  19. Microbially induced iron precipitation associated with a neutrophilic spring at Borra Caves, Vishakhapatnam, India.

    PubMed

    Baskar, Sushmitha; Baskar, Ramanathan; Thorseth, Ingunn H; Ovreås, Lise; Pedersen, Rolf B

    2012-04-01

    Betaproteobacteria. Four (4%) of the sequences could not be assigned to phylum level but were affiliating with the candidate division TM7 (2%), candidate division OP11 (1%), and candidate division WWE3 (1%). The results allow us to infer a possible relationship of microbial sheaths, EPS, and the iron precipitates to microbial community diversity in the Borra cave springs. Understanding biogenic iron oxides in caves has important astrobiological applications as it provides a potential tool for the detection of extraterrestrial life.

  20. Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula

    NASA Technical Reports Server (NTRS)

    Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III

    2002-01-01

    The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

  1. Coprecipitation of arsenate with metal oxides. 2. Nature, mineralogy, and reactivity of iron(III) precipitates.

    PubMed

    Violante, Antonio; Del Gaudio, Stefania; Pigna, Massimo; Ricciardella, Mariarosaria; Banerjee, Dipanjan

    2007-12-15

    Coprecipitation of arsenic with iron or aluminum occurs in natural environments and is a remediation technology used to remove this toxic metalloid from drinking water and hydrometallurgical solutions. In this work, we studied the nature, mineralogy, and reactivity toward phosphate of iron-arsenate coprecipitates formed at As(V)/Fe(III) molar ratios (R) of 0, 0.01, or 0.1 and at pH 4.0, 7.0, and 10.0 aged for 30 or 210 days at 50 degrees C and studied the desorption of arsenate. At R = 0, goethite and hematite (with ferrihydrite at pH 4.0 and 7.0) crystallized, whereas at R = 0.01, the formation of ferrihydrite increased and hematite crystallization was favored over goethite. In some samples, the morphology of hematite changed from rounded platy crystals to ellipsoids. At R = 0.1, ferrihydrite formed in all the coprecipitates and remained unchanged even after 210 days of aging. The surface area and chemical composition of the precipitates were affected by pH, R, and aging. Chemical dissolution of the samples showed that arsenate was present mainly in ferrihydrite, but at R = 0.01, it was partially incorporated into the structures of crystalline Fe oxides. The sorption of phosphate on to the coprecipitates was affected not only by the mineralogy and surface area of the samples but also by the amounts of arsenate present in the oxides. The samples formed at pH 4.0 and 7.0 and at R = 0.1 sorbed lower amounts of phosphate than the precipitates obtained at R = 0 or 0.01, despite the former having a larger surface area and showing only a presence of short-range ordered materials. This is mainly due to the fact that in the coprecipitates at R = 0.1 arsenate occupied many sorption sites, thus preventing phosphate sorption. Less than 20% of the arsenate present in the coprecipitates formed at R = 0.1 was removed by phosphate and more from the samples synthesized at pH 7.0 or 10.0 than at pH 4.0. Moreover, we found that more arsenate was desorbed by phosphate from a

  2. Spectroscopic characterization of co-precipitated arsenic- and iron-bearing sulfide phases at circum-neutral pH

    NASA Astrophysics Data System (ADS)

    Illera, V.; Rivera, N. A.; O'Day, P. A.

    2009-12-01

    Precipitation of arsenic- and iron-sulfide phases from porewaters is an important mechanism for removing arsenic and other contaminant metals from solution, thus reducing their bioaccessibility and potential toxicity. Although sulfide phases form readily at low pH, the identity, crystallinity, and local structure of arsenic and iron co-precipitated phases that form at circum-neutral pH are less well known. In this study, co-precipitated As+Fe sulfide phases and end-member As-sulfides and Fe-sulfides were synthesized in batch experiments and in a gas-tight reaction vessel at 25°C. Reduced conditions were maintained by keeping a constant flow of a 95%N2 /5%H2 mixture gas. Fresh saturated solutions of 0.3 M Fe(II) or Fe(III), 0.3 M S2- and 0.2 M As(III) ions were mixed and pH was maintained at pH 4, 6 and 8 by small additions of concentrated HCl or NaOH. At different time intervals, aliquots were extracted from suspensions aged from hours to 1 month and analyzed for total iron, arsenic and sulfur (by ICP-OES and ICP-MS). The Fe-S-As precipitates were characterized by X-ray diffraction (XRD) and synchrotron X-ray absorption spectroscopy (XAS). X-ray diffraction and Fe k-edge EXAFS showed the precipitation of amorphous to poorly crystalline iron sulfide when Fe(II) was co-precipitated with sulfide (no arsenic) at pH 4, 6, and 8. The precipitate that formed in ~1-4 h was nanoparticle-sized and disordered mackinawite (FeS), which showed a characteristic broad, low-intensity Bragg peaks in the XRD patterns. After aging for ~7 d, XRD patterns showed a change to more crystalline mackinawite. In contrast, co-precipitation of As(III) with Fe(II) and sulfide resulted in x-ray amorphous (both synchrotron and laboratory XRD) precipitates for all pH and aging times (~4 h to 1 m). Arsenic and iron XANES and EXAFS spectra of precipitates at pH 4 showed a mixture of amorphous orpiment-type (As2S3) and mackinawite-type (FeS) phases. At pH 6 and 8, XANES showed As sulfide and a

  3. Kinetic Parameters of Secondary Carbide Precipitation in High-Cr White Iron Alloyed by Mn-Ni-Mo-V Complex

    NASA Astrophysics Data System (ADS)

    Efremenko, V. G.; Chabak, Yu. G.; Brykov, M. N.

    2013-05-01

    This study presents kinetics of precipitation of secondary carbides in 14.55%Cr-Mn-Ni-Mo-V white cast iron during the destabilization heat treatment. The as-cast iron was heat treated at temperatures in the range of 800-1100 °C with soaking up to 6 h. Investigation was carried out by optical and electron microscopy, dilatometric analysis, Ms temperature measurement, and bulk hardness evaluation. TTT-curve of precipitation process of secondary carbides (M7C3, M23C6, M3C2) has been constructed in this study. It was determined that the precipitation occurs at the maximum rate at 950 °C where the process is started after 10 s and completed within 160 min further. The precipitation leads to significant increase of Ms temperature and bulk hardness; large soaking times at destabilization temperatures cause coarsening of secondary carbides and decrease in particles number, followed by decrease in hardness. The results obtained are discussed in terms of solubility of carbon in the austenite and diffusion activation of Cr atoms. The precipitation was found to consist of two stages with activation energies of 196.5 kJ/g-mole at the first stage and 47.1 kJ/g-mole at the second stage.

  4. Precipitation of iron in microbial mats of the spring waters of Borra Caves, Vishakapatnam, India: some geomicrobiological aspects

    NASA Astrophysics Data System (ADS)

    Baskar, Sushmitha; Baskar, R.; Lee, Natuschka; Kaushik, A.; Theophilus, P. K.

    2008-11-01

    The Borra caves, Vishakapatnam, India, can be described as a speleothem cave with significant amounts of unexplored microbial mats in spring waters. Here, we present the first observations and hypotheses on the possible impact of the microorganisms in these mats on the cave formation, focusing on their role on iron mineral precipitation. The spring waters (pH neutral 7.5 7.7) contained dissolved metals like iron and the organic mat sludge (pH 7.0 7.3) had a TOC content of approximately 5.4 wt%. Geochemically, the spring waters deep below the microbial mats contained Fe 369 ppb, Sr 198 ppb; and the organic mat sludge contained Mg 9 ppm, Fe 427 ppb, Zn 149 ppb, Sr 190 ppb. XRD observations displayed Fe minerals (dominantly hematite), minor amounts of zinc gallium sulfide and nitrofuryl compounds. At least four groups of bacteria identified by direct microscopy and SEM-EDX on the basis of morphology could be observed in all samples: Leptothrix-like organisms, entombed bacterial mineral sheaths, a few stalks of Gallionella-like organisms and some additional bacteria that could not be further identified. Leptothrix-like organisms contained 43.22 60.08 wt % Fe and the mineral precipitated near and around these bacteria (in the actual unaltered samples on site) contained 30.76 45.22 wt% Fe as identified and quantified by SEM-EDX. This study indicates that the precipitation of these iron-rich mats in the spring waters could be linked to the presence of abundant active communities of iron precipitating bacteria at Borra caves, Vishakapatanam.

  5. Influencing factors in the CO-precipitation process of superparamagnetic iron oxide nano particles: A model based study

    NASA Astrophysics Data System (ADS)

    Roth, Hans-Christian; Schwaminger, Sebastian P.; Schindler, Michael; Wagner, Friedrich E.; Berensmeier, Sonja

    2015-03-01

    The study, presented here, focuses on the impact of synthesis parameters on the co-precipitation process of superparamagnetic iron oxide nanoparticles. Particle diameters between 3 and 17 nm and saturation magnetizations from 26 to 89 Am2 kg-1 were achieved by variation of iron salt concentration, reaction temperature, ratio of hydroxide ions to iron ions and ratio of Fe3+/Fe2+. All synthesis assays were conceived according to the "design of experiments" method. The results were fitted to significant models. Subsequent validation experiments could confirm the models with an accuracy>95%. The characterization of the chemical composition, as well as structural and magnetic properties was carried out using powder X-ray diffraction, transmission electron microscopy, Raman and Mössbauer spectroscopy and superconducting quantum interference device magnetometry. The results reveal that the particles' saturation magnetization can be enhanced by the employment of high iron salt concentrations and a molar ratio of Fe3+/Fe2+ below 2:1. Furthermore, the particle size can be increased by higher iron salt concentrations and a hyperstoichiometric normal ratio of hydroxide ions to iron ions of 1.4:1. Overall results indicate that the saturation magnetization is directly related to the particle size.

  6. Removal of chromium from Cr(VI) polluted wastewaters by reduction with scrap iron and subsequent precipitation of resulted cations.

    PubMed

    Gheju, M; Balcu, I

    2011-11-30

    This work presents investigations on the total removal of chromium from Cr(VI) aqueous solutions by reduction with scrap iron and subsequent precipitation of the resulted cations with NaOH. The process was detrimentally affected by a compactly passivation film occurred at scrap iron surface, mainly composed of Cr(III) and Fe(III). Maximum removal efficiency of the Cr(total) and Fe(total) achieved in the clarifier under circumneutral and alkaline (pH 9.1) conditions was 98.5% and 100%, respectively. The optimum precipitation pH range which resulted from this study is 7.6-8.0. Fe(total) and Cr(total) were almost entirely removed in the clarifier as Fe(III) and Cr(III) species; however, after Cr(VI) breakthrough in column effluent, chromium was partially removed in the clarifier also as Cr(VI), by coprecipitation with cationic species. As long the column effluent was free of Cr(VI), the average Cr(total) removal efficiency of the packed column and clarifier was 10.8% and 78.8%, respectively. Our results clearly indicated that Cr(VI) contaminated wastewater can be successfully treated by combining reduction with scrap iron and chemical precipitation with NaOH.

  7. Structural characteristics of transition-iron-carbide precipitates formed during the first stage of tempering in 4340 steel

    SciTech Connect

    Thompson, S.W.

    2015-08-15

    Microstructural and crystallographic characteristics of fine-scale transition-iron-carbide precipitates formed in martensite during tempering of 4340 steel at 200 °C for 3.6 ks were studied via transmission electron microscopy. Precipitates of near-equiaxed shapes and about 10 nm in size were observed, and rows of closely spaced precipitates were aligned predominantly along < 100 > martensite directions. Aggregates of aligned precipitates were up to 150 nm in length, although occasional kinks were present that disrupted the alignment, and some of the adjacent precipitates possessed somewhat different crystallographic orientations. Electron-diffraction results were analyzed in detail and found to be consistent with both epsilon-carbide and eta-carbide phases. Similarities between these two phases were highlighted and discussed. Experimental electron-diffraction data were compared with data from five different unit cells, and each was found to be consistent within uncertainty ranges of ± 0.003 nm for interplanar spacings, ± 2° for angles between plane normals, and a few degrees for the orientation relationship between precipitates and the matrix.

  8. Origin of life and iron-rich clays

    NASA Technical Reports Server (NTRS)

    Hartman, H. H.

    1986-01-01

    The premise that life began with self-replicating iron-rich clays is explored. In association with these clays and UV light, polar organic molecules, such as oxalic acid, were synthesized. The carbonaceous chondrites have both iron-rich clays and organic molecules. It is convenient to classify meteoritic organic matter into 3 categories: insoluble polymer, hydrocarbons and polar organics (soluble in water). Recent work on the delta D, delta N-15 and delta C-13 has made it clear that these three fractions have been made by three different mechanisms. A significant fraction of the insoluble polymer has a delta-D which suggests that it was made in an interstellar medium. The hydrocarbons seem to have been made on a parent body by a Fischer-Tropsch mechanism. The polar organics were probably synthesized in a mixture of carbonate (NH4)2CO3, Fe(++) ion and liquid water by radiolysis. In a set of experiments the radiolysis of (NH4)2CO3 in the presence and absence of Fe(++) ion has been examined. The synthesis of glycine in the presence of Fe(++) ion is 3-4 times that in the absence of ferrous ion. The effects of the addition of hydrocarbons to this mixture are explored. Iron-rich clays at low temperature and pressure are synthesized. So far the results are not sufficiently crystalline to look for replication. It should be noted that organic chelating agents such as oxalic acid do increase the crystallinity of the clays but not sufficiently. The hydrothermal synthesis of iron-rich clays is being examined.

  9. Coprecipitation of arsenate with metal oxides. 3. Nature, mineralogy, and reactivity of iron(III)-aluminum precipitates.

    PubMed

    Violante, Antonio; Pigna, Massimo; Del Gaudio, Stefania; Cozzolino, Vincenza; Banerjee, Dipanjan

    2009-03-01

    Coprecipitation involving arsenic with aluminum or iron has been studied because this technique is considered particularly efficient for removal of this toxic element from polluted waters. Coprecipitation of arsenic with mixed iron-aluminum solutions has received scant attention. In this work we studied (i)the mineralogy, surface properties, and chemical composition of mixed iron-aluminum oxides formed at initial Fe/Al molar ratio of 1.0 in the absence or presence of arsenate [As/ Fe+Al molar ratio (R) of 0, 0.01, or 0.1] and at pH 4.0, 7.0, and 10.0 and aged for 30 and 210 days at 50 degrees C and (ii) the removal of arsenate from the coprecipitates after addition of phosphate. The amounts of short-range ordered precipitates (ferrihydrite, aluminous ferrihydrite and/or poorly crystalline boehmite) were greater than those found in iron and aluminum systems (studied in previous works), due to the capacity of both aluminum and arsenate to retard or inhibitthe transformation of the initially formed precipitates into well-crystallized oxides (gibbsite, bayerite, and hematite). As a consequence, the surface areas of the iron-aluminum oxides formed in the absence or presence of arsenate were usually much larger than those of aluminum or iron oxides formed under the same conditions. Arsenate was found to be associated mainly into short-range ordered materials. Chemical composition of all samples was affected by pH, initial R, and aging. Phosphate sorption was facilitated by the presence of short-range ordered materials, mainly those richer in aluminum, but was inhibited by arsenate present in the samples. The quantities of arsenate replaced by phosphate, expressed as percentages of its total amount present in the samples, were particularly low, ranging from 10% to 26%. A comparison of the desorption of arsenate by phosphate from aluminum-arsenate and iron-arsenate (studied in previous works) and iron-aluminum-arsenate coprecipitates evidenced that phosphate has a greater

  10. Chemical characterization of iron oxide precipitates from wetlands constructed to treat polluted mine drainage

    SciTech Connect

    Fish, C.L.; Partezana, J.M.; Hedin, R.S.

    1996-12-31

    The passive treatment of abandoned mine drainage using wetlands will produce a significant amount of iron rich sludge which will require costly removal and disposal. An alternative to disposal may be the use of this iron oxide material as pigments which could defray some of these costs. In this research, iron deposits from five alkaline mine drainage wetlands were collected and a series of standard tests were run. The tests included loss on ignition, moisture, pH, acid soluble metals, oil absorption, and water soluble matter. The results of these tests were compared to those achieved using commercially available natural and synthetic iron oxides. The results indicate that iron oxides from constructed wetlands have chemical properties that are intermediate to those of natural and synthetic iron oxide products.

  11. Bacteria attenuation by iron electrocoagulation governed by interactions between bacterial phosphate groups and Fe(III) precipitates.

    PubMed

    Delaire, Caroline; van Genuchten, Case M; Amrose, Susan E; Gadgil, Ashok J

    2016-10-15

    Iron electrocoagulation (Fe-EC) is a low-cost process in which Fe(II) generated from an Fe(0) anode reacts with dissolved O2 to form (1) Fe(III) precipitates with an affinity for bacterial cell walls and (2) bactericidal reactive oxidants. Previous work suggests that Fe-EC is a promising treatment option for groundwater containing arsenic and bacterial contamination. However, the mechanisms of bacteria attenuation and the impact of major groundwater ions are not well understood. In this work, using the model indicator Escherichia coli (E. coli), we show that physical removal via enmeshment in EC precipitate flocs is the primary process of bacteria attenuation in the presence of HCO3(-), which significantly inhibits inactivation, possibly due to a reduction in the lifetime of reactive oxidants. We demonstrate that the adhesion of EC precipitates to cell walls, which results in bacteria encapsulation in flocs, is driven primarily by interactions between EC precipitates and phosphate functional groups on bacteria surfaces. In single solute electrolytes, both P (0.4 mM) and Ca/Mg (1-13 mM) inhibited the adhesion of EC precipitates to bacterial cell walls, whereas Si (0.4 mM) and ionic strength (2-200 mM) did not impact E. coli attenuation. Interestingly, P (0.4 mM) did not affect E. coli attenuation in electrolytes containing Ca/Mg, consistent with bivalent cation bridging between bacterial phosphate groups and inorganic P sorbed to EC precipitates. Finally, we found that EC precipitate adhesion is largely independent of cell wall composition, consistent with comparable densities of phosphate functional groups on Gram-positive and Gram-negative cells. Our results are critical to predict the performance of Fe-EC to eliminate bacterial contaminants from waters with diverse chemical compositions.

  12. Thermodynamic and mechanical properties of copper precipitates in α-iron from atomistic simulations

    NASA Astrophysics Data System (ADS)

    Erhart, Paul; Marian, Jaime; Sadigh, Babak

    2013-07-01

    Precipitate hardening is commonly used in materials science to control strength by acting on the number density, size distribution, and shape of solute precipitates in the hardened matrix. The Fe-Cu system has attracted much attention over the last several decades due to its technological importance as a model alloy for Cu steels. In spite of these efforts several aspects of its phase diagram remain unexplained. Here we use atomistic simulations to characterize the polymorphic phase diagram of Cu precipitates in body-centered cubic (BCC) Fe and establish a consistent link between their thermodynamic and mechanical properties in terms of thermal stability, shape, and strength. The size at which Cu precipitates transform from BCC to a close-packed 9R structure is found to be strongly temperature dependent, ranging from approximately 4 nm in diameter (˜2700atoms) at 200 K to about 8 nm (˜22800atoms) at 700 K. These numbers are in very good agreement with the interpretation of experimental data given Monzen [Philos. Mag. APMAADG0141-861010.1080/01418610008212077 80, 711 (2000)]. The strong temperature dependence originates from the entropic stabilization of BCC Cu, which is mechanically unstable as a bulk phase. While at high temperatures the transition exhibits first-order characteristics, the hysteresis, and thus the nucleation barrier, vanish at temperatures below approximately 300 K. This behavior is explained in terms of the mutual cancellation of the energy differences between core and shell (wetting layer) regions of BCC and 9R nanoprecipitates, respectively. The proposed mechanism is not specific for the Fe-Cu system but could generally be observed in immiscible systems, whenever the minority component is unstable in the lattice structure of the host matrix. Finally, we also study the interaction of precipitates with screw dislocations as a function of both structure and orientation. The results provide a coherent picture of precipitate strength that unifies

  13. Iron

    MedlinePlus

    ... cereals and breads. White beans, lentils, spinach, kidney beans, and peas. Nuts and some dried fruits, such as raisins. Iron in food comes in two forms: heme iron and nonheme iron. Nonheme iron is found in plant foods and iron-fortified food products. Meat, seafood, ...

  14. Iron

    MedlinePlus

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  15. Precipitation hardenable iron-nickel-chromium alloy having good swelling resistance and low neutron absorbence

    DOEpatents

    Korenko, Michael K.; Merrick, Howard F.; Gibson, Robert C.

    1980-01-01

    An iron-nickel-chromium age-hardenable alloy suitable for use in fast breeder reactor ducts and cladding which utilizes the gamma-double prime strengthening phase and characterized in having a morphology of the gamma-double prime phase enveloping the gamma-prime phase and delta phase distributed at or near the grain boundaries. The alloy consists essentially of about 40-50% nickel, 7.5-14% chromium, 1.5-4% niobium, 0.25-0.75% silicon, 1-3% titanium, 0.1-0.5% aluminum, 0.02-0.1% carbon, 0.002-0.015% boron, and the balance iron. Up to 2% manganese and up to 0.01% magnesium may be added to inhibit trace element effects; up to 0.1% zirconium may be added to increase radiation swelling resistance; and up to 3% molybdenum may be added to increase strength.

  16. Co-precipitation of phosphate and iron limits mitochondrial phosphate availability in Saccharomyces cerevisiae lacking the yeast frataxin homologue (YFH1).

    PubMed

    Seguin, Alexandra; Santos, Renata; Pain, Debkumar; Dancis, Andrew; Camadro, Jean-Michel; Lesuisse, Emmanuel

    2011-02-25

    Saccharomyces cerevisiae cells lacking the yeast frataxin homologue (Δyfh1) accumulate iron in the mitochondria in the form of nanoparticles of ferric phosphate. The phosphate content of Δyfh1 mitochondria was higher than that of wild-type mitochondria, but the proportion of mitochondrial phosphate that was soluble was much lower in Δyfh1 cells. The rates of phosphate and iron uptake in vitro by isolated mitochondria were higher for Δyfh1 than wild-type mitochondria, and a significant proportion of the phosphate and iron rapidly became insoluble in the mitochondrial matrix, suggesting co-precipitation of these species after oxidation of iron by oxygen. Increasing the amount of phosphate in the medium decreased the amount of iron accumulated by Δyfh1 cells and improved their growth in an iron-dependent manner, and this effect was mostly transcriptional. Overexpressing the major mitochondrial phosphate carrier, MIR1, slightly increased the concentration of soluble mitochondrial phosphate and significantly improved various mitochondrial functions (cytochromes, [Fe-S] clusters, and respiration) in Δyfh1 cells. We conclude that in Δyfh1 cells, soluble phosphate is limiting, due to its co-precipitation with iron.

  17. The precipitation of aluminum, iron and manganese at the junction of Deer Creek with the Snake River in Summit County, Colorado

    USGS Publications Warehouse

    Theobald, P.K.; Lakin, H.W.; Hawkins, D.B.

    1963-01-01

    The oxidation of disseminated pyrite in relatively acid schists and gneisses of the Snake River drainage basin provides abundant iron sulfate and sulfuric acid to ground and surface water. This acid water dissolves large quantities of many elements, particularly aluminum and surprisingly large quantities of elements, such as magnesium and zinc, not expected to be abundant in the drainage basin. The adjoining drainage to the west, Deer Creek, is underlain by basic rocks, from which the water inherits a high pH. Despite the presence of base- and precious- metal veins in the drainage basin of Deer Creek, it carries less metal than the Snake River. The principal precipitate on the bed of the Snake River is hydrated iron oxide with small quantities of the other metals. In Deer Creek manganese oxide is precipitated with iron oxide and large quantities of other metals are carried down with this precipitate. Below the junction of these streams the pH stabilizes at a near-neutral value. Iron is removed from the Snake River water at the junction, and aluminum is precipitated for some distance downstream. The aluminum precipitate carries down other metals in concentrations slightly less than that in the manganese precipitate on Deer Creek. The natural processes observed in this junction if carried to a larger scale could provide the mechanism described by Ansheles (1927) for the formation of bauxite. In the environment described, geochemical exploration by either water or stream sediment techniques is difficult because of (1) the extreme pH differential between the streams above their junction and (2) the difference in the precipitates formed on the streambeds. ?? 1963.

  18. Vivianite precipitation and phosphate sorption following iron reduction in anoxic soils.

    PubMed

    Heiberg, Lisa; Koch, Christian Bender; Kjaergaard, Charlotte; Jensen, Henning S; Hans Christian, B Hansen

    2012-01-01

    Phosphorus retention in lowland soils depends on redox conditions. The aim of this study was to evaluate how the Fe(III) reduction degree affects phosphate adsorption and precipitation. Two similarly P-saturated, ferric Fe-rich lowland soils, a sandy and a peat soil, were incubated under anaerobic conditions. Mössbauer spectroscopy demonstrated that Fe(III) in the sandy soil was present as goethite and phyllosilicates, whereas Fe(III) in the peat soil was mainly present as polynuclear, Fe-humic complexes. Following anoxic incubation, extensive formation of Fe(II) in the solids occurred. After 100 d, the Fe(II) production reached its maximum and 34% of the citrate-bicarbonate-dithionite extractable Fe (Fe(CBD)) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of Fe(CBD) was reached after 200 d. Neoformation of a metavivianite/vivianite phase under anoxic conditions was identified by X-ray diffraction in the peat. The sandy soil exhibited small changes in the point of zero net sorption (EPC₀) and P(i) desorption with increasing Fe(III) reduction, whereas in the peat soil P desorption increased from 80 to 3100 μmol kg⁻¹ and EPC₀ increased from 1.7 to 83 μM, after 322 d of anoxic incubation. The fast Fe(III) reduction made the peat soils particularly vulnerable to changes in redox conditions. However, the precipitation of vivianite/metavivianite minerals may control soluble P(i) concentrations to between 2 and 3 μM in the long term if the soil is not disturbed.

  19. Solids precipitation in crude oils, gas-to-liquids and their blends

    NASA Astrophysics Data System (ADS)

    Ramanathan, Karthik

    Gas-to-liquids (GTL) liquids are obtained from syngas by the Fischer-Tropsch synthesis. The blending of GTL liquids produced from natural gas/coal reserves and crude oils is a possibility in the near future for multiple reasons. Solids precipitation is a major problem in pipelines and refineries leading to significant additional operating costs. The effect of the addition of a paraffinic GTL liquid to crude oils on solids precipitation was investigated in this study. A Fourier transform infrared (FT-IR) spectroscopic technique was used to obtain solid-liquid equilibria (SLE) data for the various samples. The SLE of multiple systems of model oils composed of n-alkanes was investigated preliminarily. Blends of a model oil simulating a GTL liquid composition and a crude oil showed that the wax precipitation temperature (WPT) decreased upon blending. Three crude oils from different geographic regions (Alaskan North Slope, Colorado and Venezuela) and a laboratory-produced GTL liquid were used in the preparation of blends with five different concentrations of the GTL liquid. The wax precipitation temperatures of the blends were found to decrease with the increasing addition of the GTL liquid for all the oils. This effect was attributed to the solvent effect of the low molecular weight-paraffinic GTL liquid on the crude oils. The weight percent solid precipitated that was estimated as a function of temperature did not show a uniform trend for the set of crude oils. The asphaltene onset studies done on the blends with near-infrared spectroscopy indicated that the addition of GTL liquid could have a stabilizing effect on the asphaltenes in some oils. Analytical techniques such as distillation, solvent separation, HPLC, GC, and GPC were used to obtain detailed composition data on the samples. Two sets of compositional data with 49 and 86 pseudo-components were used to describe the three crude oils used in the blending work. The wax precipitation was calculated using a

  20. Polycyclic aromatic hydrocarbon emission profiles and removal efficiency by electrostatic precipitator and wetfine scrubber in an iron ore sintering plant.

    PubMed

    Guerriero, Ettore; Lutri, Antonina; Mabilia, Rosanna; Scianò, Maria Concetta Tomasi; Rotatori, Mauro

    2008-11-01

    A monitoring campaign of polychlorinated dibenzo-p-dioxins and dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyl was carried out in an Italian iron ore sintering plant by sampling the combustion gases at the electrostatic precipitator (ESP) outlet, at the Wetfine scrubber (WS) outlet, and by collecting the ESP dust. Few data are available on these micropollutants produced in iron ore sintering plants, particularly from Italian plants. This study investigates the PAH emission profiles and the removal efficiency of ESPs and WS. PAHs were determined at the stack, ESP outlet flue gases, and in ESP dust to characterize the emission profiles and the performance of the ESP and the WS for reducing PAH emission. The 11 PAHs monitored are listed in the Italian legislative decree 152/2006. The mean total PAH sum concentration in the stack flue gases is 3.96 microg/N x m3, in ESP outlet flue gases is 9.73 microg/N x m3, and in ESP dust is 0.53 microg/g. Regarding the emission profiles, the most abundant compound is benzo(b)fluoranthene, which has a relative low BaP toxic equivalency factors (TEF) value, followed by dibenzo(a,l)pyrene, which has a very high BaP(TEF) value. The emission profiles in ESP dust and in the flue gases after the ESP show some changes, whereas the fingerprint in ESP and stack flue gases is very similar. The removal efficiency of the ESP and of WS on the total PAH concentration is 5.2 and 59.5%, respectively.

  1. Polycyclic aromatic hydrocarbon emission profiles and removal efficiency by electrostatic precipitator and wetfine scrubber in an iron ore sintering plant

    SciTech Connect

    Ettore Guerriero; Antonina Lutri; Rosanna Mabilia; Maria Concetta Tomasi Sciano; Mauro Rotatori

    2008-11-15

    A monitoring campaign of polychlorinated dibenzo-p-dioxins and dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyl was carried out in an Italian iron ore sintering plant by sampling the combustion gases at the electrostatic precipitator (ESP) outlet, at the Wetfine scrubber (WS) outlet, and by collecting the ESP dust. Few data are available on these micropollutants produced in iron ore sintering plants, particularly from Italian plants. This study investigates the PAH emission profiles and the removal efficiency of ESPs and WS. PAHs were determined at the stack, ESP outlet flue gases, and in ESP dust to characterize the emission profiles and the performance of the ESP and the WS for reducing PAH emission. The 11 PAHs monitored are listed in the Italian legislative decree 152/2006. The mean total PAH sum concentration in the stack flue gases is 3.96 {mu}g/N m{sup 3}, in ESP outlet flue gases is 9.73 {mu}g/N m{sup 3}, and in ESP dust is 0.53 {mu}g/g. Regarding the emission profiles, the most abundant compound is benzo(b)fluoranthene, which has a relative low BaP toxic equivalency factors (TEF) value, followed by dibenzo(a,l)pyrene, which has a very high BaP(TEF) value. The emission profiles in ESP dust and in the flue gases after the ESP show some changes, whereas the fingerprint in ESP and stack flue gases is very similar. The removal efficiency of the ESP and of WS on the total PAH concentration is 5.2 and 59.5%, respectively. 2 figs., 5 tabs.

  2. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.

    1999-01-01

    The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

  3. Organic matter formed from hydrolysis of metal carbides of the iron peak of cosmic elemental abundance

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco

    2003-01-01

    inside the iron peak of the cosmic abundances) has been discussed as well. A survey of the hydrolytic behaviour of other carbides has been included so that all lanthanides and actinides are considered as well as carbides of the second and third groups of the periodic table of elements and highly refractory carbides such as those of Ti, Zr, Ta and W have been briefly discussed. Furthermore, the hydrolysis of mixed metal carbides and nitrides is discussed, which gives a mixture of extremely interesting molecules that are considered the raw materials for the formation of the molecules of life: guanidine, methyl hydrazine, formic acid, hydrogen cyanide, urea, cyanamide, methylamine and formaldehyde. The hydrolysis of metal carbides has also been discussed within the framework of other reactions that are well considered in the present day in an astrochemical context: the ion-molecule reaction, the Miller-Urey and the Sagan-Kaare synthesis as well as the catalytic Fischer-Tropsch synthesis and the radiation-driven Fischer-Tropsch synthesis.

  4. Water-Rock Interaction Simulations of Iron Oxide Mobilization and Precipitation: Implications of Cross-diffusion Reactions for Terrestrial and Mars 'Blueberry' Hematite Concretions

    NASA Astrophysics Data System (ADS)

    Park, A. J.; Chan, M. A.; Parry, W. T.

    2005-12-01

    Modeling of how terrestrial concretions form can provide valuable insights into understanding water-rock interactions that led to the formation of hematite concretions at Meridiani Planum, Mars. Numerical simulations of iron oxide concretions in the Jurassic Navajo Sandstone of southern Utah provide physical and chemical input parameters for emulating conditions that may have prevailed on Mars. In the terrestrial example, iron oxide coatings on eolian sand grains are reduced and mobilized by methane or petroleum. Precipitation of goethite or hematite occurs as Fe interacts with oxygen. Conditions that produced Navajo Sandstone concretions can range from a regional scale that is strongly affected by advection of large pore volumes of water, to small sub-meter scale features that are dominantly controlled by diffusive processes. Hematite concretions are results of a small-scale cross-diffusional process, where Fe and oxygen are supplied from two opposite sides from the 'middle' zone of mixing where concretions precipitate. This is an ideal natural system where Liesegang banding and other self-organized patterns can evolve. A complicating variable here is the sedimentologic (both mineralogic and textural) heterogeneity that, in reality, may be the key factor controlling the nucleation and precipitation habits (including possible competitive growth) of hematite concretions. Sym.8 water-rock interaction simulator program was used for the Navajo Sandstone concretions. Sym.8 is a water-rock simulator that accounts for advective and diffusive mass-transfer, and equilibrium and kinetic reactions. The program uses a dynamic composite media texture model to address changing sediment composition and texture to be consistent with the reaction progress. Initial one-dimensional simulation results indicate precipitation heterogeneity in the range of sub-meters, e.g., possible banding and distribution of iron oxide nodules may be centimeters apart for published diffusivities and

  5. Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

    NASA Astrophysics Data System (ADS)

    Pušnik, Klementina; Goršak, Tanja; Drofenik, Miha; Makovec, Darko

    2016-09-01

    There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe3+/Fe2+ ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles' formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe3+ ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH.

  6. Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

    SciTech Connect

    Enrique Iglesia

    2004-09-30

    This project explores the extension of previously discovered Fe-based catalysts with unprecedented Fischer-Tropsch synthesis rate, selectivity, and ability to convert hydrogen-poor synthesis gas streams typical of those produced from coal and biomass sources. Contract negotiations were completed on December 9, 2004. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic performance previously reported. During this second reporting period, we have prepared and tested several Fe-based compositions for Fischer-Tropsch synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. These studies established modest improvements in rates and selectivities with light hydrocarbon recycle without any observed deleterious effects, opening up the opportunities for using of recycle strategies to control temperature profiles in fixed-bed Fe-based Fischer-Tropsch synthesis reactors without any detectable kinetic detriment. In a parallel study, we examined similar effects of recycle for cobalt-based catalysts; marked selectivity improvements were observed as a result of the removal of significant transport restrictions on these catalysts. Finally, we have re-examined some previously unanalyzed data dealing with the mechanism of the Fischer-Tropsch synthesis, specifically kinetic isotope effects on the rate and selectivity of chain growth reactions on Fe-based catalysts.

  7. PCDD/Fs removal efficiency by electrostatic precipitator and wetfine scrubber in an iron ore sintering plant.

    PubMed

    Guerriero, Ettore; Guarnieri, Alessandra; Mosca, Silvia; Rossetti, Gianluca; Rotatori, Mauro

    2009-12-30

    This study investigates the removal efficiency of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) by the APCDs of an iron ore sintering plant, an electrostatic precipitator (ESP) and a wetfine scrubbing system (WS). The removal efficiencies of the ESP on the total PCDD/Fs concentration and the total PCDD/Fs I-TEQ concentration are 44.3% and 41.4%, respectively, while those of the WS are 66.7% and 68.4%, respectively, but the vapor/solid phase distribution changes after APCDs abatement. At ESP inlet, the PCDD/Fs account for 31.2% in vapor phase and for 68.8% in particulate phase while, at ESP outlet, the PCDD/Fs account for 63.3% in vapor phase and for 36.7% in solid phase. The ESP removes effectively solid-phase PCDD/Fs for its effectiveness to capture the particulate while it is ineffective in removing vapor-phase PCDD/Fs. It, on the contrary, increase for the vaporization within the ESP, especially for these congeners with a lower chlorination degree, and for the PCDD/Fs "stripping" from particulate to gas-phase during the sampling. At WS inlet, the PCDD/Fs account for 63.3% in vapor phase and for 36.7% in solid phase while, at WS outlet, the PCDD/Fs account for 21.4% in vapor phase and for 78.6% in solid phase. Considering that WS outlet temperature is about 40 degrees C, the PCDD/Fs vapor-phase condense to particles: therefore, even if the particulate is removed by WS, the final result is that PCDD/Fs percentage decreases in vapor-phase and increases in solid-phase.

  8. Particle size effect for cobalt Fischer-Tropsch catalysts based on in situ CO chemisorption

    NASA Astrophysics Data System (ADS)

    Yang, Jia; Frøseth, Vidar; Chen, De; Holmen, Anders

    2016-06-01

    The cobalt particle size effect on activity and selectivity for CO hydrogenation was revisited on cobalt catalysts supported on a large variety of supports at 483 K, 1.85 bar, and H2/CO/Ar = 15/1.5/33.5 Nml/min. The size dependence of the activity and selectivity was analyzed in terms of site coverage and rate constants based on SSITKA experimental results. It was found that the Co particle size index estimated by the conventional method, namely, ex situ hydrogen chemisorption, could not correlate well the activity and selectivity as a function of the particle size index. The same holds for the site coverage of CO and intermediates leading to methane formation. However, the cobalt particle size index based on in situ CO chemisorption measured at 373 K provides a good correlation for turnover frequencies (TOFs) at reaction conditions. It was observed that TOF for CO conversion (TOFCO) increased with increasing particle size index of cobalt and SSITKA experiments showed that this was possibly due to increased site coverage of CO. The TOF for methane formation (TOFCH4) increased with particle size and remained constant at higher particle sizes possibly due to combined effect from the site coverage of intermediates leading to methane (θCHx) and the pseudo-first-order rate constant (kt). The results suggest that the support can play an important role for the size dependence of the activity and selectivity of CO hydrogenation on Co catalysts.

  9. Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

  10. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objective for this quarter was to study the effect of co-feeding a 1-olefin on the Ruhrchemie catalyst activity and selectivity, during-both conventional Fisher-Tropsch synthesis (FTS) and FTS under supercritical conditions. We used propane as the supercritical fluid and 1-dodecene (1-C{sub 12}H{sub 24}) in this test. Motivation for this study was the work of Fujimoto and co-workers who reported that suppression of methane and enhancement of high molecular weight hydrocarbons selectivities occurs with co-feeding of 1-olefins (1-heptene, 1-tetradecene, or 1-hexadecene) during FTS under supercritical conditions, but not during the conventional FTS (Co-La catalyst supported on silica in supercritical n-pentane).The diffusion coefficients of products in supercritical fluids is discussed.

  11. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, October--December 1994

    SciTech Connect

    1994-12-31

    All major tasks associated with the contract study have essentially been completed. Our activities during this quarter comprise mainly of project documentation, management and administration. Topical reports which document the accomplishments of the various tasks were issued. As a result of the current contract study, DOE/PETC is contemplating to modify the subject contract to include: replacing hydrocracking with FCC as an alternative scheme for F-T wax upgrading; enhancing the ZSM-5 reactor ASPEN modeling algorithm; incorporating the ZSM-5 reaction scheme to the Western Coal Case, and considering F-T synthesis using natural gas as feedstock. A detailed scope of work for the above tasks with a formal cost proposal was submitted to DOE/PETC for consideration.

  12. ULTRA-CLEAN FISCHER-TROPSCH FUELS PRODUCTION AND DEMONSTRATION PROJECT

    SciTech Connect

    Steve Bergin

    2004-10-18

    The Report Abstract provides summaries of the past year's activities relating to each of the main project objectives. Some of the objectives will be expanded on in greater detail further down in the report. The following objectives have their own addition sections in the report: SFP Construction and Fuel Production, Impact of SFP Fuel on Engine Performance, Fleet Testing at WMATA and Denali National Park, Demonstration of Clean Diesel Fuels in Diesel Electric Generators in Alaska, and Economic Analysis. ICRC provided overall project organization and budget management for the project. ICRC held meetings with various project participants. ICRC presented at the Department of Energy's annual project review meeting. The plant began producing fuel in October 2004. The first delivery of finished fuel was made in March of 2004 after the initial start-up period.

  13. The benefits of Fischer-Tropsch waxes in synthetic petroleum jelly.

    PubMed

    Bekker, M; Louw, N R; Jansen Van Rensburg, V J; Potgieter, J

    2013-02-01

    This article is an introduction and general discussion regarding the use of Fisher-Tropsch wax in petroleum jelly applications. Traditionally, petroleum jelly is prepared from a blend of microwax, paraffin wax and mineral oil that are all derived from crude oil. Sasol Wax has successfully prepared a petroleum jelly based on predominantly to fully synthetic Fisher-Tropsch wax. Sasol Wax was awarded a patent P53898ZP00-29 November 11 for a predominantly to fully synthetic petroleum jelly based on Fisher-Tropsch wax blends. The benefits of Fisher-Tropsch wax discussed in this article include the absence of aromatic compounds and polycyclic aromatic compounds in Fisher-Tropsch wax as well as the sustainable production that is possible with Fisher-Tropsch wax, as opposed to paraffin wax that may be affected by the closure of group I Base Oil plants. This article will be the first in a series of articles from the same authors, and follow-up articles will include solid-state nuclear magnetic resonance and crystallization studies to determine the influence of predominantly synthetic waxes on petroleum jelly network structures compared with more traditional mineral oil-derived petroleum jellies, final product performance and stability of synthetic petroleum jelly used in, for example, personal care lotions or creams. The influence of oxygenated compounds and product safety and rheological properties (including primary skin feel upon application and secondary skin feel after application) of synthetic petroleum jellies compared with traditional mineral oil-derived petroleum jellies are discussed.

  14. Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

    DOEpatents

    Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

    2001-01-01

    A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.

  15. Separation of Fischer-Tropsch Wax from Catalyst by Supercritical Extraction

    SciTech Connect

    Mark C. Thies; Patrick C. Joyce

    1998-01-31

    Further progress in achieving the objectives of the project was made in the period of January I to March 31, 1998. The direct numerical simulation of particle removal process in turbulent gas flows was completed. Variations of particle trajectories are studied. It is shown that the near wall vortices profoundly affect the particle removal process in turbulent boundary layer flows. Experimental data for transport and deposition of fibrous particles in the aerosol wind tunnel was obtained. The measured deposition velocity for irregular fibrous particles is compared with the empirical correlation and the available data for glass fibers and discussed. Additional progress on the sublayer model for evaluating the particle deposition and resuspension in turbulent flows was made.

  16. Ultra-Clean Fischer-Tropsch Fuels Production and Demonstration Project

    SciTech Connect

    Steve Bergin

    2005-10-14

    The Report Abstract provides summaries of the past year's activities relating to each of the main project objectives. Some of the objectives will be expanded on in greater detail further down in the report. The following objectives have their own addition sections in the report: Dynamometer Durability Testing, the Denali Bus Fleet Demonstration, Bus Fleet Demonstrations Emissions Analysis, Impact of SFP Fuel on Engine Performance, Emissions Analysis, Feasibility Study of SFPs for Rural Alaska, and Cold Weather Testing of Ultra Clean Fuel.

  17. Stability and effects of carbon-induced surface reconstructions in cobalt Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Ciobîcă, I. M.; van Helden, P.; van Santen, R. A.

    2016-11-01

    This computational study of carbon induced reconstruction of Co surfaces demonstrates that surface reconstruction is stable in the presence of a hydrogen at low coverage. These reconstructions can create new sites that allow for low activation energy CO dissociation. Carbon induced surface reconstruction of the edge of the FCC-Co(221) step surface will result in highly reactive step-edge sites. Such sites also provide a low activation energy for carbon to diffuse into the subsurface layer of cobalt.

  18. The benefits of Fischer-Tropsch waxes in synthetic petroleum jelly.

    PubMed

    Bekker, M; Louw, N R; Jansen Van Rensburg, V J; Potgieter, J

    2013-02-01

    This article is an introduction and general discussion regarding the use of Fisher-Tropsch wax in petroleum jelly applications. Traditionally, petroleum jelly is prepared from a blend of microwax, paraffin wax and mineral oil that are all derived from crude oil. Sasol Wax has successfully prepared a petroleum jelly based on predominantly to fully synthetic Fisher-Tropsch wax. Sasol Wax was awarded a patent P53898ZP00-29 November 11 for a predominantly to fully synthetic petroleum jelly based on Fisher-Tropsch wax blends. The benefits of Fisher-Tropsch wax discussed in this article include the absence of aromatic compounds and polycyclic aromatic compounds in Fisher-Tropsch wax as well as the sustainable production that is possible with Fisher-Tropsch wax, as opposed to paraffin wax that may be affected by the closure of group I Base Oil plants. This article will be the first in a series of articles from the same authors, and follow-up articles will include solid-state nuclear magnetic resonance and crystallization studies to determine the influence of predominantly synthetic waxes on petroleum jelly network structures compared with more traditional mineral oil-derived petroleum jellies, final product performance and stability of synthetic petroleum jelly used in, for example, personal care lotions or creams. The influence of oxygenated compounds and product safety and rheological properties (including primary skin feel upon application and secondary skin feel after application) of synthetic petroleum jellies compared with traditional mineral oil-derived petroleum jellies are discussed. PMID:23050609

  19. Baseline design/economics for advanced Fischer-Tropsch technology. Quarterly report, July--September 1994

    SciTech Connect

    1994-12-31

    This report is Bechtel`s twelfth quarterly technical progress report and covers the period of July through September, 1994. All major tasks associated with the contract study have essentially been completed. Effort is under way in preparing various topical reports for publication. The objectives of this study are to: Develop a baseline design and two alternative designs for indirect liquefaction using advanced F-T technology. The baseline design uses Illinois No. 6 Eastern Coal and conventional refining. There is an alternative refining case using ZSM-5 treatment of the vapor stream from the slurry F-T reactor and an alternative coal case using Western coal from the Powder River Basin. Prepare the capital and operating costs for the baseline design and the alternatives. Individual plant costs for the alternative cases win be prorated on capacity, wherever possible, from the baseline case. Develop a process flowsheet simulation (PFS) model; establish the baseline design and alternatives; evaluate baseline and alternative economics; develop engineering design criteria; develop a process flowsheet simulation (PFS) model; perform sensitivity studies using the PFS model; document the PFS model and develop a DOE training session on its use; and perform project management, technical coordination and other miscellaneous support functions. Tasks 1, 2, 3 and 5 have essentially been completed. Effort is under way in preparing topical reports for publication. During the current reporting period, work progressed on Tasks 4, 6 and 7. This report covers work done during this period and consists of four sections: Introduction and Summary; Task 4 - Process Flowsheet Simulation (PFS) Model and Conversion to ASPEN PLUS; Task 6 - Document the PFS model and develop a DOE training session on its use; and Project Management and Staffing Report.

  20. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions

    NASA Astrophysics Data System (ADS)

    Shibuya, Takazo; Russell, Michael J.; Takai, Ken

    2016-02-01

    Thermodynamic calculations of mixing between hypothetical seawater and hydrothermal fluid in the Hadean deep ocean were carried out to predict saturation states of mineral precipitates and redox reactions that could occur in Hadean submarine alkaline hydrothermal systems associated with the serpentinization of ultramafic rocks. In the calculations, the seawater was assumed to be weakly acidic (pH = 5.5) and to include carbon dioxide, ferrous iron and silica, with or without nitrate, while the Hadean hydrothermal fluid was assumed to be highly alkaline (pH = 11) and to contain abundant molecular hydrogen, methane and bisulfide, based on the Archean geologic record, the modern low-temperature alkaline hydrothermal vent fluid (Lost City field), and experimental and theoretical considerations. The modeling indicates that potential mineral precipitates in the mixing zone (hydrothermal chimney structures) could consist mainly of iron sulfides but also of ferrous serpentine and brucite, siderite, and ferric iron-bearing minerals such as goethite, hematite and/or magnetite as minor phases. The precipitation of ferric iron-bearing minerals suggests that chemical iron oxidation would be made possible by pH shift even under anoxic condition. In the mixing zone, comprising an inorganic barrier precipitated at the interface of the two contrasting solutions, various redox reactions release free energy with the potential to drive endergonic reactions, assuming the involvement of coupling inorganic protoenzymes. Hydrogenotrophic methanogenesis and acetogenesis - long considered the most ancient forms of biological energy metabolisms - are able to achieve higher maximum energy yield (>0.5 kJ/kg hydrothermal fluid) than those in the modern serpentinization-associated seafloor hydrothermal systems (e.g., Kairei field). Furthermore, the recently proposed methanotrophic acetogenesis pathway was also thermodynamically investigated. It is known that methanotrophic acetogenesis would

  1. Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

    SciTech Connect

    Chen, N; Jiang, D T; Cutler, J; Kotzer, T; Jia, Y F; Demopoulos, G P; Rowson, J W

    2009-12-01

    X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Fe K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the

  2. Aquifer Thermal Energy Storage as an ecosystem service for Brussels, Belgium: investigating iron (hydr)oxide precipitation with reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Anibas, Christian; Possemiers, Mathias; Huysmans, Marijke

    2016-04-01

    In an evolving energy system it is important that urbanized areas contribute to their own energy demands. To reduce greenhouse gas emissions sustainable energy systems with a high efficiency are required, e.g. using urban aquifers as an ecosystem service. Here the potential of seasonal aquifer thermal energy storage and recovery (ATES) for the Brussels-Capital Region, Belgium is investigated. An important shallow geologic formation in the Brussels Capital Region is the Brussels Sand formation, a 20-60 m thick phreatic aquifer. The Brussels Sand Formation is known for its potential for ATES systems, but also for its varying redox and hydraulic conditions. Important limiting factors for ATES systems in the Brussels Sand Formation therefore are the hydraulic conductivity and the geochemical composition of the groundwater. Near the redox boundary iron hydroxide precipitation can negatively influence ATES well performance due to clogging. The interactions between physical processes (e.g. particle transport and clogging in the wider proximity of the ATES well) and chemical processes (e.g. influence of the operation temperatures on precipitation processes) during ATES operation are complex but not well understood. Therefore we constructed numerical groundwater flow models in MODFLOW to estimate maximum pumping and injection rates of different hydraulic conditions and competing water uses in the Brussels Sand Formation. In further steps the thermal potential for ATES was quantified using MT3DMS and the reactive transport model PHT3D was applied to assess the effects of operating ATES systems near the redox boundary. Results show that initial mixing plays an important role in the development of iron(hydr)oxide precipitation around the ATES wells, with the highest concentrations around the cold wells. This behavior is enhanced by the temperature effect; temperature differences of ΔT≈10°C already influence the iron (hydr)oxide concentration. The initial injection into the

  3. Final Scientific/Technical Report--In-Situ Generation of Iron-Chromium Precipitates for Long Term Immobilization of Chromium at the Hanford Site

    SciTech Connect

    Butler, Elizabeth C.; Krumholz, Lee R.; Madden, Andrew S.; Hansel, Colleen M.

    2013-12-13

    Hexavalent chromium (Cr(VI)) is a toxic ground water contaminant widespread at the Hanford site and many other industrial facilities. A common remediation method for Cr(VI) is in situ reduction/immobilization, in which soluble Cr(VI) is reduced to the less soluble trivalent Cr (Cr(III)). If iron (Fe) minerals are present during the process, Cr(III) precipitates as a mixed Fe(III)-Cr(III) (Fe-Cr) solid. The objective of this exploratory research was to obtain preliminary evidence about the relationships among the method of Cr(VI) reduction (i.e., abiotic or microbial), the properties of the resulting Fe-Cr precipitates, and their tendencies to release soluble Cr(VI) in the presence of the common manganese oxide birnessite. The results of this exploratory research project show that the conditions of Cr(VI) reduction—specifically the ratio of Cr to Fe, and/or whether the Cr(VI) reductant is a mineral or a microorganism—can significantly affect the tendency of the resulting Fe-Cr precipitate to release Cr(VI) to the environment in the presence of birnessite. These results suggest the chosen remediation conditions have the potential to strongly influence not only the initial success of in situ Cr(VI) reduction/immobilization, but also the potential for successful long term sequestration of Cr in the form of stable soil precipitates.

  4. Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

    PubMed

    Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

    2016-01-01

    Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

  5. Iron-oxide Aerogel and Xerogel Catalyst Formulations: Characterization by 57Fe Mössbauer and XAFS Spectroscopies

    SciTech Connect

    Huggins, F.; Bali, S; Huffman, G; Eyring, E

    2010-01-01

    Iron in various iron-oxide aerogel and xerogel catalyst formulations ({ge}85% Fe{sub 2}O{sub 3}; {le}10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by {sup 57}Fe Moessbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Moessbauer spectrum was obtained from the different as-prepared and calcined catalyst formulations in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Moessbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, {chi}{sub eff}/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Moessbauer measurements for two aerogels over the range from 15 to 292 K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and

  6. Inter-relationships of MnO 2 precipitation, siderophore-Mn (III) complex formation, siderophore degradation, and iron limitation in Mn (II)-oxidizing bacterial cultures

    NASA Astrophysics Data System (ADS)

    Parker, Dorothy L.; Morita, Takami; Mozafarzadeh, Mylene L.; Verity, Rebecca; McCarthy, James K.; Tebo, Bradley M.

    2007-12-01

    To examine the pathways that form Mn (III) and Mn (IV) in the Mn (II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn (IV)O 2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn (III) complex or insoluble Mn (IV)O 2 minerals - but not both simultaneously. PVD-Mn (III) was present, and MnO 2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn (III) arose by predominantly ligand-mediated air oxidation of Mn (II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn (III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn (III), a process linked to the production of both MnO 2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn (III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO 2 to appear. These results suggest that P. putida cultures produce soluble Mn (III) or MnO 2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO 2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn (III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn (III) versus MnO 2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.

  7. The magnetic and oxidation behavior of bare and silica-coated iron oxide nanoparticles synthesized by reverse co-precipitation of ferrous ion (Fe2+) in ambient atmosphere

    NASA Astrophysics Data System (ADS)

    Mahmed, N.; Heczko, O.; Lancok, A.; Hannula, S.-P.

    2014-03-01

    The synthesis of iron oxide nanoparticles, i.e., magnetite was attempted by using only ferrous ion (Fe2+) as a magnetite precursor, under an ambient atmosphere. The room temperature reverse co-precipitation method was used, by applying two synthesis protocols. The freshly prepared iron oxide was also immediately coated with Stöber silica (SiO2) layer, forming the coreshell structure. The phase, stoichiometry, crystallite and the particle size of the synthesized powders were determined by using X-ray diffraction (XRD) and transmission electron microscope (TEM), while the magnetic and oxidation behaviors were studied by using the vibrating sample magnetometer (VSM) and Mössbauer spectroscopy. Based on the results, the bare iron oxide nanoparticles are in the stoichiometry between the magnetite and the maghemite stoichiometry, i.e., oxidation occurs. This oxidation is depending on the synthesis protocols used. With the silica coating, the oxidation can be prevented, as suggested by the fits of Mössbauer spectra and low temperature magnetic measurement.

  8. Interaction of a screw dislocation with Cu-precipitates, nanovoids and Cu-vacancy clusters in BCC iron

    NASA Astrophysics Data System (ADS)

    Terentyev, Dmitry; Malerba, Lorenzo

    2012-02-01

    In a previous work we studied the interaction of a ½<1 1 1>{1 1 0} edge dislocation with Cu-rich precipitates containing also vacancies and Ni, thereby mimicking precipitates known to form in RPV steels [1]. Here, we extend the study and consider the interaction of the Cu-rich precipitates with ½<1 1 1> screw dislocations, known to govern the slip in BCC metals and alloys below room temperature. The results show that three different mechanisms take place upon interaction of a screw dislocation with pure Cu precipitates, nanovoids and Cu-vacancy clusters. Pure Cu precipitates are always sheared, while in the reaction with nanovoids local climb, especially at high temperature, is also observed. The interaction mechanisms studied at various temperatures reveal that the penetration of the screw dislocation into Cu-vacancy clusters leads to absorption of the majority of the vacancies on the dislocation line, with the consequent formation of a helical turn. The removal of the helical turn, even a very small one, from the dislocation line requires as high stress as for the passage through a row of nanovoids of comparable size.

  9. Load partitioning between the bcc-iron matrix and NiAl-type precipitates in a ferritic alloy on multiple length scales.

    PubMed

    Sun, Zhiqian; Song, Gian; Sisneros, Thomas A; Clausen, Bjørn; Pu, Chao; Li, Lin; Gao, Yanfei; Liaw, Peter K

    2016-01-01

    An understanding of load sharing among constituent phases aids in designing mechanical properties of multiphase materials. Here we investigate load partitioning between the body-centered-cubic iron matrix and NiAl-type precipitates in a ferritic alloy during uniaxial tensile tests at 364 and 506 °C on multiple length scales by in situ neutron diffraction and crystal plasticity finite element modeling. Our findings show that the macroscopic load-transfer efficiency is not as high as that predicted by the Eshelby model; moreover, it depends on the matrix strain-hardening behavior. We explain the grain-level anisotropic load-partitioning behavior by considering the plastic anisotropy of the matrix and elastic anisotropy of precipitates. We further demonstrate that the partitioned load on NiAl-type precipitates relaxes at 506 °C, most likely through thermally-activated dislocation rearrangement on the microscopic scale. The study contributes to further understanding of load-partitioning characteristics in multiphase materials. PMID:26979660

  10. Load partitioning between the bcc-iron matrix and NiAl-type precipitates in a ferritic alloy on multiple length scales

    DOE PAGES

    Sun, Zhiqian; Song, Gian; Sisneros, Thomas A.; Clausen, Bjorn; Pu, Chao; Li, Lin; Gao, Yanfei; Liaw, Peter K.

    2016-03-16

    An understanding of load sharing among constituent phases aids in designing mechanical properties of multiphase materials. Here we investigate load partitioning between the body-centered-cubic iron matrix and NiAl-type precipitates in a ferritic alloy during uniaxial tensile tests at 364 and 506 C on multiple length scales by in situ neutron diffraction and crystal plasticity finite element modeling. Our findings show that the macroscopic load-transfer efficiency is not as high as that predicted by the Eshelby model; moreover, it depends on the matrix strain-hardening behavior. We explain the grain-level anisotropic load-partitioning behavior by considering the plastic anisotropy of the matrix andmore » elastic anisotropy of precipitates. We further demonstrate that the partitioned load on NiAl-type precipitates relaxes at 506 C, most likely through thermally-activated dislocation rearrangement on the microscopic scale. Furthermore, the study contributes to further understanding of load-partitioning characteristics in multiphase materials.« less

  11. Load partitioning between the bcc-iron matrix and NiAl-type precipitates in a ferritic alloy on multiple length scales

    PubMed Central

    Sun, Zhiqian; Song, Gian; Sisneros, Thomas A.; Clausen, Bjørn; Pu, Chao; Li, Lin; Gao, Yanfei; Liaw, Peter K.

    2016-01-01

    An understanding of load sharing among constituent phases aids in designing mechanical properties of multiphase materials. Here we investigate load partitioning between the body-centered-cubic iron matrix and NiAl-type precipitates in a ferritic alloy during uniaxial tensile tests at 364 and 506 °C on multiple length scales by in situ neutron diffraction and crystal plasticity finite element modeling. Our findings show that the macroscopic load-transfer efficiency is not as high as that predicted by the Eshelby model; moreover, it depends on the matrix strain-hardening behavior. We explain the grain-level anisotropic load-partitioning behavior by considering the plastic anisotropy of the matrix and elastic anisotropy of precipitates. We further demonstrate that the partitioned load on NiAl-type precipitates relaxes at 506 °C, most likely through thermally-activated dislocation rearrangement on the microscopic scale. The study contributes to further understanding of load-partitioning characteristics in multiphase materials. PMID:26979660

  12. Load partitioning between the bcc-iron matrix and NiAl-type precipitates in a ferritic alloy on multiple length scales

    NASA Astrophysics Data System (ADS)

    Sun, Zhiqian; Song, Gian; Sisneros, Thomas A.; Clausen, Bjørn; Pu, Chao; Li, Lin; Gao, Yanfei; Liaw, Peter K.

    2016-03-01

    An understanding of load sharing among constituent phases aids in designing mechanical properties of multiphase materials. Here we investigate load partitioning between the body-centered-cubic iron matrix and NiAl-type precipitates in a ferritic alloy during uniaxial tensile tests at 364 and 506 °C on multiple length scales by in situ neutron diffraction and crystal plasticity finite element modeling. Our findings show that the macroscopic load-transfer efficiency is not as high as that predicted by the Eshelby model; moreover, it depends on the matrix strain-hardening behavior. We explain the grain-level anisotropic load-partitioning behavior by considering the plastic anisotropy of the matrix and elastic anisotropy of precipitates. We further demonstrate that the partitioned load on NiAl-type precipitates relaxes at 506 °C, most likely through thermally-activated dislocation rearrangement on the microscopic scale. The study contributes to further understanding of load-partitioning characteristics in multiphase materials.

  13. Theoretical Investigation of Stabilizing Mechanism by Boron in Body-Centered Cubic Iron Through (Fe,Cr)23(C,B)6 Precipitates

    NASA Astrophysics Data System (ADS)

    Sahara, Ryoji; Matsunaga, Tetsuya; Hongo, Hiromichi; Tabuchi, Masaaki

    2016-05-01

    Small amounts of boron improve the mechanical properties in high-chromium ferritic heat-resistant steels. In this work, the stabilizing mechanism by boron in body-centered cubic iron (bcc Fe) through (Fe,Cr)23(C,B)6 precipitates was investigated by first-principles calculations. Formation energy analysis of (Fe,Cr)23(C,B)6 reveals that the compounds become more stable to elemental solids as the boron concentration increases. Furthermore, the interface energy of bcc Fe(110) || Fe23(C,B)6(111) also decreases with boron concentration in the compounds. The decreased interface energy caused by boron addition is explained by the balance between the change in the phase stability of the precipitates and the change in the misfit parameter for the bcc Fe matrix and the precipitates. These results show that boron stabilizes the microstructure of heat-resistant steels, which is important for understanding the origins of the creep strength in ferritic steels.

  14. IRON PRECIPITATION AND ARSENIC ATTENUATION - ASSESSMENT OF ARSENIC NATURAL ATTENUATION OF THE SUBSURFACE USING A GEOCHEMICAL MODEL (PHREEQC)

    EPA Science Inventory

    Laboratory experiments show that amorphous and poorly crystallized ferric iron hydroxides have much greater capacity to attenuate arsenic compared to clays and other aluminosilicate minerals. Studies (e.g., Lin and Qvarfort, 1996) showed that a sudden change in geochemical condit...

  15. Rare earth element systematics of the chemically precipitated component in Early Precambrian iron formations and the evolution of the terrestrial atmosphere-hydrosphere-lithosphere system

    SciTech Connect

    Bau, M.; Moeller, P. )

    1993-05-01

    The chemically precipitated component in Early Precambrian (> 2.3 Ga) iron formations (IFs) displays (Sm/Yb)[sub CN] < 1 and (Eu/Sm)[sub SN] > 1 which reflects the corresponding ratios of contemporaneous seawater. In conjunction with [epsilon][sub Nd-IF] > [epsilon][sub Nd-shale] this rare earth element (REE) signature reveals that the REE distribution in Early Precambrian IFs must be explained by mixing between a marine bottom and a surface water component, and that the REEs (and by analogy the Fe) cannot be derived from weathering of a continental source. Mixing calculations reveal that (Sm/Yb)[sub CN] in Early Precambrian marine surface waters was significantly lower than it is today. To explain this difference, two mechanisms are discussed on the basis of higher P[sub CO[sub 2

  16. Effects of ferrous iron on the precipitation and growth of CaCO3 in slightly basic aqueous solutions, from macro to nanoscale

    NASA Astrophysics Data System (ADS)

    Di Lorenzo, Fulvio; Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnación; Putnis, Christine V.; Prieto, Manuel

    2016-04-01

    The precipitation of CaCO3 and further growth of calcite has been studied in aqueous solutions containing ferrous iron (Fe2+). Two different types of bulk experiments have been carried out. Nucleation experiments have been conducted at pH 9 with five different CaTOT/FeTOT ratios: 10, 5, 2.5, 1.25 and 0.625. As well, calcite growth experiments have been conducted at pH 8.5 (following the constant composition method) with CaTOT/FeTOT ratios: 100, 50 and 25; this higher dilution partially reduces the impact of inhibition on growth of calcite occurring when CaTOT/FeTOT ≤ 25. Parameters such as the solution pH, [Ca2+], conductivity, solution transmittance (610 nm), and volume added were continuously monitored by a Titrino 905 system (Metrohm, Switzerland). After the experiments, the CaCO3 precipitates were collected, filtered, dried and characterized by powder-XRD, HRTEM, FESEM-EDX, EMPA. Solution composition was determined by ICP-MS. Additionally, in-situ Atomic Force Microscopy (AFM) flow-through growth experiments were conducted in a sealed fluid cell using freshly cleaved natural calcite (Iceland spar). The solution composition in AFM experiments was analogous to the bulk growth experiments. The results of these experiments reveal the significant influence of ferrous iron on nucleation and growth in the CaCO3-H2O system, reflected as well in polymorphic selection in this system.Finally, thermodynamic considerations for the system Ca-Fe-CO2-H2O are discussed that allow the modelling of geochemical processes involving this system, such as geological carbon storage in basaltic rocks.

  17. Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

    USGS Publications Warehouse

    Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, C.N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

    2012-01-01

    The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

  18. Simultaneous determinations of zirconium, hafnium, yttrium and lanthanides in seawater according to a co-precipitation technique onto iron-hydroxide.

    PubMed

    Raso, Maria; Censi, Paolo; Saiano, Filippo

    2013-11-15

    Very low concentrations (pg mL(-1) or sub-pg mL(-1) level) along with the high salinity are the main problems in determining trace metal contents in seawater. This problem is mainly considered for investigations of naturally occurring YLOID (Y and Lanthanides) and Zr and Hf in order to provide precise and accurate results. The inductively coupled plasma mass spectrometry (ICP-MS), both in high and low resolution, offers many advantages including simultaneous analyses of all elements and their quantitative determination with detection limits of the order of pg mL(-1). However in the analysis of YLOID in seawater, a better determination needs an efficient combination of ICP-MS measurement with a pre-concentration technique. To perform an ultra-trace analysis in seawater, we have validated an analytical procedure involving an improved modified co-precipitation on iron hydroxides to ensure the simultaneous quantitative recovery of YLOID, Zr and Hf contents with measurement by a quadrupole ICP-MS. The validity of the method was assessed through a series of co-precipitation experiments and estimation of several quality control parameters for method validation, namely working range and its linearity, detection limit, quantification limit, precision and spike recoveries, and the methodological blank choice, are introduced, evaluated and discussed. Analysis of NASS-6, is the first report on the latest seawater reference material for YLOID, hafnium and zirconium.

  19. Oxidative remobilization of biogenic uranium(IV) precipitates: effects of iron(II) and pH.

    PubMed

    Zhong, Lirong; Liu, Chongxuan; Zachara, John M; Kennedy, Dave W; Szecsody, James E; Wood, Brian

    2005-01-01

    The oxidative remobilization of uranium from biogenic U(IV) precipitates was investigated in bioreduced sediment suspensions in contact with atmospheric O2 with an emphasis on the influence of Fe(II) and pH on the rate and extent of U release from the solid to the aqueous phase. The sediment was collected from the U.S. Department of Energy Field Research Center (FRC) site at Oak Ridge, Tennessee. Biogenic U(IV) precipitates and bioreduced sediment were generated through anaerobic incubation with a dissimilatory metal reducing bacterium Shewanella putrefaciens strain CN32. The oxidative remobilization of freshly prepared and 1-yr aged biogenic U(IV) was conducted in 0.1 mol/L NaNO3 electrolyte with variable pH and Fe(II) concentrations. Biogenic U(IV)O2(s) was released into the aqueous phase with the highest rate and extent at pH 4 and 9, while the U remobilization was the lowest at circumneutral pH. Increasing Fe(II) significantly decreased U remobilization to the aqueous phase. From 70 to 100% of the U in the sediments used in all the tests was extractable at the experiment termination (41 d) with a bicarbonate solution (0.2 mol/L), indicating that biogenic U(IV) was oxidized regardless of Fe(II) concentration and pH. Sorption experiments and modeling calculations indicated that the inhibitive effect of Fe(II) on U(IV) oxidative remobilization was consistent with the Fe(III) oxide precipitation and U(VI) sorption to this secondary phase. PMID:16151228

  20. Removal of H 2S via an iron catalytic cycle and iron sulfide precipitation in the water column of dead end tributaries

    NASA Astrophysics Data System (ADS)

    Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III

    2006-11-01

    The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.

  1. An in situ XAS study of ferric iron hydrolysis and precipitation in the presence of perchlorate, nitrate, chloride and sulfate

    NASA Astrophysics Data System (ADS)

    Collins, Richard N.; Rosso, Kevin M.; Rose, Andrew L.; Glover, Chris J.; David Waite, T.

    2016-03-01

    Using a novel combination of in situ potentiometric experiments and quick-scanning XAS we present Fe K-edge XAS spectra (to k = 12 Å-1) during FeIII hydrolysis and precipitation in 0.33 M Fe(ClO4)3, Fe(NO3)3, FeCl3 and Fe2(SO4)3 solutions up to pH 4.8. Edge-sharing FeIII polymers appeared almost immediately upon hydrolysis with strong evidence for a μ-oxo dimer species forming in the Fe(ClO4)3, Fe(NO3)3 and FeCl3 solutions. The effects of SO4 on hydrolysis and polymerization pathways included inhibition of both the formation of the μ-oxo dimer and double corner FeIII bonding, ultimately resulting in the precipitation of schwertmannite. As such, under these experimental conditions, double corner FeIII bonding appears to be critical to the formation of ferrihydrite. The spectral trends indicated that the decomposition/transformation of the dimer was sudden and broadly coincident with shortening average Fe-O bond distances, increased Fe neighbors at ∼3.43 Å and a pre-edge energy transformation suggestive of decreased ligand field strength as well as increasing proportions of tetrahedral FeIII. This result suggests that the incorporation of tetrahedral FeIII into ferrihydrite occurs only at the latter stages of extended polymerization.

  2. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    was recently challenged and a new structure based on a thin film of Fe3O4(111) on α-Fe2O3(0001) was proposed. The merits of the competing models are discussed. The α-Fe2O3(1 1 bar02) "R-cut" surface is recommended as an excellent prospect for future study given its apparent ease of preparation and its prevalence in nanomaterial. In the latter sections the literature regarding adsorption on iron oxides is reviewed. First, the adsorption of molecules (H2, H2O, CO, CO2, O2, HCOOH, CH3OH, CCl4, CH3I, C6H6, SO2, H2S, ethylbenzene, styrene, and Alq3) is discussed, and an attempt is made to relate this information to the reactions in which iron oxides are utilized as a catalyst (water-gas shift, Fischer-Tropsch, dehydrogenation of ethylbenzene to styrene) or catalyst supports (CO oxidation). The known interactions of iron oxide surfaces with metals are described, and it is shown that the behaviour is determined by whether the metal forms a stable ternary phase with the iron oxide. Those that do not, (e.g. Au, Pt, Ag, Pd) prefer to form three-dimensional particles, while the remainder (Ni, Co, Mn, Cr, V, Cu, Ti, Zr, Sn, Li, K, Na, Ca, Rb, Cs, Mg, Ca) incorporate within the oxide lattice. The incorporation temperature scales with the heat of formation of the most stable metal oxide. A particular effort is made to underline the mechanisms responsible for the extraordinary thermal stability of isolated metal adatoms on Fe3O4 surfaces, and the potential application of this model system to understand single atom catalysis and sub-nano cluster catalysis is discussed. The review ends with a brief summary, and a perspective is offered including exciting lines of future research.

  3. Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

    NASA Astrophysics Data System (ADS)

    Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

    2011-08-01

    One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

  4. Kilogram-scale synthesis of iron oxy-hydroxides with improved arsenic removal capacity: study of Fe(II) oxidation--precipitation parameters.

    PubMed

    Tresintsi, Sofia; Simeonidis, Konstantinos; Vourlias, George; Stavropoulos, George; Mitrakas, Manassis

    2012-10-15

    Various iron oxy-hydroxides were synthesized in a continuous flow kilogram-scale production reactor through the precipitation of FeSO(4) and FeCl(2) in the pH range 3-12 under intense oxidative conditions to serve as arsenic adsorbents. The selection of the optimum adsorbent and the corresponding conditions of the synthesis was based not only on its maximum As(III) and As(V) adsorption capacity but also on its potential efficiency to achieve the arsenic health regulation limit in NSF challenge water. As a result, the adsorbent prepared at pH 4, which consists of schwertmannite, was selected because it exhibited the highest adsorption capacity of 13 μg As(V)/mg, while maintaining a residual arsenic concentration of 10 μg/L at an equilibrium pH 7. The high surface charge and the activation of an ion-exchange mechanism between SO(4)(2-) adsorbed in the Stern layer and arsenate ions were found to significantly contribute to the increased adsorption capacity. Adsorption capacity values observed in rapid scale column experiments illustrate the improved efficiency of the qualified adsorbent compared to the common commercial arsenic adsorbents.

  5. Process for producing dimethyl ether from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  6. Process for producing dimethyl ether form synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  7. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-alkane, branched and linear. 721.10103 Section 721.10103 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES..., branched and linear. (a) Chemical substance and significant new uses subject to reporting. (1) The...

  8. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL... provide a National Institute for Occupational Safety and Health (NIOSH) assigned protection factor...

  9. Influence of the support on the activity and selectivity of high dispersion Fe catalysts in the Fischer-Tropsch reaction

    SciTech Connect

    Cagnoli, M.V.; Marchetti, S.G.; Gallegos, N.G.; Alvarez, A.M.; Mercader, R.C.; Yeramian, A.A. Facultad de Ciencias Exactas, La Plata )

    1990-05-01

    In order to study the influence of the support on high dispersion catalysts used for the CO hydrogenation reaction, two catalysts, Fe/SiO{sub 2} and Fe/Al{sub 2}O{sub 3}, were prepared by the dry impregnation method. Selective chemisorption of CO, volumetric oxidation, and Moessbauer spectroscopy were used to determine the Fe species present as well as the metallic crystal size, the degree of dispersion, and the reduction percentage. The presence of small Fe{sup 0} crystallites with high dispersion was determined in both catalysts. Reaction rates were measured in a differential reactor and significant differences, about one order of magnitude less for the Al{sub 2}O{sub 3} than for the SiO{sub 2} supported catalysts, were found in the methane turnover frequencies. They are attributed to the interaction between the metal and the supports. The selectivity differences is also discussed in connection with distinct surface properties.

  10. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  11. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  12. Indirect liquefaction of coal. [Coal gasification plus Fischer-Tropsch, methanol or Mobil M-gasoline process

    SciTech Connect

    1980-06-30

    The most important potential environmental problems uniquely associated with indirect liquefaction appear to be related to the protection of occupational personnel from the toxic and carcinogenic properties of process and waste stream constituents, the potential public health risks from process products, by-products and emissions and the management of potentially hazardous solid wastes. The seriousness of these potential problems is related partially to the severity of potential effects (i.e., human mortality and morbidity), but even more to the uncertainty regarding: (1) the probable chemical characteristics and quantities of process and waste streams; and (2) the effectiveness and efficiencies of control technologies not yet tested on a commercial scale. Based upon current information, it is highly improbable that these potential problems will actually be manifested or pose serious constraints to the development of indirect liquefaction technologies, although their potential severity warrants continued research and evaluation. The siting of indirect liquefaction facilities may be significantly affected by existing federal, state and local regulatory requirements. The possibility of future changes in environmental regulations also represents an area of uncertainty that may develop into constraints for the deployment of indirect liquefaction processes. Out of 20 environmental issues identified as likely candidates for future regulatory action, 13 were reported to have the potential to impact significantly the commercialization of coal synfuel technologies. These issues are listed.

  13. Fischer-tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1993-07-29

    We have completed modifications of the Taylor Dispersion Apparatus so that propane can be used as a solvent. Problems were encountered initially compressing propane to the necessary pressures because of cavitation in the liquid pump. This problem was overcome by placing a check valve in the line after the pump and pressures of 2500 psi have been achieved. The system has been pressure tested by using a soap solution on exposed joints and performing a mass balance (leak test). The mass balance was made by reading the volumetric flow rate of liquid in the syringe pump and converting this to expected gas flow rate. The liquid was then vaporized and a dry gas meter measured the amount of gas at the exit of the apparatus. The expected and measured gas flow rates were in excellent agreement, indicating that there are no significant leaks in the system. Presently, we are having problems with the use of UV detection for the dim using compounds. The detector is successfully auto-zeroing with a blank cell and with Co{sub 2}. With the use of instrument grade propane, however, the detector is unable to auto-zero because of absorption of unknown impurity. We believe this problem is caused by a sulfur compound in the propane gas cylinder and we plan to install an active carbon guard bed to remove a sulfur containing compounds.

  14. Effects of Weak Surface Modification on Co/SiO2 Catalyst for Fischer-Tropsch Reaction

    PubMed Central

    Ning, Wensheng; Shen, Hehong; Jin, Yangfu; Yang, Xiazhen

    2015-01-01

    A weak surface modification is applied to Co/SiO2 catalyst by hydrothermal treatment at 180°C for 5 h. Aluminum is introduced to Co/SiO2 catalysts during the surface modification. The effects of surface modification on Co/SiO2 catalyst are studied by changing the operating sequences of surface modification and cobalt impregnation in the catalyst preparation. Surface modification before cobalt impregnation makes Co3O4 particle small and dispersed into the deep part of enlarged pore in SiO2, while surface modification after cobalt impregnation does not obviously change the particle size of Co3O4. The improved amplitude of catalytic activity is similar for the two kinds of catalysts, but they are benefited from different factors. The content of iso-hydrocarbons in the products is increased by the surface modifications. PMID:25938725

  15. URANIUM PRECIPITATION PROCESS

    DOEpatents

    Thunaes, A.; Brown, E.A.; Smith, H.W.; Simard, R.

    1957-12-01

    A method for the recovery of uranium from sulfuric acid solutions is described. In the present process, sulfuric acid is added to the uranium bearing solution to bring the pH to between 1 and 1.8, preferably to about 1.4, and aluminum metal is then used as a reducing agent to convert hexavalent uranium to the tetravalent state. As the reaction proceeds, the pH rises amd a selective precipitation of uranium occurs resulting in a high grade precipitate. This process is an improvement over the process using metallic iron, in that metallic aluminum reacts less readily than metallic iron with sulfuric acid, thus avoiding consumption of the reducing agent and a raising of the pH without accomplishing the desired reduction of the hexavalent uranium in the solution. Another disadvantage to the use of iron is that positive ferric ions will precipitate with negative phosphate and arsenate ions at the pH range employed.

  16. Process for the synthesis of iron powder

    DOEpatents

    Welbon, William W.

    1983-01-01

    A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

  17. Process for the synthesis of iron powder

    DOEpatents

    Not Available

    1982-03-06

    A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

  18. Process for the synthesis of iron powder

    DOEpatents

    Welbon, W.W.

    1983-11-08

    A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder. 2 figs.

  19. Iron-control additives improve acidizing

    SciTech Connect

    Walker, M.; Dill, W. ); Besler, M. )

    1989-07-24

    Iron sulfide and sulfur precipitation in sour wells can be controlled with iron-sequestering agents and sulfide modifiers. Oil production has been routinely increased in sour wells where precipitation of iron sulfide and elemental sulfur has been brought under control. Production increases have been especially noteworthy on wells that had a history of rapid production decline after acid stimulation. Twenty-fold production increases have been recorded. Key to the production increase has been to increase permeability with: Iron chelating agents that control precipitation of iron sulfide. A sulfide modifier that reduces precipitation of solids in the presence of excessive amounts of hydrogen sulfide and prevents precipitation of elemental sulfur.

  20. A Holocene record of endogenic iron and manganese precipitation, isotopic composition of endogenic carbonate, and vegetation history in a lake-fen complex in northwestern Minnesota

    USGS Publications Warehouse

    Dean, Walter E.; Doner, Lisa A.

    2011-01-01

    Little Shingobee Lake and Fen are part of an extensive network of lakes and wetlands in the Shingobee River headwaters area of northwestern Minnesota. Prior to about 9800 radiocarbon years, most of the lakes in the Shingobee watershed area were interconnected to form glacial Lake Willobee. From 9800 to 7700 radiocarbon years, the level of Lake Willobee fell as a result of breaching of a dam, leaving small separated basins containing the existing lakes and wetlands. The dominant components in the sediments in a 9-meter core from Little Shingobee Lake (LSL-B), and lacustrine sediments under 3.3 meters of peat in a 17-meter core from Little Shingobee Fen (LSF-10) are detrital clastic material, endogenic CaCO3, and organic matter. The detrital fraction in the Holocene section in core LSL-B varies considerably from 7 weight percent to 82 weight percent and closely parallels the concentration of detrital quartz measured by X-ray diffraction. The CaCO3 concentration, which also varies considerably from 10 weight percent to 70 weight percent, is generally antithetic to the detrital concentration owing to the dilution of detrital material by CaCO3, particularly during the early to middle Holocene (about 9000-6500 calendar years). The organic-matter content varies from 5 weight percent to 25 weight percent and, together with CaCO3, serves to dilute the allogenic detrital fraction. In both cores almost all of the iron (Fe) and manganese (Mn) is in endogenic minerals, presumed to be oxyhydroxide minerals, that are important components throughout the core; little Fe and Mn are contributed by detrital aluminosilicate minerals. The endogenic Fe mineral, calculated as Fe(OH)3, forms a larger percentage of the sediment than endogenic organic material throughout most of the Holocene section in the LSL-B core and in the lacustrine sediments below the peat in the LSF-10 core. Biogenic silica as opal (biopal; diatom debris) was not measured, but the average calculated biopal is 5

  1. Microbes: mini iron factories.

    PubMed

    Joshi, Kumar Batuk

    2014-12-01

    Microbes have flourished in extreme habitats since beginning of the Earth and have played an important role in geological processes like weathering, mineralization, diagenesis, mineral formation and destruction. Biotic mineralization is one of the most fascinating examples of how microbes have been influencing geological processes. Iron oxidizing and reducing bacteria are capable of precipitating wide varieties of iron oxides (magnetite), carbonates (siderite) and sulphides (greigite) via controlled or induced mineralization processes. Microbes have also been considered to play an important role in the history of evolution of sedimentary rocks on Earth from the formation of banded iron formations during the Archean to modern biotic bog iron and ochre deposits. Here, we discuss the role that microbes have been playing in precipitation of iron and the role and importance of interdisciplinary studies in the field of geology and biology in solving some of the major geological mysteries. PMID:25320452

  2. Microbes: mini iron factories.

    PubMed

    Joshi, Kumar Batuk

    2014-12-01

    Microbes have flourished in extreme habitats since beginning of the Earth and have played an important role in geological processes like weathering, mineralization, diagenesis, mineral formation and destruction. Biotic mineralization is one of the most fascinating examples of how microbes have been influencing geological processes. Iron oxidizing and reducing bacteria are capable of precipitating wide varieties of iron oxides (magnetite), carbonates (siderite) and sulphides (greigite) via controlled or induced mineralization processes. Microbes have also been considered to play an important role in the history of evolution of sedimentary rocks on Earth from the formation of banded iron formations during the Archean to modern biotic bog iron and ochre deposits. Here, we discuss the role that microbes have been playing in precipitation of iron and the role and importance of interdisciplinary studies in the field of geology and biology in solving some of the major geological mysteries.

  3. Current Issues in Molecular Catalysis Illustrated by Iron Porphyrins as Catalysts of the CO2-to-CO Electrochemical Conversion.

    PubMed

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

    2015-12-15

    Recent attention aroused by the reduction of carbon dioxide has as main objective the production of useful products, the "solar fuels", in which solar energy would be stored. One route to this goal is the design of photochemical schemes that would operate this conversion using directly sun light energy. An indirect approach consists in first converting sunlight energy into electricity then using it to reduce CO2 electrochemically. Conversion of carbon dioxide into carbon monoxide is thus a key step through the classical dihydrogen-reductive Fischer-Tropsch chemistry. Direct and catalytic electrochemical CO2 reduction already aroused active interest during the 1980-1990 period. The new wave of interest for these matters that has been growing since 2012 is in direct conjunction with modern energy issues. Among molecular catalysts, electrogenerated Fe(0) porphyrins have proved to be particularly efficient and robust. Recent progress in this field has closely associated the search of more and more efficient catalysts in the iron porphyrin family with an unprecedentedly rigorous deciphering of mechanisms. Accordingly, the coupling of proton transfer with electron transfer and breaking of one of the two C-O bonds of CO2 have been the subjects of relentless scrutiny and mechanistic analysis with systematic investigation of the degree of concertedness of these three events. Catalysis of the electrochemical CO2-to-CO conversion has thus been a good testing ground for the mechanism diagnostic strategies and the all concerted reactivity model proposed then. The role of added Brönsted acids, both as H-bond providers and proton donors, has been elucidated. These efforts have been a preliminary to the inclusion of the acid functionalities within the catalyst molecule, giving rise to considerable increase of the catalytic efficiency. The design of more and more efficient catalysts made it necessary to propose "catalytic Tafel plots" relating the turnover frequency to the

  4. Current Issues in Molecular Catalysis Illustrated by Iron Porphyrins as Catalysts of the CO2-to-CO Electrochemical Conversion.

    PubMed

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

    2015-12-15

    Recent attention aroused by the reduction of carbon dioxide has as main objective the production of useful products, the "solar fuels", in which solar energy would be stored. One route to this goal is the design of photochemical schemes that would operate this conversion using directly sun light energy. An indirect approach consists in first converting sunlight energy into electricity then using it to reduce CO2 electrochemically. Conversion of carbon dioxide into carbon monoxide is thus a key step through the classical dihydrogen-reductive Fischer-Tropsch chemistry. Direct and catalytic electrochemical CO2 reduction already aroused active interest during the 1980-1990 period. The new wave of interest for these matters that has been growing since 2012 is in direct conjunction with modern energy issues. Among molecular catalysts, electrogenerated Fe(0) porphyrins have proved to be particularly efficient and robust. Recent progress in this field has closely associated the search of more and more efficient catalysts in the iron porphyrin family with an unprecedentedly rigorous deciphering of mechanisms. Accordingly, the coupling of proton transfer with electron transfer and breaking of one of the two C-O bonds of CO2 have been the subjects of relentless scrutiny and mechanistic analysis with systematic investigation of the degree of concertedness of these three events. Catalysis of the electrochemical CO2-to-CO conversion has thus been a good testing ground for the mechanism diagnostic strategies and the all concerted reactivity model proposed then. The role of added Brönsted acids, both as H-bond providers and proton donors, has been elucidated. These efforts have been a preliminary to the inclusion of the acid functionalities within the catalyst molecule, giving rise to considerable increase of the catalytic efficiency. The design of more and more efficient catalysts made it necessary to propose "catalytic Tafel plots" relating the turnover frequency to the

  5. Aluminium and iron, but neither copper nor zinc, are key to the precipitation of beta-sheets of Abeta_{42} in senile plaque cores in Alzheimer's disease.

    PubMed

    Exley, Christopher

    2006-11-01

    A number of metals including Fe(II)/Fe(III), Al(III), Zn(II) and Cu(II) are found co-localised with beta-sheets of Abeta_{42} in senile plaque cores in AD brain. We know neither why nor how the co-localisation takes place or, indeed, if it is entirely aberrant or partly protective. There are data from in vitro studies which may begin to explain some of these unanswered questions and in considering these I have summised that Al(III) and Fe(III)/Fe(II) are directly involved in the precipitation of beta-sheets of Abeta_{42} in senile plaque cores whereas the presence of Cu(II) and Zn(II) is adventitious. The co-deposition of Al(III), Fe(III) and beta-sheets of Abeta_{42} could act as a source of reactive oxygen species and begin to explain some of the oxidative damage found in the immediate vicinity of senile plaques. Whether such metal-Abeta_{42} synergisms are an integral part of the aetiology of AD remains to be confirmed.

  6. A Holocene record of endogenic iron and manganese precipitation and vegetation history in a lake-fen complex in northwestern Minnesota

    USGS Publications Warehouse

    Dean, W.E.; Doner, L.A.

    2012-01-01

    Little Shingobee Lake and Fen are part of the extensive network of lakes and wetlands in the Shingobee River headwaters of northwestern Minnesota, designed to study the interactions between surface and ground waters. Prior to about 11. 2 cal. ka, most of these lakes and wetlands were interconnected to form glacial Lake Willobee, which apparently formed when a debris flow dammed the Shingobee River. Between 11. 2 and 8. 5 cal. ka, the level of Lake Willobee fell as a result of breaching of the dam, transforming the deep lake into the existing lakes and wetlands. Analyses of a 9-m core from Little Shingobee Lake (LSL-B), and lacustrine sediments under 3. 3 m of peat in a 17-m core from Little Shingobee Fen (LSF-10), show that the dominant components are allogenic clastic material, and endogenic CaCO3 and organic matter. In both cores almost all of the iron (Fe) and manganese (Mn) are incorporated in endogenic minerals, presumed to be X-ray amorphous oxyhydroxide minerals, that occur in significant quantities throughout the cores; almost no Fe and Mn are contributed from detrital aluminosilicate minerals. This suggests that, for most of the Holocene, the allogenic watershed contributions to lake chemistry were minor compared to the dissolved mineral load. In addition, prior to 3. 5 cal. ka, pollen zone boundaries coincide with large changes in lake-sediment mineralogy, indicating that both landscape and climate processes were linked to early- and mid-Holocene lake chemistry. The pollen time series, with sequential domination by spruce, pine, sagebrush-oak, birch-oak and, finally, white pine is typical of the region and reflects the changing location of the prairie-forest transition zone over time. These changes in vegetation had some profound effects on the geochemistry of the lake waters. ?? 2011 Springer Science+Business Media B.V. (outside the USA).

  7. Biogeochemistry and community composition of iron- and sulfur-precipitating microbial mats at the Chefren mud volcano (Nile Deep Sea Fan, Eastern Mediterranean).

    PubMed

    Omoregie, Enoma O; Mastalerz, Vincent; de Lange, Gert; Straub, Kristina L; Kappler, Andreas; Røy, Hans; Stadnitskaia, Alina; Foucher, Jean-Paul; Boetius, Antje

    2008-05-01

    In this study we determined the composition and biogeochemistry of novel, brightly colored, white and orange microbial mats at the surface of a brine seep at the outer rim of the Chefren mud volcano. These mats were interspersed with one another, but their underlying sediment biogeochemistries differed considerably. Microscopy revealed that the white mats were granules composed of elemental S filaments, similar to those produced by the sulfide-oxidizing epsilonproteobacterium "Candidatus Arcobacter sulfidicus." Fluorescence in situ hybridization indicated that microorganisms targeted by a "Ca. Arcobacter sulfidicus"-specific oligonucleotide probe constituted up to 24% of the total the cells within these mats. Several 16S rRNA gene sequences from organisms closely related to "Ca. Arcobacter sulfidicus" were identified. In contrast, the orange mat consisted mostly of bright orange flakes composed of empty Fe(III) (hydr)oxide-coated microbial sheaths, similar to those produced by the neutrophilic Fe(II)-oxidizing betaproteobacterium Leptothrix ochracea. None of the 16S rRNA gene sequences obtained from these samples were closely related to sequences of known neutrophilic aerobic Fe(II)-oxidizing bacteria. The sediments below both types of mats showed relatively high sulfate reduction rates (300 nmol x cm(-3) x day(-1)) partially fueled by the anaerobic oxidation of methane (10 to 20 nmol x cm(-3) x day(-1)). Free sulfide produced below the white mat was depleted by sulfide oxidation within the mat itself. Below the orange mat free Fe(II) reached the surface layer and was depleted in part by microbial Fe(II) oxidation. Both mats and the sediments underneath them hosted very diverse microbial communities and contained mineral precipitates, most likely due to differences in fluid flow patterns.

  8. Biogeochemistry and Community Composition of Iron- and Sulfur-Precipitating Microbial Mats at the Chefren Mud Volcano (Nile Deep Sea Fan, Eastern Mediterranean)▿

    PubMed Central

    Omoregie, Enoma O.; Mastalerz, Vincent; de Lange, Gert; Straub, Kristina L.; Kappler, Andreas; Røy, Hans; Stadnitskaia, Alina; Foucher, Jean-Paul; Boetius, Antje

    2008-01-01

    In this study we determined the composition and biogeochemistry of novel, brightly colored, white and orange microbial mats at the surface of a brine seep at the outer rim of the Chefren mud volcano. These mats were interspersed with one another, but their underlying sediment biogeochemistries differed considerably. Microscopy revealed that the white mats were granules composed of elemental S filaments, similar to those produced by the sulfide-oxidizing epsilonproteobacterium “Candidatus Arcobacter sulfidicus.” Fluorescence in situ hybridization indicated that microorganisms targeted by a “Ca. Arcobacter sulfidicus”-specific oligonucleotide probe constituted up to 24% of the total the cells within these mats. Several 16S rRNA gene sequences from organisms closely related to “Ca. Arcobacter sulfidicus” were identified. In contrast, the orange mat consisted mostly of bright orange flakes composed of empty Fe(III) (hydr)oxide-coated microbial sheaths, similar to those produced by the neutrophilic Fe(II)-oxidizing betaproteobacterium Leptothrix ochracea. None of the 16S rRNA gene sequences obtained from these samples were closely related to sequences of known neutrophilic aerobic Fe(II)-oxidizing bacteria. The sediments below both types of mats showed relatively high sulfate reduction rates (300 nmol·cm−3·day−1) partially fueled by the anaerobic oxidation of methane (10 to 20 nmol·cm−3·day−1). Free sulfide produced below the white mat was depleted by sulfide oxidation within the mat itself. Below the orange mat free Fe(II) reached the surface layer and was depleted in part by microbial Fe(II) oxidation. Both mats and the sediments underneath them hosted very diverse microbial communities and contained mineral precipitates, most likely due to differences in fluid flow patterns. PMID:18378658

  9. Iron Test

    MedlinePlus

    ... detect and help diagnose iron deficiency or iron overload. In people with anemia , these tests can help ... also be ordered when iron deficiency or iron overload is suspected. Early iron deficiency often goes unnoticed. ...

  10. Precipitation Recycling

    NASA Technical Reports Server (NTRS)

    Eltahir, Elfatih A. B.; Bras, Rafael L.

    1996-01-01

    The water cycle regulates and reflects natural variability in climate at the regional and global scales. Large-scale human activities that involve changes in land cover, such as tropical deforestation, are likely to modify climate through changes in the water cycle. In order to understand, and hopefully be able to predict, the extent of these potential global and regional changes, we need first to understand how the water cycle works. In the past, most of the research in hydrology focused on the land branch of the water cycle, with little attention given to the atmospheric branch. The study of precipitation recycling which is defined as the contribution of local evaporation to local precipitation, aims at understanding hydrologic processes in the atmospheric branch of the water cycle. Simply stated, any study on precipitation recycling is about how the atmospheric branch of the water cycle works, namely, what happens to water vapor molecules after they evaporate from the surface, and where will they precipitate?

  11. STRONTIUM PRECIPITATION

    DOEpatents

    McKenzie, T.R.

    1960-09-13

    A process is given for improving the precipitation of strontium from an aqueous phosphoric-acid-containing solution with nickel or cobalt ferrocyanide by simultaneously precipitating strontium or calcium phosphate. This is accomplished by adding to the ferrocyanide-containing solution calcium or strontium nitrate in a quantity to yield a concentration of from 0.004 to 0.03 and adjusting the pH of the solution to a value of above 8.

  12. Microstructure and Kinetics of Nitride Precipitation in a Quaternary Iron-Based Model Fe-2.82 at. pct Cr-0.13 at. pct Mo-0.18 at. pct V Alloy

    NASA Astrophysics Data System (ADS)

    Kang, C. W.; Meka, Sai Ramudu; Schacherl, R. E.; Mittemeijer, E. J.

    2015-01-01

    Internal nitride development in iron-based quaternary Fe-Cr-Mo-V alloy, as a model alloy for 31CrMoV9 steel, was investigated by performing controlled gaseous nitriding experiments. The nitride-precipitation process starts with the development of nanosized platelets of, coherent, cubic NaCl-type nitride, along {100} lattice planes of the ferrite matrix, in association with matrix-lattice dilation. The development of nitride platelets having a NaCl-type crystal structure, satisfying the Baker-Nutting orientation relationship with the ferrite matrix, and the nitrogen content of the nitrided zone suggest the development of a quaternary "mixed" (Cr x ,V y , Mo1- x-y)N nitride, similar to the development of "mixed" ternary nitrides as reported for nitrided Fe-Cr-Al and Fe-Cr-Ti alloys. In a later stage, the nitride platelets undergo discontinuous coarsening resulting in the development of a lamellar microstructure consisting of nitride and ferrite lamellae. Kinetic analysis demonstrated that the thermally activated nature of growth of the diffusion zone is controlled with about equal weights, by the diffusion of nitrogen in the substrate matrix and the matrix lattice solubility of nitrogen.

  13. Precipitation Matters

    ERIC Educational Resources Information Center

    McDuffie, Thomas

    2007-01-01

    Although weather, including its role in the water cycle, is included in most elementary science programs, any further examination of raindrops and snowflakes is rare. Together rain and snow make up most of the precipitation that replenishes Earth's life-sustaining fresh water supply. When viewed individually, raindrops and snowflakes are quite…

  14. Iron Chelation

    MedlinePlus

    ... iron overload and need treatment. What is iron overload? Iron chelation therapy is used when you have ... may want to perform: How quickly does iron overload happen? This is different for each person. It ...

  15. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 17, 1 November 1993--31 December 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-06-01

    Very high cobalt catalysts have been prepared on steamed and acid-washed y zeolite. These catalysts are very active. Some of them have proven to be very stable. Additionally, if provisions are made to control the temperature build up on the catalyst bed, low methane selectivities result. Additional work is indicated, for instance, perhaps even higher activity catalysts can result from higher levels of cobalt or changes in the catalyst preparation procedure. Since the issue of whether small amounts of ruthenium can promote the catalyst is not completely resolved, catalyst preparation procedure experiments should continue with ruthenium vs. ruthenium-free catalysts. For instance, different methods of impregnation and/or activation should be investigated.

  16. Heating and Efficiency Comparison of a Fischer-Tropsch (FT) Fuel, JP-8+100, and Blends in a Three-Cup Combustor Sector

    NASA Technical Reports Server (NTRS)

    Thomas, Anna E.; Shouse, Dale T.; Neuroth, Craig; Lynch, Amy; Frayne, Charles W.; Stutrud, Jeffrey S.; Corporan, Edwin; Hankins, Terry; Saxena, Nikita T.; Hendricks, Robert C.

    2012-01-01

    In order to realize alternative fueling for military and commercial use, the industry has set forth guidelines that must be met by each fuel. These aviation fueling requirements are outlined in MIL-DTL-83133F(2008) or ASTM D 7566-Annex standards and are classified as drop-in fuel replacements. This paper provides combustor performance data for synthetic-paraffinic-kerosene- (SPK-) type (Fisher-Tropsch (FT)) fuel and blends with JP-8+100, relative to JP-8+100 as baseline fueling. Data were taken at various nominal inlet conditions: 75 psia (0.52 MPa) at 500 aF (533 K), 125 psia (0.86 MPa) at 625 aF (603 K), 175 psia (1.21 MPa) at 725 aF (658 K), and 225 psia (1.55 MPa) at 790 aF (694 K). Combustor performance analysis assessments were made for the change in flame temperatures, combustor efficiency, wall temperatures, and exhaust plane temperatures at 3%, 4%, and 5% combustor pressure drop (% P) for fuel:air ratios (F/A) ranging from 0.010 to 0.025. Significant general trends show lower liner temperatures and higher flame and combustor outlet temperatures with increases in FT fueling relative to JP-8+100 fueling. The latter affects both turbine efficiency and blade/vane life. In general, 100% SPK-FT fuel and blends with JP-8+100 produce less particulates and less smoke and have lower thermal impact on combustor hardware.

  17. A new hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust: A structural promoter of cobalt catalyst for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Pankina, G. V.; Chernavskii, P. A.; Lunin, V. V.

    2016-09-01

    Aspects of the physicochemical properties of a hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust are studied. The use of a hydrocarbon material based on sea buckthorn sawdust as a structural promoter of Co/CHip cobalt catalyst in the reaction of CO hydrogenation is shown to require an additional cycling stage in the mode of reduction and oxidation. The resulting mean size of the Co particles is found to be 18-19 nm and is considered acceptable for the synthesis of C5+ liquid hydrocarbons.

  18. Effect of pretreatment on the activity of a Ru-promoted Co/Al{sub 2}O{sub 3} Fischer-Tropsch catalyst

    SciTech Connect

    Belambe, A.R.; Oukaci, R.; Goodwin, J.G. Jr.

    1997-02-01

    The effect of calcination and reduction temperatures on the activity of a Ru-promoted Co/Al{sub 2}O{sub 3} catalyst for the CO hydrogenation reaction has been studied. The catalyst was prepared by the incipient wetness impregnation method and calcined and reduced at various temperatures. Along with overall steady-state rate analysis, steady-state isotopic transient kinetic analysis was used to investigate the effect of the pretreatment conditions on the intrinsic activity and coverages of surface intermediates. Catalyst characterization techniques such as XRD, TPR, and hydrogen chemisorption were also used. The calcination temperature was found to have a pronounced effect on the overall activity of the catalyst but not on the intrinsic activity of the catalyst sites. On the other hand, the reduction temperature had only a negligible effect on the overall and intrinsic activities. The decrease in rate at high calcination temperatures was caused by a decrease in the number of surface active sites due to a decrease in the reducibility of the catalyst. Neither the reduction nor the calcination conditions had any effect on chain growth probability. Calcination temperature did have, however, a small effect on CH{sub 4} selectivity. 38 refs., 5 figs., 5 tabs.

  19. Electrostatic precipitator with precipitator electrodes

    SciTech Connect

    Junkers, G.

    1980-12-16

    The invention relates to an electrostatic precipitator with collecting electrodes which are arranged in rows adjacent to each other and in respective pairs at equal distances from a respective discharge electrode with which they cooperate. Spring elements are provided between the collecting electrodes and influence the stiffness and oscillating properties of the array of the collecting electrodes.

  20. Acidic precipitation

    SciTech Connect

    Martin, H.C.

    1987-01-01

    At the International Symposium on Acidic Precipitation, over 400 papers were presented, and nearly 200 of them are included here. They provide an overview of the present state of the art of acid rain research. The Conference focused on atmospheric science (monitoring, source-receptor relationships), aquatic effects (marine eutrophication, lake acidification, impacts on plant and fish populations), and terrestrial effects (forest decline, soil acidification, etc.).

  1. Characterization of Catalyst Materials for Production of Aerospace Fuels

    NASA Technical Reports Server (NTRS)

    DeLaRee, Ana B.; Hepp, Aloysius F.

    2011-01-01

    Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

  2. Characterization of Catalyst Materials for Production of Aerospace Fuels

    NASA Technical Reports Server (NTRS)

    Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

    2012-01-01

    Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

  3. Electrostatic precipitator

    SciTech Connect

    Hayashi, T.

    1982-08-03

    An electrostatic precipitator comprising a plurality of flat plate dust-collecting electrodes, arranged in substantially equally spaced and parallel relationship with one another and each having a discharge electrode, or electrodes, on and along the edge of one side thereof with the discharge electrodes of the adjacent dust-collecting electrodes alternately facing in opposite directions; the edges having the discharge electrodes are arranged in a setback relation by some distance in relation to the nearby edges of the adjacent dust-collecting plates, where no discharge electrodes are provided, so that uniform and nonuniform electric fields may be produced.

  4. Use of phosphate for separation of cobalt from iron

    USGS Publications Warehouse

    North, V.; Wells, R.C.

    1942-01-01

    The well-known tendency of cobalt to be retained by the iron-alumina precipitate produced by ammonia has generally been ascribed to a specific adsorption by the large surface of this gelatinous precipitate. Whatever its cause, it can be overcome by precipitating the iron as phosphate at a pH of 3.5. The precipitate is easily filterable and practically all the cobalt passes into the filtrate.

  5. Iron biomineralization by anaerobic neutrophilic iron-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Miot, Jennyfer; Benzerara, Karim; Morin, Guillaume; Kappler, Andreas; Bernard, Sylvain; Obst, Martin; Férard, Céline; Skouri-Panet, Fériel; Guigner, Jean-Michel; Posth, Nicole; Galvez, Matthieu; Brown, Gordon E., Jr.; Guyot, François

    2009-02-01

    Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate-dependent iron-oxidizing bacterium Acidovorax sp. strain BoFeN1 in the presence of dissolved Fe(II) using electron microscopy and Scanning Transmission X-ray Microscopy (STXM). All detected minerals consisted mainly of amorphous iron phosphates, but based on their morphology and localization, three types of precipitates could be discriminated: (1) mineralized filaments at distance from the cells, (2) globules of 100 ± 25 nm in diameter, at the cell surface and (3) a 40-nm thick mineralized layer within the periplasm. All of those phases were shown to be intimately associated with organic molecules. Periplasmic encrustation was accompanied by an accumulation of protein moieties. In the same way, exopolysaccharides were associated with the extracellular mineralized filaments. The evolution of cell encrustation was followed by TEM over the time course of a culture: cell encrustation proceeded progressively, with rapid precipitation in the periplasm (in a few tens of minutes), followed by the formation of surface-bound globules. Moreover, we frequently observed an asymmetric mineral thickening at the cell poles. In parallel, the evolution of iron oxidation was quantified by STXM: iron both contained in the bacteria and in the extracellular precipitates reached complete oxidation within 6 days. While a progressive oxidation of Fe in the bacteria and in the medium could be observed, spatial redox (oxido-reduction state) heterogeneities were detected at the cell poles and in the extracellular precipitates after 1 day. All these findings provide new information to further the understanding of molecular processes involved in iron biomineralization by anaerobic iron-oxidizing bacteria and

  6. Microbial reduction of iron ore

    DOEpatents

    Hoffmann, M.R.; Arnold, R.G.; Stephanopoulos, G.

    1989-11-14

    A process is provided for reducing iron ore by treatment with microorganisms which comprises forming an aqueous mixture of iron ore, microorganisms operable for reducing the ferric iron of the iron ore to ferrous iron, and a substrate operable as an energy source for the microbial reduction; and maintaining the aqueous mixture for a period of time and under conditions operable to effect the reduction of the ore. Preferably the microorganism is Pseudomonas sp. 200 and the reduction conducted anaerobically with a domestic wastewater as the substrate. An aqueous solution containing soluble ferrous iron can be separated from the reacted mixture, treated with a base to precipitate ferrous hydroxide which can then be recovered as a concentrated slurry. 11 figs.

  7. Microbial reduction of iron ore

    DOEpatents

    Hoffmann, Michael R.; Arnold, Robert G.; Stephanopoulos, Gregory

    1989-01-01

    A process is provided for reducing iron ore by treatment with microorganisms which comprises forming an aqueous mixture of iron ore, microorganisms operable for reducing the ferric iron of the iron ore to ferrous iron, and a substrate operable as an energy source for the microbial reduction; and maintaining the aqueous mixture for a period of time and under conditions operable to effect the reduction of the ore. Preferably the microorganism is Pseudomonas sp. 200 and the reduction conducted anaerobically with a domestic wastewater as the substrate. An aqueous solution containing soluble ferrous iron can be separated from the reacted mixture, treated with a base to precipitate ferrous hydroxide which can then be recovered as a concentrated slurry.

  8. Microbial iron uptake as a mechanism for dispersing iron from deep-sea hydrothermal vents.

    PubMed

    Li, Meng; Toner, Brandy M; Baker, Brett J; Breier, John A; Sheik, Cody S; Dick, Gregory J

    2014-01-01

    Deep-sea hydrothermal vents are a significant source of oceanic iron. Although hydrothermal iron rapidly precipitates as inorganic minerals on mixing with seawater, it can be stabilized by organic matter and dispersed more widely than previously recognized. The nature and source of this organic matter is unknown. Here we show that microbial genes involved in cellular iron uptake are highly expressed in the Guaymas Basin deep-sea hydrothermal plume. The nature of these microbial iron transporters, taken together with the low concentration of dissolved iron and abundance of particulate iron in the plume, indicates that iron minerals are the target for this microbial scavenging and uptake. Our findings indicate that cellular iron uptake is a major process in plume microbial communities and suggest new mechanisms for generating Fe-C complexes. This 'microbial iron pump' could represent an important mode of converting hydrothermal iron into bioavailable forms that can be dispersed throughout the oceans.

  9. Iron-tolerant Cyanobacteria as a Tool to Study Terrestrial and Extraterrestrial Iron Deposition

    NASA Technical Reports Server (NTRS)

    Brown, I. I.; Mummey, D.; Cooksey, K. E.; McKay, D. S.

    2005-01-01

    We are investigating biological mechanisms of terrestrial iron deposition as analogs for Martian hematite recently confirmed by. Possible terrestrial analogs include iron oxide hydrothermal deposits, rock varnish, iron-rich laterites, ferricrete soils, moki balls, and banded iron formations (BIFs). With the discovery of recent volcanic activity in the summit craters of five Martian volcanoes, renewed interest in the iron dynamics of terrestrial hydrothermal environments and associated microorganisms is warranted. In this study we describe a new genus and species of CB exhibiting elevated dissolved iron tolerance and the ability to precipitate hematite on the surface of their exopolymeric sheathes.

  10. Iron deficiency.

    PubMed

    Scrimshaw, N S

    1991-10-01

    The world's leading nutritional problem is iron deficiency. 66% of children and women aged 15-44 years in developing countries have it. Further, 10-20% of women of childbearing age in developed countries are anemic. Iron deficiency is identified with often irreversible impairment of a child's learning ability. It is also associated with low capacity for adults to work which reduces productivity. In addition, it impairs the immune system which reduces the body's ability to fight infection. Iron deficiency also lowers the metabolic rate and the body temperature when exposed to cold. Hemoglobin contains nearly 73% of the body's iron. This iron is always being recycled as more red blood cells are made. The rest of the needed iron does important tasks for the body, such as binds to molecules that are reservoirs of oxygen for muscle cells. This iron comes from our diet, especially meat. Even though some plants, such as spinach, are high in iron, the body can only absorb 1.4-7% of the iron in plants whereas it can absorb 20% of the iron in red meat. In many developing countries, the common vegetarian diets contribute to high rates of iron deficiency. Parasitic diseases and abnormal uterine bleeding also promote iron deficiency. Iron therapy in anemic children can often, but not always, improve behavior and cognitive performance. Iron deficiency during pregnancy often contributes to maternal and perinatal mortality. Yet treatment, if given to a child in time, can lead to normal growth and hinder infections. However, excess iron can be damaging. Too much supplemental iron in a malnourished child promotes fatal infections since the excess iron is available for the pathogens use. Many countries do not have an effective system for diagnosing, treating, and preventing iron deficiency. Therefore a concerted international effort is needed to eliminate iron deficiency in the world.

  11. Electrostatic precipitator manual

    SciTech Connect

    McDonald, J.R.; Dean, A.H.

    1982-01-01

    Studies performed by various individuals and organizations on the application of electrostatic precipitators to the collection of fly ash produced in the combustion of pulverized fuel are summarized in this manual. The scope of the studies evaluated include full scale precipitators and laboratory investigations. It covers measurement of fly ash resistivity, rapping reentrainment, conditioning agents, fundamental operations of hot-side precipitators. The major chapter headings are: Terminology and General Design Features Associated with Electrostatic Precipitators Used to Collect Fly Ash Particles; Fundamental Principles of Electrostatic Precipitation; Limiting Factors Affecting Precipitator Performance; Use of Electrostatic Precipitators for the Collection of Fly Ash; Analysis of Factors influencing ESP Performance; Emissions from Electrostatic Precipitators; Choosig an Electrostatic Precipitator: Cold-side versus Hot-side; Safety Aspects of Working with Electrostatic Precipitators; Maintenance Procedures; Troubleshooting; An Electrostatic Precipitator Computer Model; Features of a Well-equipped Electrostatic Precipitator.

  12. Iron Meteorite

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    A meteorite composed mainly of nickel-iron, with traces of other metals; also referred to simply as an iron, and formerly known as a siderite. Irons account for over 6% of all known meteorite specimens. They are the easiest type to identify, being heavy, magnetic and rust-colored; their metallic sheen tarnishes quickly on the Earth's surface, but otherwise irons show better resistance to weatheri...

  13. Iron (Oxyhydr)Oxide Biosignatures in the Brushy Basin Member of the Jurassic Morrison Formation, Colorado Plateau, USA: Analog for Martian Diagenetic Iron

    NASA Astrophysics Data System (ADS)

    Potter-McIntyre, S. L.; Chan, M. A.; McPherson, B. J.

    2012-03-01

    Iron precipitates in modern microbial mats compared with iron cements in Jurassic alkaline saline lake sediments show that morphological and chemical biosignatures are present and preserved in oxidized, evaporative environments analogous to Mars.

  14. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J. R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Jung-Keuk, Kang; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. These processes are discussed.

  15. PRECIPITATION OF PLUTONOUS PEROXIDE

    DOEpatents

    Barrick, J.G.; Manion, J.P.

    1961-08-15

    A precipitation process for recovering plutonium values contained in an aqueous solution is described. In the process for precipitating plutonium as plutonous peroxide, hydroxylamine or hydrazine is added to the plutoniumcontaining solution prior to the addition of peroxide to precipitate plutonium. The addition of hydroxylamine or hydrazine increases the amount of plutonium precipitated as plutonous peroxide. (AEC)

  16. Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2011-01-01

    When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

  17. Precipitating Condensation Clouds in Substellar Atmospheres

    NASA Technical Reports Server (NTRS)

    Ackerman, Andrew S.; Marley, Mark S.; Gore, Warren J. (Technical Monitor)

    2000-01-01

    We present a method to calculate vertical profiles of particle size distributions in condensation clouds of giant planets and brown dwarfs. The method assumes a balance between turbulent diffusion and precipitation in horizontally uniform cloud decks. Calculations for the Jovian ammonia cloud are compared with previous methods. An adjustable parameter describing the efficiency of precipitation allows the new model to span the range of predictions from previous models. Calculations for the Jovian ammonia cloud are found to be consistent with observational constraints. Example calculations are provided for water, silicate, and iron clouds on brown dwarfs and on a cool extrasolar giant planet.

  18. Progressive Silicification of Iron Microbes — Preliminary Observations from a Two Year Experiment

    NASA Astrophysics Data System (ADS)

    Schieber, J.

    2010-03-01

    Iron microbe mats were stored at 50°C in a silica-rich solution for two years and intermittently examined by SEM. The results suggest a high potential for morphological preservation of iron microbes in silica precipitating environments.

  19. DETERMINATION OF THE RATES AND PRODUCTS OF FERROUS IRON OXIDATION IN ARSENIC-CONTAMINATED POND WATER.

    EPA Science Inventory

    Dissolved ferrous iron and arsenic in the presence of insufficient oxygenated ground water is released into a pond. When the mixing of ferrous iron and oxygenated water within the pond occurs, the ferrous iron is oxidized and precipitated as an iron oxide. Groups of experiments...

  20. Direct Biohydrometallurgical Extraction of Iron from Ore

    SciTech Connect

    T.C. Eisele

    2005-10-01

    A completely novel approach to iron extraction was investigated, based on reductive leaching of iron by anaerobic bacteria. Microorganisms were collected from an anaerobic bog where natural seepage of dissolved iron was observed. This mixed culture was used to reduce insoluble iron in a magnetite ore to the soluble ferrous (Fe{sup +2}) state. While dissolution rates were slow, concentrations of dissolved iron as high as 3487 mg/l could be reached if sufficient time was allowed. A factorial study of the effects of trace nutrients and different forms of organic matter indicated that the best dissolution rates and highest dissolved iron concentrations were achieved using soluble carbohydrate (sucrose) as the bacterial food source, and that nutrients other than nitrogen, phosphorus, potassium, sodium, and acetate were not necessary. A key factor in reaching high levels of dissolved iron was maintaining a high level of carbon dioxide in solution, since the solubility of iron carbonates increases markedly as the quantity of dissolved carbon dioxide increases. Once the iron is dissolved, it has been demonstrated that the ferrous iron can then be electroplated from solution, provided that the concentration of iron is sufficiently high and the hydrogen ion concentration is sufficiently low. However, if the leaching solution is electrolyzed directly, organic matter precipitates at the cathode along with the metallic iron. To prevent this problem, the ferrous iron should be separated from the bulk solution in a more concentrated, purified form. One route to accomplishing this is to take advantage of the change in solubility of ferrous iron as a function of carbon dioxide concentration. By cycling the concentration of carbon dioxide in solution, it is possible to produce an iron-rich concentrate that should be suitable for electrolysis. This represents the first viable hydrometallurgical method for leaching iron directly from ore and producing metallic iron.

  1. Iron refractory iron deficiency anemia

    PubMed Central

    De Falco, Luigia; Sanchez, Mayka; Silvestri, Laura; Kannengiesser, Caroline; Muckenthaler, Martina U.; Iolascon, Achille; Gouya, Laurent; Camaschella, Clara; Beaumont, Carole

    2013-01-01

    Iron refractory iron deficiency anemia is a hereditary recessive anemia due to a defect in the TMPRSS6 gene encoding Matriptase-2. This protein is a transmembrane serine protease that plays an essential role in down-regulating hepcidin, the key regulator of iron homeostasis. Hallmarks of this disease are microcytic hypochromic anemia, low transferrin saturation and normal/high serum hepcidin values. The anemia appears in the post-natal period, although in some cases it is only diagnosed in adulthood. The disease is refractory to oral iron treatment but shows a slow response to intravenous iron injections and partial correction of the anemia. To date, 40 different Matriptase-2 mutations have been reported, affecting all the functional domains of the large ectodomain of the protein. In vitro experiments on transfected cells suggest that Matriptase-2 cleaves Hemojuvelin, a major regulator of hepcidin expression and that this function is altered in this genetic form of anemia. In contrast to the low/undetectable hepcidin levels observed in acquired iron deficiency, in patients with Matriptase-2 deficiency, serum hepcidin is inappropriately high for the low iron status and accounts for the absent/delayed response to oral iron treatment. A challenge for the clinicians and pediatricians is the recognition of the disorder among iron deficiency and other microcytic anemias commonly found in pediatric patients. The current treatment of iron refractory iron deficiency anemia is based on parenteral iron administration; in the future, manipulation of the hepcidin pathway with the aim of suppressing it might become an alternative therapeutic approach. PMID:23729726

  2. Tubular precipitation and redox gradients on a bubbling template

    PubMed Central

    Stone, David A.; Goldstein, Raymond E.

    2004-01-01

    Tubular structures created by precipitation abound in nature, from chimneys at hydrothermal vents to soda straws in caves. Their formation is controlled by chemical gradients within which precipitation occurs, defining a surface that templates the growing structure. We report a self-organized periodic templating mechanism producing tubular structures electrochemically in iron-ammonium-sulfate solutions; iron oxides precipitate on the surface of bubbles that linger at the tube rim and then detach, leaving behind a ring of material. The acid–base and redox gradients spontaneously generated by diffusion of ammonia from the bubble into solution organize radial compositional layering within the tube wall, a mechanism studied on a larger scale by complex Liesegang patterns of iron oxides formed as ammonia diffuses through a gel containing FeSO4. When magnetite forms within the wall, a tube may grow curved in an external magnetic field. Connections with free-boundary problems in speleothem formation are emphasized. PMID:15284444

  3. Fossilized iron bacteria reveal a pathway to the biological origin of banded iron formation.

    PubMed

    Chi Fru, Ernest; Ivarsson, Magnus; Kilias, Stephanos P; Bengtson, Stefan; Belivanova, Veneta; Marone, Federica; Fortin, Danielle; Broman, Curt; Stampanoni, Marco

    2013-01-01

    Debates on the formation of banded iron formations in ancient ferruginous oceans are dominated by a dichotomy between abiotic and biotic iron cycling. This is fuelled by difficulties in unravelling the exact processes involved in their formation. Here we provide fossil environmental evidence for anoxygenic photoferrotrophic deposition of analogue banded iron rocks in shallow marine waters associated with an Early Quaternary hydrothermal vent field on Milos Island, Greece. Trace metal, major and rare earth elemental compositions suggest that the deposited rocks closely resemble banded iron formations of Precambrian origin. Well-preserved microbial fossils in combination with chemical data imply that band formation was linked to periodic massive encrustation of anoxygenic phototrophic biofilms by iron oxyhydroxide alternating with abiotic silica precipitation. The data implicate cyclic anoxygenic photoferrotrophy and their fossilization mechanisms in the construction of microskeletal fabrics that result in the formation of characteristic banded iron formation bands of varying silica and iron oxide ratios. PMID:23784372

  4. Catalyst for selective conversion of synthesis gas and method of making the catalyst

    DOEpatents

    Dyer, Paul N.; Pierantozzi, Ronald

    1986-01-01

    A Fischer-Tropsch (F-T) catalyst, a method of making the catalyst and an F-T process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range. In general, the selective and notably stable catalyst, consists of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of an F-T metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

  5. Study of synthesis gas conversion over metal oxides. Progress report, August 1, 1983-July 31, 1984

    SciTech Connect

    Ekerdt, J.G.

    1984-01-01

    The primary objectives of the research are identification of the reaction intermediates present during CO hydrogenation reactions, determination of the reaction pathways whereby the intermediates are converted into products, identification of the active sites for the various steps in CO hydrogenation and the development of an understanding of the causes for catalytic activity and selectivity. Iron oxide and zirconium dioxide catalysts were used to study the Fischer-Tropsch and isosynthesis processes, respectively. Both involve CO hydrogenation but display very different selectivity and catalytic chemistry. The presence of acyl intermediates and their role, if any, in the Fischer-Tropsch process over iron-based catalysts was studied at one to ten atm total pressure and 225/sup 0/C. The studies involved introducing a scavenger into the CO/H/sub 2/ feed mixture which would selectively react with acyl species and form a compound which was easily identified. The significance of our experiments and their interpretation is difficult to assess at present. We were unable to correlate the concentration of hydrocarbon or oxygenated synthesis products, chiefly methanol and ethanol, with the concentrations of trialkyl amines. A correlation may have suggested if acyl species are formed during the propagation reaction or if they are formed as precursors to aldehyde and alcohol products. The diethyl amine studies do provide consistent evidence that CO insertion does occur over a heterogeneous surface during Fischer-Tropsch synthesis. The isosynthesis studies have included work at 35 atm and at 1 atm. The high pressure work is examining the branching reaction and the C/sub 2/-C/sub 4/ isosynthesis products. The 1 atm studies are examining the C/sub 1/ surface species which may initiate the reaction as well as participate in the formation of C/sub 2/+ products and are examining the role of surface sites in CO/H/sub 2/ reactions over ZrO/sub 2/. 20 references, 2 figures.

  6. Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

    NASA Technical Reports Server (NTRS)

    Cowen, Jonathan E.; Hepp, Aloysius F.; Duffy, Norman V.; Jose, Melanie J.; Choi, D. B.; Brothers, Scott M.; Baird, Michael F.; Tomsik, Thomas M.; Duraj, Stan A.; Williams, Jennifer N.; Kulis, Michael J.; Gaier, James R.

    2009-01-01

    We describe several related studies where simple iron, nickel, and cobalt complexes were prepared, decomposed, and characterized for aeronautics (Fischer-Tropsch catalysts) and space (high-fidelity lunar regolith simulant additives) applications. We describe the synthesis and decomposition of several new nickel dithiocarbamate complexes. Decomposition resulted in a somewhat complicated product mix with NiS predominating. The thermogravimetric analysis of fifteen tris(diorganodithiocarbamato)iron(III) has been investigated. Each undergoes substantial mass loss upon pyrolysis in a nitrogen atmosphere between 195 and 370 C, with major mass losses occurring between 279 and 324 C. Steric repulsion between organic substituents generally decreased the decomposition temperature. The product of the pyrolysis was not well defined, but usually consistent with being either FeS or Fe2S3 or a combination of these. Iron nanoparticles were grown in a silica matrix with a long-term goal of introducing native iron into a commercial lunar dust simulant in order to more closely simulate actual lunar regolith. This was also one goal of the iron and nickel sulfide studies. Finally, cobalt nanoparticle synthesis is being studied in order to develop alternatives to crude processing of cobalt salts with ceramic supports for Fischer-Tropsch synthesis.

  7. Global Precipitation Measurement

    NASA Technical Reports Server (NTRS)

    Hou, Arthur Y.; Skofronick-Jackson, Gail; Kummerow, Christian D.; Shepherd, James Marshall

    2008-01-01

    This chapter begins with a brief history and background of microwave precipitation sensors, with a discussion of the sensitivity of both passive and active instruments, to trace the evolution of satellite-based rainfall techniques from an era of inference to an era of physical measurement. Next, the highly successful Tropical Rainfall Measuring Mission will be described, followed by the goals and plans for the Global Precipitation Measurement (GPM) Mission and the status of precipitation retrieval algorithm development. The chapter concludes with a summary of the need for space-based precipitation measurement, current technological capabilities, near-term algorithm advancements and anticipated new sciences and societal benefits in the GPM era.

  8. Selective Precipitation of Proteins.

    PubMed

    Matulis, Daumantas

    2016-01-01

    Selective precipitation of proteins can be used as a bulk method to recover the majority of proteins from a crude lysate, as a selective method to fractionate a subset of proteins from a protein solution, or as a very specific method to recover a single protein of interest from a purification step. This unit describes a number of methods suitable for selective precipitation. In each of the protocols that are outlined, the physical or chemical basis of the precipitation process, the parameters that can be varied for optimization, and the basic steps for developing an optimized precipitation are described.

  9. METABOLISM OF IRON STORES

    PubMed Central

    SAITO, HIROSHI

    2014-01-01

    ABSTRACT Remarkable progress was recently achieved in the studies on molecular regulators of iron metabolism. Among the main regulators, storage iron, iron absorption, erythropoiesis and hepcidin interact in keeping iron homeostasis. Diseases with gene-mutations resulting in iron overload, iron deficiency, and local iron deposition have been introduced in relation to the regulators of storage iron metabolism. On the other hand, the research on storage iron metabolism has not advanced since the pioneering research by Shoden in 1953. However, we recently developed a new method for determining ferritin iron and hemosiderin iron by computer-assisted serum ferritin kinetics. Serum ferritin increase or decrease curves were measured in patients with normal storage iron levels (chronic hepatitis C and iron deficiency anemia treated by intravenous iron injection), and iron overload (hereditary hemochromatosis and transfusion dependent anemia). We thereby confirmed the existence of two iron pathways where iron flows followed the numbered order (1) labile iron, (2) ferritin and (3) hemosiderin in iron deposition and mobilization among many previously proposed but mostly unproven routes. We also demonstrated the increasing and decreasing phases of ferritin iron and hemosiderin iron in iron deposition and mobilization. The author first demonstrated here the change in proportion between pre-existing ferritin iron and new ferritin iron synthesized by removing iron from hemosiderin in the course of iron removal. In addition, the author disclosed the cause of underestimation of storage iron turnover rate which had been reported by previous investigators in estimating storage iron turnover rate of normal subjects. PMID:25741033

  10. PRECIPITATION OF PROTACTINIUM

    DOEpatents

    Moore, R.L.

    1958-07-15

    An lmprovement in the separation of protactinium from aqueous nitric acid solutions is described. 1t covers the use of lead dioxide and tin dioxide as carrier precipitates for the protactinium. In carrying out the process, divalent lead or divalent tin is addcd to the solution and oxidized, causing formation of a carrier precipitate of lead dioxide or stannic oxide, respectively.

  11. Electrostatic precipitator efficiency enhancement

    SciTech Connect

    Polizzotti, D.M.; Steelhammer, J.C.

    1983-05-24

    Method for enhancing the removal of particles from a particleladen gas stream utilizing an electrostatic precipitator, which comprises treating the gas with morpholine or derivatives thereof. Treated particles are found to also have desirable flow characteristics. Particularly effective compositions for the purpose comprise a combination of the morpholine, or derivative thereof, with an electrostatic precipitator efficiency enhancer, and in particular an alkanolamine.

  12. Features of the interaction of Cu-rich precipitates with irradiation-produced defects in α-Fe.

    SciTech Connect

    Arokiam, Alan; Barashev, Aleksandr; Bacon, David J; Osetskiy, Yury N

    2005-01-01

    The interaction between copper-rich precipitates in {alpha}-iron and either vacancies or self-interstitial atoms and their clusters is studied by atomic-scale modeling. Results are compared with predictions of elasticity theory and interpreted in terms of size misfit of precipitates and defects, and the modulus and cohesive energy differences between iron and copper. Interstitial defects are repelled by precipitates at large distance but, like vacancies, attracted at small distance. Hence, copper precipitates in iron can be sinks for both vacancy and interstitial defects, and can act as strong recombination centers under irradiation conditions. This leads to a tentative explanation for the mixed Cu-Fe structure of precipitates and the absence of precipitate growth under neutron irradiation conditions. More generally, both vacancy and interstitial defects may be strongly bound to precipitates with weaker cohesion than the matrix.

  13. Arsenic removal from acidic solutions with biogenic ferric precipitates.

    PubMed

    Ahoranta, Sarita H; Kokko, Marika E; Papirio, Stefano; Özkaya, Bestamin; Puhakka, Jaakko A

    2016-04-01

    Treatment of acidic solution containing 5g/L of Fe(II) and 10mg/L of As(III) was studied in a system consisting of a biological fluidized-bed reactor (FBR) for iron oxidation, and a gravity settler for iron precipitation and separation of the ferric precipitates. At pH 3.0 and FBR retention time of 5.7h, 96-98% of the added Fe(II) precipitated (99.1% of which was jarosite). The highest iron oxidation and precipitation rates were 1070 and 28mg/L/h, respectively, and were achieved at pH 3.0. Subsequently, the effect of pH on arsenic removal through sorption and/or co-precipitation was examined by gradually decreasing solution pH from 3.0 to 1.6 (feed pH). At pH 3.0, 2.4 and 1.6, the highest arsenic removal efficiencies obtained were 99.5%, 80.1% and 7.1%, respectively. As the system had ferric precipitates in excess, decreased arsenic removal was likely due to reduced co-precipitation at pH<2.4. As(III) was partially oxidized to As(V) in the system. In shake flask experiments, As(V) sorbed onto jarosite better than As(III). Moreover, the sorption capacity of biogenic jarosite was significantly higher than that of synthetic jarosite. The developed bioprocess simultaneously and efficiently removes iron and arsenic from acidic solutions, indicating potential for mining wastewater treatment. PMID:26705889

  14. Iron-Tolerant Cyanobacteria: Ecophysiology and Fingerprinting

    NASA Technical Reports Server (NTRS)

    Brown, I. I.; Mummey, D.; Lindsey, J.; McKay, D. S.

    2006-01-01

    Although the iron-dependent physiology of marine and freshwater cyanobacterial strains has been the focus of extensive study, very few studies dedicated to the physiology and diversity of cyanobacteria inhabiting iron-depositing hot springs have been conducted. One of the few studies that have been conducted [B. Pierson, 1999] found that cyanobacterial members of iron depositing bacterial mat communities might increase the rate of iron oxidation in situ and that ferrous iron concentrations up to 1 mM significantly stimulated light dependent consumption of bicarbonate, suggesting a specific role for elevated iron in photosynthesis of cyanobacteria inhabiting iron-depositing hot springs. Our recent studies pertaining to the diversity and physiology of cyanobacteria populating iron-depositing hot springs in Great Yellowstone area (Western USA) indicated a number of different isolates exhibiting elevated tolerance to Fe(3+) (up to 1 mM). Moreover, stimulation of growth was observed with increased Fe(3+) (0.02-0.4 mM). Molecular fingerprinting of unialgal isolates revealed a new cyanobacterial genus and species Chroogloeocystis siderophila, an unicellular cyanobacterium with significant EPS sheath harboring colloidal Fe(3+) from iron enriched media. Our preliminary data suggest that some filamentous species of iron-tolerant cyanobacteria are capable of exocytosis of iron precipitated in cytoplasm. Prior to 2.4 Ga global oceans were likely significantly enriched in soluble iron [Lindsay et al, 2003], conditions which are not conducive to growth of most contemporary oxygenic cyanobacteria. Thus, iron-tolerant CB may have played important physiological and evolutionary roles in Earths history.

  15. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  16. Planktonic marine iron oxidizers drive iron mineralization under low-oxygen conditions.

    PubMed

    Field, E K; Kato, S; Findlay, A J; MacDonald, D J; Chiu, B K; Luther, G W; Chan, C S

    2016-09-01

    Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypothesis was that cyanobacteria produced oxygen which oxidized iron abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to banded iron formations (BIFs) and other ferruginous deposits. However, there is currently little evidence for planktonic marine iron oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 μm O2 , <0.2 μm H2 S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Cyanobacteria may be providing oxygen for microaerophilic iron oxidation through a symbiotic relationship; at high Fe(II) levels, cyanobacteria would gain protection against Fe(II) toxicity. A Zetaproteobacteria isolate from this site oxidized iron at rates sufficient to account for deposition of geologic iron formations. In sum, our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron oxidizers were likely important drivers of iron mineralization in ancient oceans. PMID:27384464

  17. Economy of precipitating agent application in municipal wastewater treatment facilities

    NASA Technical Reports Server (NTRS)

    Neis, U.; Geppert, B.; Hahn, H. H.; Gleisberg, D.

    1983-01-01

    Purification by precipitation in this study is not considered primarily as a means of phosphate removal but as a method for reduction of suspended solids BOD and COD. A dynamic calculation procedure is used to allow for exact determination of time dependent variation of costs. The results show that costs of wastewater treatment by precipitation may equal those of conventional primary clarification and secondary biological treatment, especially with low-cost iron-II-salts in simultaneous precipitation and in larger plants ( 20,000 PF). Cost advantages may be accrued in smaller plants by using the more expensive trivalent salts in pre-precipitation as compared to conventional low-load biological treatment. This is due mainly to better effluent quality and, consequently, lower wastewater fees (Wastewater Discharge Act). If the precipitant is dosed temporarily only during periods of highest pollution the savings can be about 5 to 10%.

  18. Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

    NASA Astrophysics Data System (ADS)

    Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.; Emerson, David; Banfield, Jillian F.

    2009-07-01

    Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence (μXRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolated from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.

  19. Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

    SciTech Connect

    Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.; Emerson, David; Banfield, Jillian F.

    2010-06-22

    Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence ({mu}XRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolated from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.

  20. Cloud and Precipitation Radar

    NASA Astrophysics Data System (ADS)

    Hagen, Martin; Höller, Hartmut; Schmidt, Kersten

    Precipitation or weather radar is an essential tool for research, diagnosis, and nowcasting of precipitation events like fronts or thunderstorms. Only with weather radar is it possible to gain insights into the three-dimensional structure of thunderstorms and to investigate processes like hail formation or tornado genesis. A number of different radar products are available to analyze the structure, dynamics and microphysics of precipitation systems. Cloud radars use short wavelengths to enable detection of small ice particles or cloud droplets. Their applications differ from weather radar as they are mostly orientated vertically, where different retrieval techniques can be applied.

  1. Iron and alloys of iron. [lunar resources

    NASA Technical Reports Server (NTRS)

    Sastri, Sankar

    1992-01-01

    All lunar soil contains iron in the metallic form, mostly as an iron-nickel alloy in concentrations of a few tenths of 1 percent. Some of this free iron can be easily separated by magnetic means. It is estimated that the magnetic separation of 100,000 tons of lunar soil would yield 150-200 tons of iron. Agglutinates contain metallic iron which could be extracted by melting and made into powder metallurgy products. The characteristics and potential uses of the pure-iron and iron-alloy lunar products are discussed. Processes for working iron that might be used in a nonterrestrial facility are also addressed.

  2. IMERG Global Precipitation Rates

    NASA Video Gallery

    NASA's Global Precipitation Measurement mission has produced its first global map of rainfall and snowfall. The GPM Core Observatory launched one year ago on Feb. 27, 2014 as a collaboration betwee...

  3. My NASA Data Precipitation

    NASA Video Gallery

    This lesson has two activities that help students develop a basic understanding of the relationship between cloud type and the form of precipitation and the relationship between the amount of water...

  4. Precipitation Estimates for Hydroelectricity

    NASA Technical Reports Server (NTRS)

    Tapiador, Francisco J.; Hou, Arthur Y.; de Castro, Manuel; Checa, Ramiro; Cuartero, Fernando; Barros, Ana P.

    2011-01-01

    Hydroelectric plants require precise and timely estimates of rain, snow and other hydrometeors for operations. However, it is far from being a trivial task to measure and predict precipitation. This paper presents the linkages between precipitation science and hydroelectricity, and in doing so it provides insight into current research directions that are relevant for this renewable energy. Methods described include radars, disdrometers, satellites and numerical models. Two recent advances that have the potential of being highly beneficial for hydropower operations are featured: the Global Precipitation Measuring (GPM) mission, which represents an important leap forward in precipitation observations from space, and high performance computing (HPC) and grid technology, that allows building ensembles of numerical weather and climate models.

  5. Chemisorption And Precipitation Reactions

    EPA Science Inventory

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  6. Iron and iron derived radicals

    SciTech Connect

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fastexclamation Think smallexclamation In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab.

  7. Recovery of iron oxide from coal fly ash

    DOEpatents

    Dobbins, Michael S.; Murtha, Marlyn J.

    1983-05-31

    A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

  8. Co-precipitated and collocated carbides and Cu-rich precipitates in a Fe-Cu steel characterized by atom-probe tomography.

    PubMed

    Kolli, R Prakash; Seidman, David N

    2014-12-01

    The composition of co-precipitated and collocated NbC carbide precipitates, Fe3C iron carbide (cementite), and Cu-rich precipitates are studied experimentally by atom-probe tomography (APT). The Cu-rich precipitates located at a grain boundary (GB) are also studied. The APT results for the carbides are supplemented with computational thermodynamics predictions of composition at thermodynamic equilibrium. Two types of NbC carbide precipitates are distinguished based on their stoichiometric ratio and size. The Cu-rich precipitates at the periphery of the iron carbide and at the GB are larger than those distributed in the α-Fe (body-centered cubic) matrix, which is attributed to short-circuit diffusion of Cu along the GB. Manganese segregation is not observed at the heterophase interfaces of the Cu-rich precipitates that are located at the periphery of the iron carbide or at the GB, which is unlike those located at the edge of the NbC carbide precipitates or distributed in the α-Fe matrix. This suggests the presence of two populations of NiAl-type (B2 structure) phases at the heterophase interfaces in multicomponent Fe-Cu steels.

  9. as the Strengthening Precipitates

    NASA Astrophysics Data System (ADS)

    Lu, Qi; Xu, Wei; van der Zwaag, Sybrand

    2014-12-01

    Generally, Laves phase and M23C6 are regarded as undesirable phases in creep-resistant steels due to their very high-coarsening rates and the resulting depletion of beneficial alloying elements from the matrix. In this study, a computational alloy design approach is presented to develop martensitic steels strengthened by Laves phase and/or M23C6, for which the coarsening rates are tailored such that they are at least one order of magnitude lower than those in existing alloys. Their volume fractions are optimized by tuning the chemical composition in parallel. The composition domain covering 10 alloying elements at realistic levels is searched by a genetic algorithm to explore the full potential of simultaneous maximization of the volume fraction and minimization of the precipitates coarsening rate. The calculations show that Co and W can drastically reduce the coarsening rate of Laves and M23C6 and yield high-volume fractions of precipitates. Mo on the other hand was shown to have a minimal effect on coarsening. The strengthening effects of Laves phase and M23C6 in the newly designed alloys are compared to existing counterparts, showing substantially higher precipitation-strengthening contributions especially after a long service time. New alloys were designed in which both Laves phase and M23C6 precipitates act as strengthening precipitates. Successfully combining MX and M23C6 was found to be impossible.

  10. Iron isotope composition of some Archean and Proterozoic iron formations

    NASA Astrophysics Data System (ADS)

    Planavsky, Noah; Rouxel, Olivier J.; Bekker, Andrey; Hofmann, Axel; Little, Crispin T. S.; Lyons, Timothy W.

    2012-03-01

    Fe isotopes can provide new insight into redox-dependent biogeochemical processes. Precambrian iron formations (IF) are deserving targets for Fe isotope studies because they are composed predominantly of authigenic Fe phases and record a period of unprecedented iron deposition in Earth's history. We present Fe isotope data for bulk samples from 24 Archean and Proterozoic IF and eight Phanerozoic Fe oxide-rich deposits. These data reveal that many Archean and early Paleoproterozoic iron formations were a sink for isotopically heavy Fe, in contrast to later Proterozoic and Phanerozoic Fe oxide-rich rocks. The positive δ56Fe values in IF are best explained by delivery of particulate ferric oxides formed in the water column to the sediment-water interface. Because IF are a net sink for isotopically heavy Fe, there must be a corresponding pool of isotopically light Fe in the sedimentary record. Earlier work suggested that Archean pyritic black shales were an important part of this light sink before 2.35 billion years ago (Ga). It is therefore likely that the persistently and anomalously low δ56Fe values in shales are linked with the deposition of isotopically heavy Fe in IF in the deeper parts of basins. IF deposition produced a residual isotopically light dissolved Fe pool that was captured by pyritic Fe in shales. Local dissimilatory Fe reduction in porewater and associated diagenetic reactions resulting in pyrite and carbonate precipitation may have further enhanced Fe isotope heterogeneity in marine sediments, and an 'iron shuttle' may have transported isotopically light Fe from shelf sediments to the basin. Nevertheless, water-column processing of hydrothermally delivered Fe likely had the strongest influence on the bulk iron isotope composition of Archean and Paleoproterozoic iron formations and other marine sediments.

  11. Technology development for cobalt F-T catalysts. Topical report No.3, Zirconia promotion of Fischer-Tropsch cobalt catalysts: Behavior in fixed-bed and slurry bubble column reactors

    SciTech Connect

    Oukaci, R.; Marcelin, G.; Goodwin, J.G. Jr.

    1995-01-17

    A series of cobalt-based F-T catalysts supported on alumina and silica were prepared with different loadings of Zr and different sequences of impregnation of Co and Zr. All catalysts were extensively characterized by different methods. The catalysts were evaluated in terms of their activity and selectivity both in fixed bed and slurry bubble column reactors. Addition of ZrO{sub 2} to both Co/SiO{sub 2} and Co/Al{sub 2}O{sub 3} catalysts resulted in at least a twofold increase in the catalyst activity for F-T synthesis in the fixed bed reactor. In the slurry bubble column reactor, a similar promotion effect was observed for the SiO{sub 2}-supported catalysts, while the addition of Zr to a cobalt/alumina catalyst had a less significant effect.

  12. Precipitating factors of asthma.

    PubMed

    Lee, T H

    1992-01-01

    Asthma is characterised by bronchial hyperresponsiveness. This feature of the asthmatic diathesis predisposes patients to wheezing in response to a number of different factors. These precipitating factors include specific allergen acting via sensitised mediator cells through an IgE-dependent mechanism. There are irritants which may work through a non-specific manner, or stimuli such as exercise and hyperventilation, which probably also act through mediator release via a non-IgE-dependent manner. The mechanism whereby physical stimuli such as exercise induce bronchoconstriction is of interest, because it increases the context in which the mast cell may participate in acute asthmatic bronchoconstriction. Respiratory infections also commonly provoke asthma, especially in infants and may, indeed, precipitate the asthmatic state itself. Finally, drugs can often trigger asthma attacks and the mechanisms of asthma precipitated by non-steroidal anti-inflammatory drugs such as aspirin have been the subject of recent research.

  13. FORMATION OF URANIUM PRECIPITATES

    DOEpatents

    Googin, J.M. Jr.

    1959-03-17

    A method is described for precipitation of uranium peroxide from uranium- containing solutions so as to obtain larger aggregates which facilitates washings decantations filtrations centrifugations and the like. The desired larger aggregate form is obtained by maintaining the pH of the solution in the approximate range of 1 to 3 and the temperature at about 25 deg C or below while carrytng out the precipitation. Then prior to removal of the precipitate a surface active sulfonated bicarboxyacids such as di-octyl sodium sulfo-succinates is incorporated in an anount of the order of 0.01 to 0.05 percent by weights and the slurry is allowed to ripen for about one-half hour at a temperatare below 10 deg C.

  14. Precipitation-Regulated Feedback

    NASA Astrophysics Data System (ADS)

    Voit, Mark

    2016-07-01

    Star formation in the central galaxies of galaxy clusters appears to be fueled by precipitation of cold clouds out of hot circumgalactic gas via thermal instability. I will present both observational and theoretical support for the precipitation mode in large galaxies and discuss how it can be implemented in cosmological simulations of galaxy evolution. Galaxy cluster cores are unique laboratories for studying the astrophysics of thermal instability and may be teaching us valuable lessons about how feedback works in galaxies spanning the entire mass spectrum.

  15. Electrostatic particle precipitator

    SciTech Connect

    Uchiya, T.; Hikizi, S.; Yabuta, H.

    1984-04-03

    An electrostatic particle precipitator for removing dust particles from a flue gas. The precipitator includes a plurality of collecting electrodes in the shape of plates mounted on endless chains and moving between a first region through which flue gas to be treated flows and a second region where the flow of gas is extremely scarce. A dust removal mechanism is positioned in the second region to remove dust which accumulates on the electrode plates. The moving speed of the collecting electrodes is controlled within a certain range to maintain a prescribed thickness of dust on the electrodes whereby the ocurrence of reverse ionization phenomenon is prevented.

  16. Acid Precipitation; (USA)

    SciTech Connect

    Rushing, J.W.; Hicks, S.C.

    1991-01-01

    This publication, Acid Precipitation (APC) announces on a monthly basis the current worldwide information on acid precipitation and closely related subjects, including wet and dry deposition, long-range transport, environmental effects, modeling, and socioeconomic factors. Information on the following subjects is included within the scope of this publication, but all subjects may not appear in each issue: Pollution sources and pollution control technology; atmospheric transport and chemistry; terrestrial transport and chemistry; aquatic transport and chemistry; biological effects; corrosive effects; and socioeconomics, policy, and legislation.

  17. Immobilisation of arsenic by iron(II)-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Kappler, A.; Hohmann, C.; Winkler, E.; Muehe, M.; Morin, G.

    2008-12-01

    Arsenic-contaminated groundwater is an environmental problem that affects about 1-2% of the world's population. As arsenic-contaminated water is also used for irrigating rice fields, the uptake of arsenic via rice is in some cases even higher than via drinking water. Arsenic is often of geogenic origin and in many cases bound to iron(III) minerals. Microbial iron(III) reduction leads to dissolution of Fe(III) minerals and thus the arsenic bound to these minerals is released to the environment. In turn, iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation followed by iron(III) mineral formation. Here, we present work on arsenic co-precipitation and immobilization by anaerobic and aerobic iron(II)-oxidizing bacteria. Co-precipitation batch experiments with pure cultures of nitrate-dependent, phototrophic, and microaerophilic Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation. Iron and arsenic speciation and redox state are determined by X- ray diffraction and synchrotron-based X-ray absorption methods (EXAFS, XANES). Microcosm experiments are set-up either with liquid media or with rice paddy soil amended with arsenic. Rice paddy soil from arsenic contaminated rice fields in China that include a natural population of Fe(II)-oxidizing microorganisms is used as inoculum. Dissolved and solid-phase arsenic and iron are quantified, Arsenic speciation is determined and the iron minerals are identified. Additionally, Arsenic uptake into the rice plant is quantified and a gene expression pattern in rice (Oryza sativa cv Gladia) is determined by microarrays as a response to the presence of Fe(II)-oxidizing bacteria.

  18. Redox reactions between iron and quinones: Thermodynamic constraints

    NASA Astrophysics Data System (ADS)

    Uchimiya, Minori; Stone, Alan T.

    2006-03-01

    Iron is the most abundant redox-active metallic element on the earth's surface. Quinones, a term that encompasses dihydroxybenzenes (catechol and hydroquinone), semiquinone radicals, and benzoquinones, are abundant moieties within natural organic matter. Separately or in concert, iron species (both dissolved and precipitated) and quinones are believed to be key participants in a wide range of environmental redox reactions. Here, we investigate how pH, quinone structure, and iron speciation impose thermodynamic constraints on possible reactions. The steps outlined in this work must be followed to evaluate whether postulated redox processes involving iron and quinones are energetically feasible.

  19. Pharmacology of Iron Transport

    PubMed Central

    Byrne, Shaina L.; Krishnamurthy, Divya; Wessling-Resnick, Marianne

    2013-01-01

    Elucidating the molecular basis for the regulation of iron uptake, storage, and distribution is necessary to understand iron homeostasis. Pharmacological tools are emerging to identify and distinguish among different iron transport pathways. Stimulatory or inhibitory small molecules with effects on iron uptake can help characterize the mechanistic elements of iron transport and the roles of the transporters involved in these processes. In particular, iron chelators can serve as potential pharmacological tools to alleviate diseases of iron overload. This review focuses on the pharmacology of iron transport, introducing iron transport membrane proteins and known inhibitors. PMID:23020294

  20. The Global Precipitation Mission

    NASA Technical Reports Server (NTRS)

    Braun, Scott; Kummerow, Christian

    2000-01-01

    The Global Precipitation Mission (GPM), expected to begin around 2006, is a follow-up to the Tropical Rainfall Measuring Mission (TRMM). Unlike TRMM, which primarily samples the tropics, GPM will sample both the tropics and mid-latitudes. The primary, or core, satellite will be a single, enhanced TRMM satellite that can quantify the 3-D spatial distributions of precipitation and its associated latent heat release. The core satellite will be complemented by a constellation of very small and inexpensive drones with passive microwave instruments that will sample the rainfall with sufficient frequency to be not only of climate interest, but also have local, short-term impacts by providing global rainfall coverage at approx. 3 h intervals. The data is expected to have substantial impact upon quantitative precipitation estimation/forecasting and data assimilation into global and mesoscale numerical models. Based upon previous studies of rainfall data assimilation, GPM is expected to lead to significant improvements in forecasts of extratropical and tropical cyclones. For example, GPM rainfall data can provide improved initialization of frontal systems over the Pacific and Atlantic Oceans. The purpose of this talk is to provide information about GPM to the USWRP (U.S. Weather Research Program) community and to discuss impacts on quantitative precipitation estimation/forecasting and data assimilation.