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Sample records for biocatalytic desulfurization project

  1. The Biocatalytic Desulfurization Project

    SciTech Connect

    David Nunn; James Boltz; Philip M. DiGrazia; Larry Nace

    2006-03-03

    The material in this report summarizes the Diversa technical effort in development of a biocatalyst for the biodesulfurization of Petro Star diesel as well as an economic report of standalone and combined desulfurization options, prepared by Pelorus and Anvil, to support and inform the development of a commercially viable process. We will discuss goals of the projected as originally stated and their modification as guided by parallel efforts to evaluate commercialization economics and process parameters. We describe efforts to identify novel genes and hosts for the generation of an optimal biocatalyst, analysis of diesel fuels (untreated, chemically oxidized and hydrotreated) for organosulfur compound composition and directed evolution of enzymes central to the biodesulfurization pathway to optimize properties important for their use in a biocatalyst. Finally we will summarize the challenges and issues that are central to successful development of a viable biodesulfurization process.

  2. THE BIOCATALYTIC DESULFURIZATION PROJECT

    SciTech Connect

    Steven E. Bonde; David Nunn

    2003-01-01

    During the first quarter of the Biological Desulfurization project several activities were pursued. A project kickoff meeting was held at the Diversa facility in San Diego, CA. Activities that were in process before the meeting and begun afterwards by Diversa Corporation and Petro Star Inc. include: Technology transfer in the form of information generated by Enchira to Diversa, the purchase and installation of equipment by Diversa, development of synthetic methods and preparation of organo-sulfur substrates for use in determining enzyme activities, production of extract via Petro Star's CED process, detailed analysis of Petro Star Inc. diesel and CED extract, and several activities in molecular biology. Diversa Corporation, in the area of molecular biology, engaged in several activities in support of the task list of the contract. These included: construction of a genomic library; development and utilization of a sequence-based gene discovery effort; a parallel discovery approach based on functional expression of enzymes with the ability to oxidize organosulfur compounds. Biodesulfurization genes have already been identified and are being sequenced and subcloned for expression in heterologous biological hosts. Diversa has evaluated and adapted assays developed by Enchira used to assess the activities of DBT and DBTO{sub 2} monooxygenases. Finally, Diversa personnel have developed two novel selection/screen strategies for the improvement of biocatalyst strains by directed evolution.

  3. THE BIOCATALYTIC DESULFURIZATION PROJECT

    SciTech Connect

    Scott Collins; David Nunn

    2003-10-01

    The analysis of Petro Star diesel sulfur species is complete and a report is attached. Further analytical efforts will concentrate on characterization of diesel fuel, hydrodesulfurized to varying degrees, in order to determine sulfur species that may be problematic to hydrogen treatment and represent potential target substrates for biodesulfurization in a combined HDS-BDS process. Quotes have been received and are being considered for the partial treatment of Petro Star Inc. marine diesel fuel. Direction of research is changing slightly; economic analysis of the hyphenated--BDSHDS, BDS-CED--has shown the highest probability of success to be with a BDS-HDS process where the biodesulfurization precedes hydrodesulfurization. Thus, the microorganisms will be tailored to focus on those compounds that tend to be recalcitrant to hydrodesulfurization and decrease the severity of the hydrodesulfurization step. A separate, detailed justification for this change is being prepared. Research activities have continued in the characterization of the desulfurization enzymes from multiple sources. Genes for all DszA, -B, -C and -D enzymes (and homologs) have been cloned and expressed. Activity determinations, on a variety of substituted benzothiophene and dibenzothiophene substrates, have been carried out and continue. In addition, chemical synthesis efforts have been carried out to generate additional substrates for analytical standards and activity determinations. The generation of a GSSM mutant library of the ''Rhodococcus IGTS8 dszA'' gene has been completed and development of protocols for a high throughput screen to expand substrate specificity are nearing completion. In an effort to obtain improved hosts as biocatalyst, one hundred-thirty ''Rhodococcus'' and related strains are being evaluated for growth characteristics and other criteria deemed important for an optimal biocatalyst strain. We have also begun an effort to generate derivatives of the entire IGTS8 BDS plasmid

  4. Biocatalytic desulfurization (BDS) of petrodiesel fuels.

    PubMed

    Mohebali, Ghasemali; Ball, Andrew S

    2008-08-01

    Oil refineries are facing many challenges, including heavier crude oils, increased fuel quality standards, and a need to reduce air pollution emissions. Global society is stepping on the road to zero-sulfur fuel, with only differences in the starting point of sulfur level and rate reduction of sulfur content between different countries. Hydrodesulfurization (HDS) is the most common technology used by refineries to remove sulfur from intermediate streams. However, HDS has several disadvantages, in that it is energy intensive, costly to install and to operate, and does not work well on refractory organosulfur compounds. Recent research has therefore focused on improving HDS catalysts and processes and also on the development of alternative technologies. Among the new technologies one possible approach is biocatalytic desulfurization (BDS). The advantage of BDS is that it can be operated in conditions that require less energy and hydrogen. BDS operates at ambient temperature and pressure with high selectivity, resulting in decreased energy costs, low emission, and no generation of undesirable side products. Over the last two decades several research groups have attempted to isolate bacteria capable of efficient desulfurization of oil fractions. This review examines the developments in our knowledge of the application of bacteria in BDS processes, assesses the technical viability of this technology and examines its future challenges.

  5. THE BIOCATALYTIC DESULFURIZATION PROJECT

    SciTech Connect

    Steven E. Bonde; David Nunn

    2003-04-01

    Research activities in the second quarter have largely been a continuation of efforts previously described in the first quarterly report as well as a degree of redirection of effort as a result of discussions during the first quarterly meeting held in San Diego. Chemical synthesis efforts have been refined and are currently being used to support generation of substrates for evaluation and evolution of enzymes for their oxidation. Analysis of the sulfur species in Petro Star diesel, CED extract and refinement of the speciation data is nearly complete. Molecular biology efforts continue with the cloning, expression and characterization of the DszA and DszC proteins as well as the flavin reductases to support regeneration of the essential FMN cofactors. In addition, we have initiated an evolution effort for the extension and improvement of DszA enzyme activity using Diversa's Gene Site Saturation Mutagenesis (GSSM{trademark}) technology. To support the evolution effort as well as of characterization of enzyme activities on a variety of substrates, a high-throughput mass spectroscopy-based assay has been developed. Two selection/screen strategies for the discovery and evolution of biocatalyst enzyme have been developed and are being evaluated for performance using gene libraries constructed from known biodesulfurization strains and environmental libraries.

  6. Biocatalytic desulfurization of thiophenic compounds and crude oil by newly isolated bacteria.

    PubMed

    Mohamed, Magdy El-Said; Al-Yacoub, Zakariya H; Vedakumar, John V

    2015-01-01

    Microorganisms possess enormous highly specific metabolic activities, which enable them to utilize and transform nearly every known chemical class present in crude oil. In this context, one of the most studied biocatalytic processes is the biodesulfurization (BDS) of thiophenic sulfur-containing compounds such as benzothiophene (BT) and dibenzothiophene (DBT) in crude oils and refinery streams. Three newly isolated bacterial strains, which were affiliated as Rhodococcus sp. strain SA11, Stenotrophomonas sp. strain SA21, and Rhodococcus sp. strain SA31, were enriched from oil contaminated soil in the presence of DBT as the sole S source. GC-FID analysis of DBT-grown cultures showed consumption of DBT, transient formation of DBT sulfone (DBTO2) and accumulation of 2-hydroxybiphenyl (2-HBP). Molecular detection of the plasmid-borne dsz operon, which codes for the DBT desulfurization activity, revealed the presence of dszA, dszB, and dszC genes. These results point to the operation of the known 4S pathway in the BDS of DBT. The maximum consumption rate of DBT was 11 μmol/g dry cell weight (DCW)/h and the maximum formation rate of 2-HBP formation was 4 μmol/g DCW/h. Inhibition of both cell growth and DBT consumption by 2-HBP was observed for all isolates but SA11 isolate was the least affected. The isolated biocatalysts desulfurized other model DBT alkylated homologs. SA11 isolate was capable of desulfurizing BT as well. Resting cells of SA11 exhibited 10% reduction in total sulfur present in heavy crude oil and 18% reduction in total sulfur present in the hexane-soluble fraction of the heavy crude oil. The capabilities of the isolated bacteria to survive and desulfurize a wide range of S compounds present in crude oil are desirable traits for the development of a robust BDS biocatalyst to upgrade crude oils and refinery streams.

  7. LIFAC Sorbent Injection Desulfurization Demonstration Project

    SciTech Connect

    Not Available

    1992-01-01

    Sorbent injection is a potentially important alternative to conventional wet lime and limestone scrubbing, and this project is another effort to test alternative sorbent injection approaches. In comparison to wet systems, LIFAC, with recirculation of the sorbent, removes less sulfur dioxide - 75--85% relative to 90% or greater for conventional scrubbers -- and requires more reagent material. However, if the demonstration is wet scrubbing systems: LIFAC is relatively easy to retrofit to an existing boiler and requires less area than conventional wet FGD systems. LIFAC is less expensive to install than conventional wet FGD processes. LIFAC's overall costs measured on a dollar-per-ton SO[sub 2] removed basis are less, an important advantage in a regulatory regime with trading of emission allocations. LIFAC produces a dry, readily disposable waste by-product versus a wet product. LIFAC is relatively simple to operate.

  8. LIFAC Sorbent Injection Desulfurization Demonstration Project

    SciTech Connect

    Not Available

    1992-01-01

    The LIFAC technology has similarities to other sorbent injection technologies using humidification, but employs a unique patented vertical reaction chamber located down-stream of the boiler to facilitate and control the sulfur capture and other chemical reactions. This chamber improves the overall reaction efficiency enough to allow the use of pulverized limestone rather than more expensive reagents such as lime which are often used to increase the efficiency of other sorbent injection processes. Sorbent injection is a potentially important alternative to conventional wet lime and limestone scrubbing, and this project is another effort to test alternative sorbent injection approaches. In comparison to wet systems, LIFAC, with recirculation of the sorbent, removes less sulfur dioxide - 75--85% relative to 90% or greater for conventional scrubbers - and requires more reagent material. However, if the demonstration is successful, LIFAC will offer these important advantages over wet scrubbing systems: LIFAC is relatively easy to retrofit to an existing boiler and requires less area than conventional wet FGD systems; LIFAC is less expensive to install than conventional wet FGD processes; LIFAC's overall costs measured on a dollar-per-ton S0{sub 2} removed basis are less, an important advantage in a regulatory regime with trading of emission allocations. LIFAC produces a dry, readily disposable waste by-product versus a wet product; and LIFAC is relatively simple to operate.

  9. Advanced Flue Gas Desulfurization (AFGD) demonstration project: Volume 2, Project performance and economics. Final technical report

    SciTech Connect

    1996-04-30

    The project objective is to demonstrate removal of 90--95% or more of the SO{sub 2} at approximately one-half the cost of conventional scrubbing technology; and to demonstrate significant reduction of space requirements. In this project, Pure Air has built a single SO{sub 2} absorber for a 528-MWe power plant. The absorber performs three functions in a single vessel: prequencher, absorber, and oxidation of sludge to gypsum. Additionally, the absorber is of a co- current design, in which the flue gas and scrubbing slurry move in the same direction and at a relatively high velocity compared to conventional scrubbers. These features all combine to yield a state- of-the-art SO{sub 2} absorber that is more compact and less expensive than conventional scrubbers. The project incorporated a number of technical features including the injection of pulverized limestone directly into the absorber, a device called an air rotary sparger located within the base of the absorber, and a novel wastewater evaporation system. The air rotary sparger combines the functions of agitation and air distribution into one piece of equipment to facilitate the oxidation of calcium sulfite to gypsum. Additionally, wastewater treatment is being demonstrated to minimize water disposal problems inherent in many high-chloride coals. Bituminous coals primarily from the Indiana, Illinois coal basin containing 2--4.5% sulfur were tested during the demonstration. The Advanced Flue Gas Desulfurization (AFGD) process has demonstrated removal of 95% or more of the SO{sub 2} while providing a commercial gypsum by-product in lieu of solid waste. A portion of the commercial gypsum is being agglomerated into a product known as PowerChip{reg_sign} gypsum which exhibits improved physical properties, easier flowability and more user friendly handling characteristics to enhance its transportation and marketability to gypsum end-users.

  10. Advanced fuel gas desulfurization (AFGD) demonstration project. Technical progress report No. 19, July 1, 1994--September 30, 1994

    SciTech Connect

    1995-12-01

    The {open_quotes}Advanced Flue Gas Desulfurization (AFGD) Demonstration Project{close_quotes} is a $150.5 million cooperative effort between the U.S. Department of Energy and Pure Air, a general partnership of Air Products and Chemicals, Inc. and Mitsubishi Heavy Industries America, Inc. The AFGD process is one of several alternatives to conventional flue gas desulfurization (FGD) being demonstrated under the Department of Energy`s Clean Coal Technology Demonstration Program. The AFGD demonstration project is located at the Northern Indiana Public Service Company`s Bailly Generating Station, about 12 miles northeast of Gary, Indiana.

  11. Advanced Flue Gas Desulfurization (AFGD) Demonstration Project, A DOE Assessment

    SciTech Connect

    National Energy Technology Laboratory

    2001-08-31

    The AFGD process as demonstrated by Pure Air at the Bailly Station offers a reliable and cost-effective means of achieving a high degree of SO{sub 2} emissions reduction when burning high-sulfur coals. Many innovative features have been successfully incorporated in this process, and it is ready for widespread commercial use. The system uses a single-loop cocurrent scrubbing process with in-situ oxidation to produce wallboard-grade gypsum instead of wet sludge. A novel wastewater evaporation system minimizes effluents. The advanced scrubbing process uses a common absorber to serve multiple boilers, thereby saving on capital through economies of scale. Major results of the project are: (1) SO{sub 2} removal of over 94 percent was achieved over the three-year demonstration period, with a system availability exceeding 99.5 percent; (2) a large, single absorber handled the combined flue gas of boilers generating 528 MWe of power, and no spares were required; (3) direct injection of pulverized limestone into the absorber was successful; (4) Wastewater evaporation eliminated the need for liquid waste disposal; and (5) the gypsum by-product was used directly for wallboard manufacture, eliminating the need to dispose of waste sludge.

  12. Biocatalytic removal of organic sulfur from coal

    SciTech Connect

    Webster, D.A.; Kilbane, J.J. II

    1994-09-09

    The objective is to characterize more completely the biochemical ability of the bacterium, Rhodococcus rhodochrous IGTS8, to cleave carbon-sulfur bonds with emphasis on data that will allow the development of a practical coal biodesulfurization process. Another approach for increasing the desulfurization activity of the IGTS8 cultures is to produce strains genetically that have higher activity. The goal of this part of research is to achieve strain improvement by introducing a stronger promoter using genetic engineering techniques. The promoter regulates the transcription of the genes for the desulfurization enzymes, and a stronger promoter, would up-regulate the expression of these genes, resulting in cells with higher desulfurization activity. Promoter probe vectors are used to identify and isolate promoters from a DNA library of the experimental organism. The major accomplishments have been to obtain high biodesulfurization activity in nonaqueous, media, especially using freeze-dried cells, and to have isolated strong promoters from R. rhodochrous IGTS8 which will be used to engineer the organism to produce strains with higher biocatalytic activity.

  13. Advanced Flue Gas Desulfurization (AFGD) Demonstration Project. Technical progress report No. 15, July 1, 1993--September 30, 1993

    SciTech Connect

    Not Available

    1994-08-01

    The goal of this project is to demonstrate that, by combining state-of-the-art technology, highly efficient plant operation and maintenance capabilities and by-product gypsum sales, significant reductions of SO{sub 2} emissions can be achieved at approximately one-half the life cycle cost of a conventional Flue Gas Desulfurization (FGD) system. Further, this emission reduction is achieved without generating solid waste and while minimizing liquid wastewater effluent. Basically, this project entails the design, construction and operation of a nominal 600 MWe AFGD facility to remove SO{sub 2} from coal-fired power plant flue gas at the Northern Indiana Public Service Company`s Bailly Generating Station.

  14. LIFAC sorbent injection desulfurization demonstration project. Final report, volume II: Project performance and economics

    SciTech Connect

    1996-01-01

    This publication discusses the demonstration of the LIFAC sorbent injection technology at Richmond Power and Light`s Whitewater Valley Unit No. 2, performed under the auspices of the U.S. Department of Energy`s (DOE) Clean Coal Technology Program. LIFAC is a sorbent injection technology capable of removing 75 to 85 percent of a power plant`s SO{sub 2} emissions using limestone at calcium to sulfur molar ratios of between 2 and 2.5 to 1. The site of the demonstration is a coal-fired electric utility power plant located in Richmond, Indiana. The project is being conducted by LIFAC North America (LIFAC NA), a joint venture partnership of Tampella Power Corporation and ICF Kaiser Engineers, in cooperation with DOE, RP&L, and Research Institute (EPRI), the State of Indiana, and Black Beauty Coal Company. The purpose of Public Design Report Volume 2: Project Performance and Economics is to consolidate, for public use, the technical efficiency and economy of the LIFAC Process. The report has been prepared pursuant to the Cooperative Agreement No. DE-FC22-90PC90548 between LIFAC NA and the U.S. Department of Energy.

  15. Biocatalytic portfolio of Basidiomycota.

    PubMed

    Schmidt-Dannert, Claudia

    2016-04-01

    Basidiomycota fungi have received little attention for applications in biocatalysis and biotechnology and remain greatly understudied despite their importance for carbon recycling, ecosystem functioning and medicinal properties. The steady influx of genome data has facilitated detailed studies aimed at understanding the evolution and function of fungal lignocellulose degradation. These studies and recent explorations into the secondary metabolomes have uncovered large portfolios of enzymes useful for biocatalysis and biosynthesis. This review will provide an overview of the biocatalytic repertoires of Basidiomycota characterized to date with the hope of motivation more research into the chemical toolkits of this diverse group of fungi.

  16. Biocatalytic material comprising multilayer enzyme coated fiber

    DOEpatents

    Kim, Jungbae [Richland, WA; Kwak, Ja Hun [Richland, WA; Grate, Jay W [West Richland, WA

    2009-11-03

    The present invention relates generally to high stability, high activity biocatalytic materials and processes for using the same. The materials comprise enzyme aggregate coatings having high biocatalytic activity and stability useful in heterogeneous environment. These new materials provide a new biocatalytic immobilized enzyme system with applications in bioconversion, bioremediation, biosensors, and biofuel cells.

  17. LIFAC Sorbent Injection Desulfurization Demonstration Project. Quarterly report No. 9, October--December 1992

    SciTech Connect

    Not Available

    1992-12-31

    Sorbent injection is a potentially important alternative to conventional wet lime and limestone scrubbing, and this project is another effort to test alternative sorbent injection approaches. In comparison to wet systems, LIFAC, with recirculation of the sorbent, removes less sulfur dioxide - 75--85% relative to 90% or greater for conventional scrubbers -- and requires more reagent material. However, if the demonstration is wet scrubbing systems: LIFAC is relatively easy to retrofit to an existing boiler and requires less area than conventional wet FGD systems. LIFAC is less expensive to install than conventional wet FGD processes. LIFAC`s overall costs measured on a dollar-per-ton SO{sub 2} removed basis are less, an important advantage in a regulatory regime with trading of emission allocations. LIFAC produces a dry, readily disposable waste by-product versus a wet product. LIFAC is relatively simple to operate.

  18. LIFAC Sorbent Injection Desulfurization Demonstration Project. Quarterly report No. 10, January--March 1993

    SciTech Connect

    Not Available

    1993-09-01

    Sorbent injection is a potentially important alternative to conventional wet lime and limestone scrubbing, and this project is another effort to test alternative sorbent injection approaches. in comparison to wet systems, LIFAC, with recirculation of the sorbent, removes less sulfur dioxide -- 75--85% relative to 90% or greater for conventional scrubbers and requires more reagent material. However, if the demonstration is successful, LIFAC will offer these important advantages over wet scrubbing systems: Relatively easy to retrofit to an existing boiler and requires less area than conventional wet FGD systems; less expensive to install than conventional wet FGD processes; overall costs measured on a dollar-per-ton SO{sub 2} removed basis are less; produces a dry, readily disposable waste by-product versus a wet product; and is relatively simple to operate. The site for the LIFAC demonstration is Richmond Power and Light`s Whitewater Valley 2 pulverized coal-fired power station (60 MW), located in Richmond, Indiana.

  19. LIFAC Sorbent Injection Desulfurization Demonstration Project. Quarterly report No. 6, January--March 1992

    SciTech Connect

    Not Available

    1992-09-01

    The LIFAC technology has similarities to other sorbent injection technologies using humidification, but employs a unique patented vertical reaction chamber located down-stream of the boiler to facilitate and control the sulfur capture and other chemical reactions. This chamber improves the overall reaction efficiency enough to allow the use of pulverized limestone rather than more expensive reagents such as lime which are often used to increase the efficiency of other sorbent injection processes. Sorbent injection is a potentially important alternative to conventional wet lime and limestone scrubbing, and this project is another effort to test alternative sorbent injection approaches. In comparison to wet systems, LIFAC, with recirculation of the sorbent, removes less sulfur dioxide - 75--85% relative to 90% or greater for conventional scrubbers - and requires more reagent material. However, if the demonstration is successful, LIFAC will offer these important advantages over wet scrubbing systems: LIFAC is relatively easy to retrofit to an existing boiler and requires less area than conventional wet FGD systems; LIFAC is less expensive to install than conventional wet FGD processes; LIFAC`s overall costs measured on a dollar-per-ton S0{sub 2} removed basis are less, an important advantage in a regulatory regime with trading of emission allocations. LIFAC produces a dry, readily disposable waste by-product versus a wet product; and LIFAC is relatively simple to operate.

  20. Biocatalytic conversion of lignocellulose to platform chemicals.

    PubMed

    Jäger, Gernot; Büchs, Jochen

    2012-09-01

    Naturally occurring lignocellulose can be used as a renewable resource for the sustainable production of platform chemicals that can in turn be converted to valuable fine chemicals, polymers, and fuels. The biocatalytic conversion of lignocellulose is a very promising approach due to its high selectivity, mild conditions, and low exergy loss. However, such biocatalytic processes are still seldom applied at the industrial scale since the single conversion steps (pretreatment, hydrolysis, and fermentation) may exhibit low conversion rates, low efficiencies, or high costs. The biocatalytic conversion of lignocellulose to platform chemicals is reviewed in this work. Structures and production rates of lignocellulose are described, and platform chemicals that may be produced from lignocellulose are summarized. Biocatalytic conversion of lignocellulose is distinguished from conventional non-selective approaches. All essential conversion steps used in biocatalytic approaches (pretreatment, hydrolysis, and fermentation) are reviewed in detail. Finally, potential interactions between these conversion steps are highlighted and the advantages as well as disadvantages of integrated process configurations are elucidated. In conclusion, a comprehensive understanding of the biocatalytic conversion of lignocellulose is provided in this review.

  1. Crude oil desulfurization

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Hsu, G. C.; Ernest, J. B. (Inventor)

    1982-01-01

    High sulfur crude oil is desulfurized by a low temperature (25-80 C.) chlorinolysis at ambient pressure in the absence of organic solvent or diluent but in the presence of water (water/oil=0.3) followed by a water and caustic wash to remove sulfur and chlorine containing reaction products. The process described can be practiced at a well site for the recovery of desulfurized oil used to generate steam for injection into the well for enhanced oil recovery.

  2. Advanced sulfur control concepts for hot gas desulfurization technology

    SciTech Connect

    1998-09-01

    The objective of this project is to develop a hot-gas desulfurization process scheme for control of H{sub 2}S in HTHP coal gas that can be more simply and economically integrated with known regenerable sorbents in DOE/METC-sponsored work than current leading hot-gas desulfurization technologies. In addition to being more economical, the process scheme to be developed must yield an elemental sulfur byproduct.

  3. Fluidized bed coal desulfurization

    NASA Technical Reports Server (NTRS)

    Ravindram, M.

    1983-01-01

    Laboratory scale experiments were conducted on two high volatile bituminous coals in a bench scale batch fluidized bed reactor. Chemical pretreatment and posttreatment of coals were tried as a means of enhancing desulfurization. Sequential chlorination and dechlorination cum hydrodesulfurization under modest conditions relative to the water slurry process were found to result in substantial sulfur reductions of about 80%. Sulfur forms as well as proximate and ultimate analyses of the processed coals are included. These studies indicate that a fluidized bed reactor process has considerable potential for being developed into a simple and economic process for coal desulfurization.

  4. Biocatalytic Processing Polymers in Supercritical Fluids

    DTIC Science & Technology

    1994-01-01

    Russell, A.J and Beckman, E.J. (1991) Appl. Bioch . Biotech., 31, 197-211. Enzyme activity in supercritical fluids. 22. *Russell, A.J and Beckman, E.J...S., Jacob , J., Beckman, E.J. and Russell, A.J. (1991) Enz. Microb. Technol., 13, 519. Biocatalytic synthesis of acrylates in supercritical fluids. 24

  5. Enzymatic desulfurization of coal

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.

    1991-05-16

    The overall objective of this program was to investigate the feasibility of an enzymatic desulfurization process specifically intended for organic sulfur removal from coal. Toward that end, a series of specific objectives were defined: (1) establish the feasibility of (bio)oxidative pretreatment followed by biochemical sulfate cleavage for representative sulfur-containing model compounds and coals using commercially-available enzymes; (2) investigate the potential for the isolation and selective use of enzyme preparations from coal-utilizing microbial systems for desulfurization of sulfur-containing model compounds and coals; and (3) develop a conceptual design and economic analysis of a process for enzymatic removal of organic sulfur from coal. Within the scope of this program, it was proposed to carry out a portion of each of these efforts concurrently. (VC)

  6. The Industrial Age of Biocatalytic Transamination

    PubMed Central

    Fuchs, Michael; Farnberger, Judith E; Kroutil, Wolfgang

    2015-01-01

    During the last decade the use of ω-transaminases has been identified as a very powerful method for the preparation of optically pure amines from the corresponding ketones. Their immense potential for the preparation of chiral amines, together with their ease of use in combination with existing biocatalytic methods, have made these biocatalysts a competitor to any chemical methodology for (asymmetric) amination. An increasing number of examples, especially from industry, shows that this biocatalytic technology outmaneuvers existing chemical processes by its simple and flexible nature. In the last few years numerous publications and patents on synthetic routes, mainly to pharmaceuticals, involving ω-transaminases have been published. The review gives an overview of the application of ω-transaminases in organic synthesis with a focus on active pharmaceutical ingredients (APIs) and the developments during the last few years. PMID:26726292

  7. Enzymatic desulfurization of coal

    SciTech Connect

    Marquis, J.K. . School of Medicine); Kitchell, J.P. )

    1988-12-15

    Our current efforts to develop clean coal technology emphasize the advantages of enzymatic desulfurization techniques and have specifically addressed the potential of using partially-purified extracellular microbial enzymes or commercially available enzymes. Our work is focused on the treatment of model'' organic sulfur compounds such as dibenzothiophene (DBT) and ethylphenylsulfide (EPS). Furthermore, we are designing experiments to facilitate the enzymatic process by means of a hydrated organic solvent matrix.

  8. Fluidized bed desulfurization

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kallvinskas, J. J. (Inventor)

    1985-01-01

    High sulfur content carbonaceous material, such as coal is desulfurized by continuous fluidized suspension in a reactor with chlorine gas, inert dechlorinating gas and hydrogen gas. A source of chlorine gas, a source of inert gas and a source of hydrogen gas are connected to the bottom inlet through a manifold and a heater. A flow controler operates servos in a manner to continuously and sequentially suspend coal in the three gases. The sulfur content is reduced at least 50% by the treatment.

  9. Microbial desulfurization of coal

    NASA Technical Reports Server (NTRS)

    Dastoor, M. N.; Kalvinskas, J. J.

    1978-01-01

    Experiments indicate that several sulfur-oxidizing bacteria strains have been very efficient in desulfurizing coal. Process occurs at room temperature and does not require large capital investments of high energy inputs. Process may expand use of abundant reserves of high-sulfur bituminous coal, which is currently restricted due to environmental pollution. On practical scale, process may be integrated with modern coal-slurry transportation lines.

  10. Coal Liquefaction desulfurization process

    DOEpatents

    Givens, Edwin N.

    1983-01-01

    In a solvent refined coal liquefaction process, more effective desulfurization of the high boiling point components is effected by first stripping the solvent-coal reacted slurry of lower boiling point components, particularly including hydrogen sulfide and low molecular weight sulfur compounds, and then reacting the slurry with a solid sulfur getter material, such as iron. The sulfur getter compound, with reacted sulfur included, is then removed with other solids in the slurry.

  11. Enzymatic desulfurization of coal

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V. ); Marquis, J.K. . School of Medicine)

    1989-06-16

    Our current efforts to develop clean coal technology emphasize the advantages of enzymatic desulfurization techniques and have specifically addressed the potential of using partially-purified extracellular microbial enzymes as well as commercially available enzymes. Our work is focused on the treatment of model'' organic sulfur compounds such as dibenzothiophene (DBT) and ethylphenylsulfide (EPS). Furthermore, we are designing experiments to facilitate the enzymatic process by means of a hydrated organic solvent matrix.

  12. Efficient Biocatalytic Synthesis of Chiral Chemicals.

    PubMed

    Zhang, Zhi-Jun; Pan, Jiang; Ma, Bao-Di; Xu, Jian-He

    2016-01-01

    Chiral chemicals are a group of important chiral synthons for the synthesis of a series of pharmaceuticals, agrochemicals, and fine chemicals. In past decades, a number of biocatalytic approaches have been developed for the green and effective synthesis of various chiral chemicals. However, the practical application of these biocatalytic processes is still hindered by the lack of highly efficient and robust biocatalysts, which usually results in the low volumetric productivity and high cost of the bioprocesses. Further step forward of biocatalysis in industrial application strongly requires the development of versatile and highly efficient biocatalysts, aiming to increase the process efficiency and facilitate the downstream processing. Recently, the fast growth of genome sequences in the database in post-genomic era offers great opportunities for accessing numerous biocatalysts with practical application potential, and the so-called genome mining approach provides time-effective and highly specific strategy for the fast identification of target enzymes with desired properties and outperforms the traditional screening of soil samples for microbial enzyme producers of interest. A number of biocatalytic processes with industrial application potential were developed thereafter. Further development of protein engineering strategies, process optimization, and cooperative work between biologists, organic chemists, and engineers is expected to make biocatalysis technology the first choice approach for the eco-friendly, highly efficient, and cost-effective synthesis of chiral chemicals in the near future.

  13. Coal desulfurization with iron pentacarbonyl

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.

    1979-01-01

    Coal desulfurization with iron pentacarbonyl treatment under mild conditions removes up to eighty percent of organic sulfur. Preliminary tests on treatment process suggest it may be economical enough to encourage investigation of use for coal desulfurization. With mild operating conditions, process produces environmentally-acceptable clean coal at reasonable cost.

  14. Coal desulfurization by cyclonic whirl

    SciTech Connect

    Jianguo, Y.; Wenjun, Z.; Yuling, W.

    1999-07-01

    The crux of coal desulfurization is how to improve separation efficiency for 3--0.1mm materials. Cyclonic whirl produce centrifugal force and shearing force, heavy medium cyclone uses former, and cyclone flotation column uses both of them. A new system with heavy medium cyclone and cyclone flotation column is provided and testified to be very efficient in commercial desulfurization.

  15. Hot Gas Desulfurization Using Transport Reactors

    SciTech Connect

    Moorehead, E.L.

    1996-12-31

    Sierra Pacific Power Company is building a 100 MW, IGCC power plant based on KRW fluid bed gasifier technology that utilizes transport reactors for hot gas desulfurization and sorbent regeneration. Use of a transport absorber avoids the need for pre-filtration of dust-laden gasifier effluent, while a transport regenerator allows for the use of 100% air without the need for heat exchange equipment. Selection of transport reactors for hot gas desulfurization using a proprietary sorbent, based on testing performed in a transport reactor test unit (TRTU) at the M. W. Kellogg Technology Development Center and in a fixed bed reactor at Morgantown Energy Technology Center (METC), is outlined. The results obtained in these two test facilities and reasons for selecting transport reactors for the IGCC power plant in preference to either fixed bed or fluidized bed reactors are discussed. This paper reviews the evolution of the hot gas desulfurization system designs and includes selected results on H{sub 2}S absorption and regeneration of sulfided sorbent over several absorption/regeneration cycles conducted in the TRTU and the METC fixed bed reactor. The original design for the Sierra Pacific Project was based on fixed bed reactors with zinc ferrite as the sorbent. Owing to the high steam requirements of this sorbent, zinc titanate was selected and tested in a fixed bed reactor and was found unacceptable due to loss of strength on cyclic absorption/regeneration operation. Another sorbent evaluated was Z-Sorb{reg_sign}, a proprietary sorbent developed by Phillips Petroleum Company, was found to have excellent sulfur capacity, structural strength and regenerability. Steam was found unsuitable as fixed bed regenerator diluent, this results in a requirement for a large amount of inert gas, whereas a transport regenerator requires no diluent. The final Sierra design features transport reactors for both desulfurization and regeneration steps using neat air. 3 refs., 3 figs., 2 tabs.

  16. Microbial Desulfurization of Alkylated Dibenzothiophenes from a Hydrodesulfurized Middle Distillate by Rhodococcus erythropolis I-19

    PubMed Central

    Folsom, B. R.; Schieche, D. R.; DiGrazia, P. M.; Werner, J.; Palmer, S.

    1999-01-01

    Rhodococcus erythropolis I-19, containing multiple copies of key dsz genes, was used to desulfurize alkylated dibenzothiophenes (Cx-DBTs) found in a hydrodesulfurized middle-distillate petroleum (MD 1850). Initial desulfurization rates of dibenzothiophene (DBT) and MD 1850 by I-19 were 5.0 and 2.5 μmol g dry cell weight−1 min−1, more than 25-fold higher than that for wild-type bacteria. According to sulfur K-edge X-ray absorption near-edge structure (XANES) analysis, thiophenic compounds accounted for >95% of the total sulfur found in MD 1850, predominantly Cx-DBTs and alkylated benzothiophenes. Extensive biodesulfurization resulted in a 67% reduction of total sulfur from 1,850 to 615 ppm S. XANES analysis of the 615-ppm material gave a sulfur distribution of 75% thiophenes, 11% sulfides, 2% sulfoxides, and 12% sulfones. I-19 preferentially desulfurized DBT and C1-DBTs, followed by the more highly alkylated Cx-DBTs. Shifting zero- to first-order (first-order) desulfurization rate kinetics were observed when MD 1850 was diluted with hexadecane. Apparent saturation rate constant (K0) and half-saturation rate constant (K1) values were calculated to be 2.8 μmol g dry cell weight−1 min−1 and 130 ppm, respectively. However, partial biocatalytic reduction of MD 1850 sulfur concentration followed by determination of initial rates with fresh biocatalyst led to a sigmoidal kinetic behavior. A competitive-substrate model suggested that the apparent K1 values for each group of Cx-DBTs increased with increasing alkylation. Overall desulfurization rate kinetics with I-19 were affected by the concentration and distribution of Cx-DBTs according to the number and/or lengths of alkyl groups attached to the basic ring structure. PMID:10543810

  17. Irradiation pretreatment for coal desulfurization

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.

    1979-01-01

    Process using highly-penetrating nuclear radiation (Beta and Gamma radiation) from nuclear power plant radioactive waste to irradiate coal prior to conventional desulfurization procedures increases total extraction of sulfur.

  18. Desulfurization Sorbents for Transport-Bed Applications

    SciTech Connect

    Gupta, Raghubir P.; Turk, Brian S.; Vierheilig, Albert A.

    1997-07-01

    This project extends the prior work on the development of fluidizable zinc titanate particles using a spray-drying technique to impart high reactivity and attrition resistance. The specific objectives are: (1) To develop highly reactive and attrition-resistant zinc titanate sorbents in 40- to 150-{micro}m particle size range for transport reactor applications; (2) To transfer sorbent production technology to private sector; and (3) To provide technical support to Sierra Pacific Clean Coal Technology Demonstration plant and FETC's Hot-Gas Desulfurization Process Development Unit (PDU), both employing a transport reactor system.

  19. Advanced Hot-Gas Desulfurization Sorbents

    SciTech Connect

    Jothimurugesan, K.; Adeyiga, A.; Gangwal, S.K.

    1996-12-31

    The objective of this project is to develop advanced hot-gas desulfurization sorbents for relatively low temperature application that show stable and high sulfidation reactivity at 343 to 538 {degrees}C. A number of zinc-based formulations will be prepared and screened for testing in a fixed-bed reactor at high pressure (1 to 20 atm) and high temperatures using simulated coal-derived fuel gases. One of the superior formulations will be tested for long- term durability and chemical reactivity in the reactor. To prevent sulfation, catalyst additives will be investigated, which would promote a lower regeneration temperature.

  20. Biocatalytic Desulfurization Capabilities of a Mixed Culture during Non-Destructive Utilization of Recalcitrant Organosulfur Compounds

    PubMed Central

    Ismail, Wael; El-Sayed, Wael S.; Abdul Raheem, Abdul Salam; Mohamed, Magdy E.; El Nayal, Ashraf M.

    2016-01-01

    We investigated the biodesulfurization potential of a mixed culture AK6 enriched from petroleum hydrocarbons-polluted soil with dibenzothiophene (DBT) as a sulfur source. In addition to DBT, AK6 utilized the following compounds as sulfur sources: 4-methyldibenzothiophene (4-MDBT), benzothiophene (BT), and 4,6- dimethyldibenzothiophene (4,6-DM-DBT). None of these compounds supported the growth of AK6 as the sole carbon and sulfur source. AK6 could not grow on dibenzylsulfide (DBS) as a sulfur source. The AK6 community structure changed according to the provided sulfur source. The major DGGE bands represented members of the genera Sphingobacterium, Klebsiella, Pseudomonas, Stenotrophomonas, Arthrobacter, Mycobacterium, and Rhodococcus. Sphingobacterium sp. and Pseudomonas sp. were abundant across all cultures utilizing any of the tested thiophenic S-compounds. Mycobacterium/Rhodococcus spp. were restricted to the 4-MDBT culture. The 4-MDBT culture had the highest species richness and diversity. Biodesulfurization of DBT by resting cells of AK6 produced 2-hydroxybiphenyl (2-HBP) in addition to trace amounts of phenylacetate. AK6 transformed DBT to 2-hydroxybiphenyl with a specific activity of 9 ± 0.6 μM 2-HBP g dry cell weight−1 h−1. PCR confirmed the presence in the AK6 community of the sulfur-specific (4S) pathway genes dszB and dszC. Mixed cultures hold a better potential than axenic ones for the development of a biodesulfurization technology. PMID:26973637

  1. Process of desulfurization

    SciTech Connect

    Colley, J.D.

    1989-10-24

    This patent describes an improvement in a process for the desulfurization of flue gas utilizing limestone as absorbent in a double loop system, wherein the flue gas is introduced into a quenching zone for contact with a first slurry of the limestone, and thereafter passes to an absorbing zone for further contact with a second slurry of the limestone. The second slurry being supplied from a mixing zone into which water and limestone are charged. The first slurry being supplied from the solids rich stream from a solid-liquid separator which is supplied from the mixing zone, and wherein air is introduced into the quenching zone to convert the calcium sulfite present therein to gypsum. The improvement comprises supplying air to the mixing zone to convert calcium sulfite therein to large gypsum crystals which are preferentially separated into the first slurry.

  2. Enzymatic desulfurization of coal

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V. ); Marquis, J.K. . School of Medicine)

    1989-11-07

    Our experimental approach focuses on the use of enzymes which catalyze the addition of oxygen to organic compounds. In tailoring the application of these enzymes to coal processing, we are particularly interested in ensuring that oxidation occurs at sulfur and not at carbon-carbon bonds. Previous studies with DBT have shown that the reaction most frequently observed in microbial oxidative pathways is one in which DBT is oxidized at ring carbons. These reactions, as we have said, are accompanied by a considerable decrease in the energy content of the compound. In addition, microbial pathways have been identified in which the sulfur atom is sequentially oxidized to sulfoxide, to sulfone, to sulfonate, and finally to sulfuric acid. In this case, the fuel value of the desulfurized compounds is largely retained. We are evaluating the potential of commercially available enzymes to selectively catalyze oxidation at sulfur.

  3. Enzymatic desulfurization of coal

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.

    1990-03-23

    Our experimental approach focuses on the use of enzymes which catalyze the addition of oxygen to organic compounds. In tailoring the application of these enzymes to coal processing, we are particularly interested in ensuring that oxidation occurs at sulfur and not at carbon-carbon bonds. Previous studies with DBT have shown that the reaction most frequently observed in microbial oxidative pathways is one in which DBT is oxidized at ring carbons. These reactions, as we have said, are accompanied by a considerable decrease in the energy content of the compound. In addition, microbial pathways have been identified in which the sulfur atom is sequentially oxidized to sulfoxide, to sulfone, to sulfonate, and finally to sulfuric acid. In this case, the fuel value of the desulfurized compounds is largely retained. We are evaluating the potential of commercially available enzymes to perform this function.

  4. Comprehensive report to Congress: Clean Coal Technology Program: LIFAC sorbent injection desulfurization demonstration project: A project proposed by: LIFAC North America, Inc

    SciTech Connect

    Not Available

    1990-10-01

    This report describes a project proposed by LIFAC North America, Inc., (LIFAC NA). The host site will be a coal-fired powerplant of Richmond Power Light in Indiana. LIFAC technology uses upper-furnace limestone injection with patented humidification of the flue gas to remove 75--80% of the sulfur dioxide (SO{sub 2}) in the flue gas. In the LIFAC process, limestone is injected into the upper part of the furnace where the temperatures are sufficiently high to calcine the calcium carbonate (CaCO{sub 3}) to lime (CaO), which reacts with the SO{sub 2} in the flue gas to form calcium sulfite (CaSO{sub 3}), some of which oxidizes to form calcium sulfate (CaSO{sub 4}). The flue gas leaving the boiler then enters LIFAC's unique humidification chamber which increases the water content of the flue gas and activates the lime to enhance SO{sub 2} removal. Reduction of SO{sub 2} emissions are approximately 75--80%. Spent sorbent is then removed, along with the fly ash by an existing electrostatic precipitator (ESP) or baghouse. 6 figs., 1 tab.

  5. Desulfurization of hydrocarbons

    SciTech Connect

    Eberly, P.E. Jr.

    1986-06-03

    A process is described for reforming a sulfur-containing naphtha feed, wherein is included in combination, a hydrofiner which contains a metal catalyst, the metallic component of which is selected from Group VIB and Group VIII, with which the sulfur-containing naphtha feed is contacted with hydrogen, at reaction conditions inclusive of temperatures ranging from about 400/sup 0/F to about 850/sup 0/F to remove sulfur and provide a product naphtha which contains from about 5 wppm to about 50 wppm, and higher, sulfur, a guard chamber filled with a sorbent into which the partially desulfurized hydrofined naphtha is injected to flow therethrough to effect further removal of sulfur, and a reforming unit which contains a plurality of sulfur sensitive catalyst-containing on-stream reactors connected in series, the naphtha feed to which flows in sequence from one reactor of the series of another to contact the catalyst contained therein at reforming conditions, the improvement comprising maintaining within the guard chamber a sorbent comprised of nickel in concentration ranging from about 10 percent to about 70 percent, calculated as metallic nickel based on the total weight of the sorbent, iron in concentration ranging from about 1 percent to about 15 percent, calculated as metallic iron based on the total weight of the sorbent, and a porous, refractory inorganic oxide, at temperatures ranging above about 350/sup 0/F, to produce a reformer feedstock containing no more than about 2 wppm sulfur.

  6. Desulfurization apparatus and method

    SciTech Connect

    Rong, Charles; Jiang, Rongzhong; Chu, Deryn

    2013-06-18

    A method and system for desulfurization comprising first and second metal oxides; a walled enclosure having an inlet and an exhaust for the passage of gas to be treated; the first and second metal oxide being combinable with hydrogen sulfide to produce a reaction comprising a sulfide and water; the first metal oxide forming a first layer and the second metal oxide forming a second layer within the walled surroundings; the first and second layers being positioned so the first layer removes the bulk amount of the hydrogen sulfide from the treated gas prior to passage through the second layer, and the second layer removes substantially all of the remaining hydrogen sulfide from the treated gas; the first metal oxide producing a stoichiometrical capacity in excess of 500 mg sulfur/gram; the second metal oxide reacts with the hydrogen sulfide more favorably but has a stoichometrical capacity which is less than the first reactant; whereby the optimal amount by weight of the first and second metal oxides is achieved by utilizing two to three units by weight of the first metal oxide for every unit of the second metal oxide.

  7. METC hot gas desulfurization program overview

    SciTech Connect

    Cicero, D.C.

    1994-10-01

    This overview provides a frame of reference for the Morgantown Energy Technology Center`s (METC`S) on-going hot gas desulfurization research. Although there are several methods to separate contaminant gases from fuel gases, that method receiving primary development is absorption through the use of metal oxides. Research into high-temperature and high-pressure control of sulfur species includes primarily those sorbents made of mixed-metal oxides, which offer the advantages of regenerability. These are predominantly composed of zinc and are made into media that can be utilized in reactors of either fixed-bed, moving-bed, fluidized-bed, or transport configurations. Zinc Ferrite (ZnO-Fe{sub 2}O{sub 3}), Zinc Titanate (ZnO-TiO{sub 2}), Z-SORP{reg_sign}, and METC-2/METC-6 are the current mixed-metal sorbents being investigated. The METC desulfurization program is composed of three major components: bench-scale research, pilot-plant operation, and demonstration that is a portion of the Clean Coal Demonstration projects.

  8. Nanopropulsion by biocatalytic self-assembly.

    PubMed

    Leckie, Joy; Hope, Alexander; Hughes, Meghan; Debnath, Sisir; Fleming, Scott; Wark, Alastair W; Ulijn, Rein V; Haw, Mark D

    2014-09-23

    A number of organisms and organelles are capable of self-propulsion at the micro- and nanoscales. Production of simple man-made mimics of biological transportation systems may prove relevant to achieving movement in artificial cells and nano/micronscale robotics that may be of biological and nanotechnological importance. We demonstrate the propulsion of particles based on catalytically controlled molecular self-assembly and fiber formation at the particle surface. Specifically, phosphatase enzymes (acting as the engine) are conjugated to a quantum dot (the vehicle), and are subsequently exposed to micellar aggregates (fuel) that upon biocatalytic dephosphorylation undergo fibrillar self-assembly, which in turn causes propulsion. The motion of individual enzyme/quantum dot conjugates is followed directly using fluorescence microscopy. While overall movement remains random, the enzyme-conjugates exhibit significantly faster transport in the presence of the fiber forming system, compared to controls without fuel, a non-self-assembling substrate, or a substrate which assembles into spherical, rather than fibrous structures upon enzymatic dephosphorylation. When increasing the concentration of the fiber-forming fuel, the speed of the conjugates increases compared to non-self-assembling substrate, although directionality remains random.

  9. Vinylation of Unprotected Phenols Using a Biocatalytic System.

    PubMed

    Busto, Eduardo; Simon, Robert C; Kroutil, Wolfgang

    2015-09-07

    Readily available substituted phenols were coupled with pyruvate in buffer solution under atmospheric conditions to afford the corresponding para-vinylphenol derivatives while releasing only one molecule of CO2 and water as the by-products. This transformation was achieved by designing a biocatalytic system that combines three biocatalytic steps, namely the C-C coupling of phenol and pyruvate in the presence of ammonia, which leads to the corresponding tyrosine derivative, followed by deamination and decarboxylation. The biocatalytic transformation proceeded with high regioselectivity and afforded exclusively the desired para products. This method thus represents an environmentally friendly approach for the direct vinylation of readily available 2-, 3-, or 2,3-disubstituted phenols on preparative scale (0.5 mmol) that provides vinylphenols in high yields (65-83 %).

  10. Desulfurization from Bauxite Water Slurry (BWS) Electrolysis

    NASA Astrophysics Data System (ADS)

    Gong, Xuzhong; Ge, Lan; Wang, Zhi; Zhuang, Siyuan; Wang, Yuhua; Ren, Lihui; Wang, Mingyong

    2016-02-01

    Feasibility of high-sulfur bauxite electrolysis desulfurization was examined using the electrochemical characterization, XRD, DTA, and FTIR. The cyclic voltammetry curves indicated that bauxite water slurry (BWS) electrolysis in NaOH system was controlled by diffusion. Additionally, the desulfurization effect of NaCl as the electrolyte was significantly better than that of NaOH as an electrolyte. As the stirring rate increased, the desulfurization ratio in NaCl system was not increased obviously, while the desulfurization ratio in NaOH system increased significantly, indicating further that electrolysis desulfurization in NaOH solution was controlled by diffusion. According to XRD, DTA, and FTIR analysis, the characteristic peaks of sulfur-containing phase in bauxite after electrolysis weakened or disappeared, indicating that the pyrite in bauxite was removed from electrolysis. Finally, the electrolytic desulfurization technology of bauxite was proposed based on the characteristics of BWS electrolysis.

  11. Coal desulfurization by aqueous chlorination

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Vasilakos, N.; Corcoran, W. H.; Grohmann, K.; Rohatgi, N. K. (Inventor)

    1982-01-01

    A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

  12. Development of advanced hot-gas desulfurization sorbents. Final report

    SciTech Connect

    Jothimurugesan, K.; Adeyiga, A.A.; Gangwal, S.K.

    1997-10-01

    The objective of this project was to develop hot-gas desulfurization sorbent formulations for relatively lower temperature application, with emphasis on the temperature range from 343--538 C. The candidate sorbents include highly dispersed mixed metal oxides of zinc, iron, copper, cobalt, nickel and molybdenum. The specific objective was to develop suitable sorbents, that would have high and stable surface area and are sufficiently reactive and regenerable at the relatively lower temperatures of interest in this work. Stability of surface area during regeneration was achieved by adding stabilizers. To prevent sulfation, catalyst additives that promote the light-off of the regeneration reaction at lower temperature was considered. Another objective of this study was to develop attrition-resistant advanced hot-gas desulfurization sorbents which show stable and high sulfidation reactivity at 343 to 538 C and regenerability at lower temperatures than leading first generation sorbents.

  13. DEEP DESULFURIZATION OF DIESEL FUELS BY A NOVEL INTEGRATED APPROACH

    SciTech Connect

    Xiaoliang Ma; Uday Turaga; Shingo Watanabe; Subramani Velu; Chunshan Song

    2004-05-01

    The overall objective of this project is to explore a new desulfurization system concept, which consists of efficient separation of the refractory sulfur compounds from diesel fuel by selective adsorption, and effective hydrodesulfurization of the concentrated fraction of the refractory sulfur compounds in diesel fuels. Our approaches focused on (1) selecting and developing new adsorbents for selective adsorption of sulfur or sulfur compounds in commercial diesel fuel; (2) conducting the adsorption desulfurization of model fuels and real diesel fuels by the selective-adsorption-for-removing-sulfur (PSUSARS) process over various developed adsorbents, and examining the adsorptive desulfurization performance of various adsorbents; (3) developing and evaluating the regeneration methods for various spent adsorbent; (4) developing new catalysts for hydrodesulfurization of the refractory sulfur existing in the commercial diesel fuel; (5) on the basis of the fundamental understanding of the adsorptive performance and regeneration natures of the adsorbents, further confirming and improving the conceptual design of the novel PSU-SARS process for deep desulfurization of diesel fuel Three types of adsorbents, the metal-chloride-based adsorbents, the activated nickel-based adsorbents and the metal-sulfide-based adsorbents, have been developed for selective adsorption desulfurization of liquid hydrocarbons. All of three types of the adsorbents exhibit the significant selectivity for sulfur compounds, including alkyl dibenzothiophenes (DBTs), in diesel fuel. Adsorption desulfurization of real diesel fuels (regular diesel fuel (DF), S: 325 ppmw; low sulfur diesel fuel (LSD-I), S: 47 ppmw) over the nickel-based adsorbents (A-2 and A-5) has been conducted at different conditions by using a flowing system. The adsorption capacity of DF over A-2 corresponding to an outlet sulfur level of 30 ppmw is 2.8 mg-S/g-A. The adsorption capacity of LSD-I over A-5 corresponding to the break

  14. Low temperature aqueous desulfurization of coal

    DOEpatents

    Slegeir, W.A.; Healy, F.E.; Sapienza, R.S.

    1985-04-18

    This invention describes a chemical process for desulfurizing coal, especially adaptable to the treatment of coal-water slurries, at temperatures as low as ambient, comprising treating the coal with aqueous titanous chloride whereby hydrogen sulfide is liberated and the desulfurized coal is separated with the conversion of titanous chloride to titanium oxides.

  15. Low temperature aqueous desulfurization of coal

    DOEpatents

    Slegeir, William A.; Healy, Francis E.; Sapienza, Richard S.

    1985-01-01

    This invention describes a chemical process for desulfurizing coal, especially adaptable to the treatment of coal-water slurries, at temperatures as low as ambient, comprising treating the coal with aqueous titanous chloride whereby hydrogen sulfide is liberated and the desulfurized coal is separated with the conversion of titanous chloride to titanium oxides.

  16. ADVANCED SULFUR CONTROL CONCEPTS FOR HOT GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    1998-09-30

    The objective of this project is to develop a hot-gas desulfurization process scheme for control of H2S in HTHP coal gas that can be more simply and economically integrated with known regenerable sorbents in DOE/METC-sponsored work than current leading hot-gas desulfurization technologies. In addition to being more economical, the process scheme to be developed must yield an elemental sulfur byproduct. The Direct Sulfur Recovery Process (DSRP), a leading process for producing an elemental sulfur byproduct in hot-gas desulfurization systems, incurs a coal gas use penalty, because coal gas is required to reduce the SO2 in regeneration off-gas to elemental sulfur. Alternative regeneration schemes, which avoid coal gas use and produce elemental sulfur, will be evaluated. These include (i) regeneration of sulfided sorbent using SO2 ; (ii) partial oxidation of sulfided sorbent in an O2 starved environment; and (iii) regeneration of sulfided sorbent using steam to produce H2S followed by direct oxidation of H2S to elemental sulfur. Known regenerable sorbents will be modified to improve the feasibility of the above alternative regeneration approaches. Performance characteristics of the modified sorbents and processes will be obtained through lab- and bench-scale testing. Technical and economic evaluation of the most promising processes concept(s) will be carried out.

  17. A new approach to the deposition of nanostructured biocatalytic films

    NASA Astrophysics Data System (ADS)

    Troitsky, V. I.; Berzina, T. S.; Pastorino, L.; Bernasconi, E.; Nicolini, C.

    2003-06-01

    In the present work, monolayer engineering was used to fabricate biocatalytic nanostructured thin films based on the enzyme penicillin G acylase. The biocatalytic films with enhanced characteristics were produced by the deposition of alternate-layer assemblies with a predetermined structure using a combination of Langmuir-Blodgett and adsorption techniques. The value of enzyme activity and the level of protein detachment were measured in dependence on the variation of film composition and on the sequence of layer alternation. As a result, highly active and stable structures were found, which could be promising candidates for practical applications. The method of modification of the deposition method to provide continuous film formation on large-area supports is discussed.

  18. CONVERSION EXTRACTION DESULFURIZATION (CED) PHASE III

    SciTech Connect

    James Boltz

    2005-03-01

    This project was undertaken to refine the Conversion Extraction Desulfurization (CED) technology to efficiently and economically remove sulfur from diesel fuel to levels below 15-ppm. CED is considered a generic term covering all desulfurization processes that involve oxidation and extraction. The CED process first extracts a fraction of the sulfur from the diesel, then selectively oxidizes the remaining sulfur compounds, and finally extracts these oxidized materials. The Department of Energy (DOE) awarded Petro Star Inc. a contract to fund Phase III of the CED process development. Phase III consisted of testing a continuous-flow process, optimization of the process steps, design of a pilot plant, and completion of a market study for licensing the process. Petro Star and the Degussa Corporation in coordination with Koch Modular Process Systems (KMPS) tested six key process steps in a 7.6-centimeter (cm) (3.0-inch) inside diameter (ID) column at gas oil feed rates of 7.8 to 93.3 liters per hour (l/h) (2.1 to 24.6 gallons per hour). The team verified the technical feasibility with respect to hydraulics for each unit operation tested and successfully demonstrated pre-extraction and solvent recovery distillation. Test operations conducted at KMPS demonstrated that the oxidation reaction converted a maximum of 97% of the thiophenes. The CED Process Development Team demonstrated that CED technology is capable of reducing the sulfur content of light atmospheric gas oil from 5,000-ppm to less than 15-ppm within the laboratory scale. In continuous flow trials, the CED process consistently produced fuel with approximately 20-ppm of sulfur. The process economics study calculated an estimated process cost of $5.70 per product barrel. The Kline Company performed a marketing study to evaluate the possibility of licensing the CED technology. Kline concluded that only 13 refineries harbored opportunity for the CED process. The Kline study and the research team's discussions with

  19. LIFAC sorbent injection desulfurization demonstration project

    SciTech Connect

    Not Available

    1991-01-01

    LIFAC combines upper-furnace limestone injection followed by post-furnace humidification in an activation reactor located between the air preheater and the ESP. The process produces a dry and stable waste product that is partially removed from the bottom of the activation reactor and partially removed at the ESP.

  20. Biocatalytic approaches applied to the synthesis of nucleoside prodrugs.

    PubMed

    Iglesias, Luis E; Lewkowicz, Elizabeth S; Medici, Rosario; Bianchi, Paola; Iribarren, Adolfo M

    2015-01-01

    Nucleosides are valuable bioactive molecules, which display antiviral and antitumour activities. Diverse types of prodrugs are designed to enhance their therapeutic efficacy, however this strategy faces the troublesome selectivity issues of nucleoside chemistry. In this context, the aim of this review is to give an overview of the opportunities provided by biocatalytic procedures in the preparation of nucleoside prodrugs. The potential of biocatalysis in this research area will be presented through examples covering the different types of nucleoside prodrugs: nucleoside analogues as prodrugs, nucleoside lipophilic prodrugs and nucleoside hydrophilic prodrugs.

  1. Biocatalytic routes to chiral amines and amino acids.

    PubMed

    Gotor-Fernández, Vicente; Gotor, Vicente

    2009-11-01

    Biocatalysis is a well-known and well-established technology that allows clean and straightforward stereoselective transformations to be conducted under mild reaction conditions. Traditionally, hydrolases, oxidoreductases and lyases have been used for these transformations to give the final products in excellent yields and with a high level of enantiopurity. Particular attention has been focused on biocatalytic routes because of the increasing demand for economic and environmentally friendly processes for the manufacture of single enantiomer drugs and high added-value compounds by the industrial sector. Recent advances in the field of biotransformations applied to the production of chiral amines and amino acids are reviewed.

  2. Method for desulfurization of coal

    DOEpatents

    Kelland, David R.

    1987-01-01

    A process and apparatus for desulfurizing coal which removes sulfur in the inorganic and organic form by preferentially heating the inorganic iron sulfides in coal in a flowing gas to convert some of the inorganic iron sulfides from a pyrite form FeS.sub.2 to a troilite FeS form or a pyrrhotite form Fe.sub.1-x S and release some of the sulfur as a gaseous compound. The troilite and pyrrhotite forms are convenient catalyst for removing the organic sulfur in the next step, which is to react the coal with chemical agents such as alcohol, thus removing the organic sulfur as a liquid or a gas such as H.sub.2 S. The remaining inorganic sulfur is left in the predominantly higher magnetic form of pyrrhotite and is then removed by magnetic separation techniques. Optionally, an organic flocculant may be added after the organic sulfur has been removed and before magnetic separation. The flocculant attaches non-pyrite minerals with the pyrrhotite for removal by magnetic separation to reduce the ash-forming contents.

  3. Method for desulfurization of coal

    DOEpatents

    Kelland, D.R.

    1987-07-07

    A process and apparatus are disclosed for desulfurizing coal which removes sulfur in the inorganic and organic form by preferentially heating the inorganic iron sulfides in coal in a flowing gas to convert some of the inorganic iron sulfides from a pyrite form FeS[sub 2] to a troilite FeS form or a pyrrhotite form Fe[sub 1[minus]x]S and release some of the sulfur as a gaseous compound. The troilite and pyrrhotite forms are convenient catalyst for removing the organic sulfur in the next step, which is to react the coal with chemical agents such as alcohol, thus removing the organic sulfur as a liquid or a gas such as H[sub 2]S. The remaining inorganic sulfur is left in the predominantly higher magnetic form of pyrrhotite and is then removed by magnetic separation techniques. Optionally, an organic flocculant may be added after the organic sulfur has been removed and before magnetic separation. The flocculant attaches non-pyrite minerals with the pyrrhotite for removal by magnetic separation to reduce the ash-forming contents. 2 figs.

  4. Process for desulfurizing an exhaust gas

    SciTech Connect

    Shinoda, N.; Okino, S.; Oshima, M.; Shigeta, S.; Tatani, A.; Ukawa, N.

    1983-12-13

    A process is disclosed for desulfurizing an exhaust gas which comprises desulfurizing an exhaust gas containing SO/sub 2/ by bringing it into contact with a slurry containing calcium compounds and aluminum compounds, characterized in that the concentration of the dissolved aluminum ion in said slurry is detected and a manganese compound is supplied into said slurry in such a manner that the ratio of the concentration of manganese (including both solid and liquid) to said concentration of the dissolved aluminum ion may be maintained in a molar ratio of less than 1 in said slurry.

  5. Bench-scale development of mild gasification char desulfurization. Technical report, 1 March--31 May 1994

    SciTech Connect

    Knight, R.A.

    1994-09-01

    The goal of this project is to scale up a process, developed under a previous ICCI grant, for desulfurization of mild gasification char by treatment with hydrogen-rich process-derived fuel gas at 650--760 C and 7--15 atm. The char can be converted into a low-sulfur metallurgical form coke. In the prior study, IBC-105 coal with 4.0 wt% sulfur was converted to chars with less than 1.0 wt% sulfur in a laboratory-scale batch reactor. The susceptibility of the char to desulfurization was correlated with physicochemical char properties and mild gasification conditions. Acid pretreatment of the coal prior to mild gasification was also shown to significantly enhance subsequent sulfur removal. In this study, IGT is conducting continuous bench-scale tests in a 1-lb/h fluidized-bed reactor to determine the preferred process conditions and obtain steady-state data necessary for process design and scale-up. The desulfurized chars are to be used to produce low-sulfur form coke, which will be evaluated for density, reactivity, and strength properties relevant to utilization in blast furnaces. This quarter, 2,500 g of mild gasification char was produced from untreated IBC-105 coal in the bench-scale reactor. Half of this char will be subjected to sulfuric acid treatment to enhance subsequent desulfurization. Char-producing runs were also initiated with acid-pretreated coal, which will produce about 1,250 g of char.

  6. Desulfurization, demetalation and denitrogenation of coal

    SciTech Connect

    Farcasiu, M.; Mitchell, T.O.; Whitehurst, D.D.

    1981-12-01

    The specification discloses a desulfurization, demetalation and denitrogenation process for coal and coal liquid charge stocks. The process comprises contacting the charge stock in the absence of externally added hydrogen with a hydrogen donor solvent in the presence of a catalytic amount of naturally occurring porous metal ores such as manganese nodules, bog iron, bog manganese, nickel laterites, bauxite or spent bauxite.

  7. Recombinant DNA encoding a desulfurization biocatalyst

    DOEpatents

    Rambosek, J.; Piddington, C.S.; Kovacevich, B.R.; Young, K.D.; Denome, S.A.

    1994-10-18

    This invention relates to a recombinant DNA molecule containing a gene or genes which encode a biocatalyst capable of desulfurizing a fossil fuel which contains organic sulfur molecules. For example, the present invention encompasses a recombinant DNA molecule containing a gene or genes of a strain of Rhodococcus rhodochrous. 13 figs.

  8. Recombinant DNA encoding a desulfurization biocatalyst

    DOEpatents

    Rambosek, John; Piddington, Chris S.; Kovacevich, Brian R.; Young, Kevin D.; Denome, Sylvia A.

    1994-01-01

    This invention relates to a recombinant DNA molecule containing a gene or genes which encode a biocatalyst capable of desulfurizing a fossil fuel which contains organic sulfur molecules. For example, the present invention encompasses a recombinant DNA molecule containing a gene or genes of a strain of Rhodococcus rhodochrous.

  9. Low-Cost Aqueous Coal Desulfurization

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Vasilakos, N.; Corcoran, W. H.; Grohmann, K.; Rohatgi, N. K.

    1982-01-01

    Water-based process for desulfurizing coal not only eliminates need for costly organic solvent but removes sulfur more effectively than an earlier solvent-based process. New process could provide low-cost commercial method for converting high-sulfur coal into environmentally acceptable fuel.

  10. Biocompatible enzymatic roller pens for direct writing of biocatalytic materials: "do-it-yourself" electrochemical biosensors.

    PubMed

    Bandodkar, Amay J; Jia, Wenzhao; Ramírez, Julian; Wang, Joseph

    2015-06-03

    The development of enzymatic-ink-based roller pens for direct drawing of biocatalytic sensors, in general, and for realizing renewable glucose sensor strips, in particular, is described. The resulting enzymatic-ink pen allows facile fabrication of high-quality inexpensive electrochemical biosensors of any design by the user on a wide variety of surfaces having complex textures with minimal user training. Unlike prefabricated sensors, this approach empowers the end user with the ability of "on-demand" and "on-site" designing and fabricating of biocatalytic sensors to suit their specific requirement. The resulting devices are thus referred to as "do-it-yourself" sensors. The bio-active pens produce highly reproducible biocatalytic traces with minimal edge roughness. The composition of the new enzymatic inks has been optimized for ensuring good biocatalytic activity, electrical conductivity, biocompati-bility, reproducible writing, and surface adherence. The resulting inks are characterized using spectroscopic, viscometric, electrochemical, thermal and microscopic techniques. Applicability to renewable blood glucose testing, epidermal glucose monitoring, and on-leaf phenol detection are demonstrated in connection to glucose oxidase and tyrosinase-based carbon inks. The "do-it-yourself" renewable glucose sensor strips offer a "fresh," reproducible, low-cost biocatalytic sensor surface for each blood test. The ability to directly draw biocatalytic conducting traces even on unconventional surfaces opens up new avenues in various sensing applications in low-resource settings and holds great promise for diverse healthcare, environmental, and defense domains.

  11. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    PubMed

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics.

  12. Microfluidic multi-input reactor for biocatalytic synthesis using transketolase.

    PubMed

    Lawrence, James; O'Sullivan, Brian; Lye, Gary J; Wohlgemuth, Roland; Szita, Nicolas

    2013-11-01

    Biocatalytic synthesis in continuous-flow microreactors is of increasing interest for the production of specialty chemicals. However, the yield of production achievable in these reactors can be limited by the adverse effects of high substrate concentration on the biocatalyst, including inhibition and denaturation. Fed-batch reactors have been developed in order to overcome this problem, but no continuous-flow solution exists. We present the design of a novel multi-input microfluidic reactor, capable of substrate feeding at multiple points, as a first step towards overcoming these problems in a continuous-flow setting. Using the transketolase-(TK) catalysed reaction of lithium hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose (ERY), we demonstrate the transposition of a fed-batch substrate feeding strategy to our microfluidic reactor. We obtained a 4.5-fold increase in output concentration and a 5-fold increase in throughput compared with a single input reactor.

  13. Microfluidic multi-input reactor for biocatalytic synthesis using transketolase☆

    PubMed Central

    Lawrence, James; O'Sullivan, Brian; Lye, Gary J.; Wohlgemuth, Roland; Szita, Nicolas

    2013-01-01

    Biocatalytic synthesis in continuous-flow microreactors is of increasing interest for the production of specialty chemicals. However, the yield of production achievable in these reactors can be limited by the adverse effects of high substrate concentration on the biocatalyst, including inhibition and denaturation. Fed-batch reactors have been developed in order to overcome this problem, but no continuous-flow solution exists. We present the design of a novel multi-input microfluidic reactor, capable of substrate feeding at multiple points, as a first step towards overcoming these problems in a continuous-flow setting. Using the transketolase-(TK) catalysed reaction of lithium hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose (ERY), we demonstrate the transposition of a fed-batch substrate feeding strategy to our microfluidic reactor. We obtained a 4.5-fold increase in output concentration and a 5-fold increase in throughput compared with a single input reactor. PMID:24187515

  14. [Performance of desulfurizing absorbent of roasted navajoite].

    PubMed

    Chen, Fang; Yang, Chun-ping; Gan, Hai-ming; Wu, Ting; Chen, Hai-lin; Chen, Hong; Xu, Ke-hui; Xie, Geng-xin

    2010-04-01

    An innovative flue gas desulfurization (FGD) coupling process was proposed in this study to overcome the problems in wet-type limestone/lime processes which include fouling, clogging, and difficulty of selling the by-products and the problems in traditional process for vanadium extraction from navajoite ore such as excessive consumption of sulfuric acid and emissions of pollutants. The performance of a jet bubbling reactor (JBR) at pilot-scale was evaluated using navajoite ore produced in the process of extracting vanadium pentoxide as desulfurization absorbent. Results showed that navajoite ore slurry achieved better desulfurization performance than limestone slurry. When the inlet flue gas pressure drop was 3.0 kPa, the gas flow was about 2350 m3 x h(-1) and the pH of the navajoite ore slurry was higher than 4.5, the desulfurization efficiency was stable about 90%. The SO2 removal efficiency appeared to increase along with the increasing of absorbent cycle-index. The efficiency of the second circulation was improved 3.5% compared to the first circulation. After an operating duration of 40 minutes, the leaching rate of vanadium pentoxide was about 20%, and reached 60% when the by-products were leached with 5% dilute sulfuric acid for 10 hours. The by-product from this process not only could be used to produce vanadium pentoxide which is a valuable industrial product, but also could significantly overcome the pollution problem existing in the traditional refining process of vanadium pentoxide when navajoite ore is used as the feed material. This FGD process using roasted navajoite slurry as absorbent is environmental sound and cost-effective, and shows the potential for application in the field of flue gas desulfurization as well as hydrometallurgy.

  15. METC`s pilot-scale hot-gas desulfurization Process Development Unit

    SciTech Connect

    McMillian, M.H.; Bissett, L.A.

    1996-12-31

    801The Morgantown Energy Technology Center (METC) has designed and is currently constructing an on-site, hot gas desulfurization (HGD) Process Development Unit (PDU). The PDU is designed to use regenerable solid metal oxide sorbents that absorb hydrogen sulfide from high-temperature, high-pressure simulated coal-gasification fuel gas that is generated by a METC-designed syngas generator. The simulated coal gas is a mixture of partially combusted natural gas, water, carbon dioxide and hydrogen sulfide. PDU process conditions will be representative of anticipated commercial applications in terms of temperatures, pressures, compositions, velocities, and sorbent cycling. The PDU supports the Integrated Gasification Combined Cycle (IGCC) mission at METC by providing a test bed for development of IGCC cleanup systems that offer low capital cost, operating costs, and costs of electricity. METC intends to develop additional industrial involvement opportunities as the project progresses towards operations. Objectives The primary objectives of the PDU are to: (1) fill the gap between small-scale testing and large-scale demonstration projects by providing a cost effective test site for transport and fluid-bed desulfurization reactor and sorbent development, (2) demonstrate sorbent suitability over a wide range of parameters and (3) generate significant information on process control for transport and fluidized bed based desulfurization. PDU data is expected to be used to optimize process performance by expanding the experience for larger-scale demonstration projects, such as Sierra Pacific Power Company`s Clean Coal Technology project.

  16. ADVANCED SULFUR CONTROL CONCEPTS FOR HOT-GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    A. LOPEZ ORTIZ; D.P. HARRISON; F.R. GROVES; J.D. WHITE; S. ZHANG; W.-N. HUANG; Y. ZENG

    1998-10-31

    This research project examined the feasibility of a second generation high-temperature coal gas desulfurization process in which elemental sulfur is produced directly during the sorbent regeneration phase. Two concepts were evaluated experimentally. In the first, FeS was regenerated in a H2O-O2 mixture. Large fractions of the sulfur were liberated in elemental form when the H2O-O2 ratio was large. However, the mole percent of elemental sulfur in the product was always quite small (<<1%) and a process based on this concept was judged to be impractical because of the low temperature and high energy requirements associated with condensing the sulfur. The second concept involved desulfurization using CeO2 and regeneration of the sulfided sorbent, Ce2O2S, using SO2 to produce elemental sulfur directly. No significant side reactions were observed and the reaction was found to be quite rapid over the temperature range of 500°C to 700°C. Elemental sulfur concentrations (as S2) as large as 20 mol% were produced. Limitations associated with the cerium sorbent process are concentrated in the desulfurization phase. High temperature and highly reducing coal gas such as produced in the Shell gasification process are required if high sulfur removal efficiencies are to be achieved. For example, the equilibrium H2S concentration at 800°C from a Shell gas in contact with CeO2 is about 300 ppmv, well above the allowable IGCC specification. In this case, a two-stage desulfurization process using CeO2 for bulk H2S removal following by a zinc sorbent polishing step would be required. Under appropriate conditions, however, CeO2 can be reduced to non-stoichiometric CeOn (n<2) which has significantly greater affinity for H2S. Pre-breakthrough H2S concentrations in the range of 1 ppmv to 5 ppmv were measured in sulfidation tests using CeOn at 700°C in highly reducing gases, as measured by equilibrium O2 concentration, comparable to the Shell gas. Good sorbent durability was indicated in

  17. Pore structure and reactivity changes in hot coal gas desulfurization sorbents

    SciTech Connect

    Sotirchos, S.V.

    1991-05-01

    The primary objective of the project was the investigation of the pore structure and reactivity changes occurring in metal/metal oxide sorbents used for desulfurization of hot coal gas during sulfidation and regeneration, with particular emphasis placed on the effects of these changes on the sorptive capacity and efficiency of the sorbents. Commercially available zinc oxide sorbents were used as model solids in our experimental investigation of the sulfidation and regeneration processes.

  18. Application research of integrated desulfurization and dust removal technology

    SciTech Connect

    Fei, S.; Hongsun, J.

    1999-07-01

    The conclusion about the emission control characteristics of the coal-fired power plants is drawn on the basis of investigation in Northeast of China. A simple, reliable and low cost integrated technology instead of many mature but expensive FGD technologies was developed to achieve overall desulfurization and dust removal qualification simultaneously. With the adoption of limestone injection into furnace and three-phase fluidized packing column transformation, the technology is especially suitable for retrofit of existing units between 50MW and 200MW that are commonly equipped with wet scrubbers. The feasibility of retrofit application to a 220t/h boiler is demonstrated according to technical and economic research and design. The new FGD project is capable of meeting environment demand with minimal modification and capital and operating cost, while ensuring uninterrupted and safe power generation.

  19. Desulfurizing Coal With an Alkali Treatment

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kalvinskas, J. J.

    1987-01-01

    Experimental coal-desulfurization process uses alkalies and steam in fluidized-bed reactor. With highly volatile, high-sulfur bituminous coal, process removed 98 percent of pyritic sulfur and 47 percent of organic sulfur. Used in coal liquefaction and in production of clean solid fuels and synthetic liquid fuels. Nitrogen or steam flows through bed of coal in reactor. Alkalies react with sulfur, removing it from coal. Nitrogen flow fluidizes bed while heating or cooling; steam is fluidizing medium during reaction.

  20. Zirconia-silica based mesoporous desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

    Palomino, Jessica M.; Tran, Dat T.; Kareh, Ana R.; Miller, Christopher A.; Gardner, Joshua M. V.; Dong, Hong; Oliver, Scott R. J.

    2015-03-01

    We report a series of mesoporous silicate sorbent materials templated by long-chain primary alkylamines that display record level of desulfurization of the jet fuel JP-8. Pure silica frameworks and those with a Si:Zr synthesis molar ratio ranging from 44:1 to 11:1 were investigated. The optimum sorbent was identified as dodecylamine-templated silica-zirconia synthesized from a gel with Si:Zr molar ratio of 15:1. With an optimized silver loading of 11 wt.%, a saturation adsorption capacity of 39.4 mgS g-1 and a silver efficiency of 1.21 molS mol Ag-1 were observed for JP-8. This sorbent displayed exceptional regenerability, maintaining 86% of its initial capacity in model fuel after solvent regeneration with diethyl ether. Low-cost, portable and reusable sorbents for the desulfurization of JP-8 jet fuel are needed to make solid oxide fuel cells (SOFCs) a reality for military power needs. SOFCs require ultra-low sulfur content fuel, which traditional desulfurization methods cannot achieve.

  1. Reclamation of abandoned surface coal mined land using flue gas desulfurization products

    SciTech Connect

    Chen, L.; Kost, D.; Dick, W.A.

    2009-07-01

    Details are given of a field-scale research project where the Fleming site, in Ohio, of highly degraded and acid-forming abandoned surface coal-mined land, was reclaimed using a dry flue gas desulfurization product from an atmospheric fluidized bed combustion burner at a General Motors plant Pontiac, MI, which burned eastern Ohio coal and used dolomitic limestone for desulfurization. Plots were seeded with a mixture of grasses, wheat and clover, in 1994 and soil and water samples were analysed in 1995 and in 2009. It was found that FGD-treated plots promoted good regenerative growth, similar to that in plots using more concentrated re-soil material. The FGD treatment also greatly improved overall water quality. 3 figs., 4 tabs.

  2. Characterization and fixed-bed testing of a nickel-based hot gas desulfurization sorbent

    SciTech Connect

    Gasper-Galvin, L.D.; Swisher, J.H.; Hammerbeck, K.

    1994-10-01

    The objective of this project was to (1) extend a preliminary investigation completed earlier on dispersed nickel sorbents by developing new processing methods, characterizing sorbent materials more extensively, and evaluating the materials in fixed bed reactor tests, and (2) to determine the feasibility of using dispersed nickel sorbents with reductive regeneration for hot gas desulfurization. One of the properties of nickel that is somewhat unique is that it forms a liquid sulfide at sufficiently high temperatures with high sulfur potentials or H{sub 2}S levels. A eutectic exists in the Ni-S phase diagram at 637 C and a composition of 33.4 wt% or 21.5 wt% S. Under controlled conditions, the formation of a liquid phase can be used to advantage in hot gas desulfurization. Sorbent preparation, the experimental unit, and experimental procedure are described. Results from the sorbent, 24Ni-7Cu-Al{sub 2}O{sub 3}, are given.

  3. Separation of Mercury from Flue Gas Desulfurization Scrubber Produced Gypsum

    SciTech Connect

    Hensman, Carl, E., P.h.D; Baker, Trevor

    2008-06-16

    Frontier Geosciences (Frontier; FGS) proposed for DOE Grant No. DE-FG02-07ER84669 that mercury control could be achieved in a wet scrubber by the addition of an amendment to the wet-FGD scrubber. To demonstrate this, a bench-scale scrubber and synthetic flue-gas supply was designed to simulate the limestone fed, wet-desulfurization units utilized by coal-fired power plants. Frontier maintains that the mercury released from these utilities can be controlled and reduced by modifying the existing equipment at installations where wet flue-gas desulfurization (FGD) systems are employed. A key element of the proposal was FGS-PWN, a liquid-based mercury chelating agent, which can be employed as the amendment for removal of all mercury species which enter the wet-FGD scrubber. However, the equipment design presented in the proposal was inadequate to demonstrate these functions and no significant progress was made to substantiate these claims. As a result, funding for a Phase II continuation of this work will not be pursued. The key to implementing the technology as described in the proposal and report appears to be a high liquid-to-gas ratio (L/G) between the flue-gas and the scrubber liquor, a requirement not currently implemented in existing wet-FGD designs. It may be that this constraint can be reduced through parametric studies, but that was not apparent in this work. Unfortunately, the bench-scale system constructed for this project did not function as intended and the funds and time requested were exhausted before the separation studies could occur.

  4. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

    Berggren, M.H.; Jha, M.C.

    1989-10-01

    AMAX Research Development Center (AMAX R D) investigated methods for enhancing the reactivity and durability of zinc ferrite desulfurization sorbents. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For this program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such as size, strength, and specific surface area during 10 cycles of sulfidation and oxidation. Two base case sorbents, a spherical pellet and a cylindrical extrude used in related METC-sponsored projects, were used to provide a basis for the aimed enhancement in durability and reactivity. Sorbent performance was judged on the basis of physical properties, single particle kinetic studies based on thermogravimetric (TGA) techniques, and multicycle bench-scale testing of sorbents. A sorbent grading system was utilized to quantify the characteristics of the new sorbents prepared during the program. Significant enhancements in both reactivity and durability were achieved for the spherical pellet shape over the base case formulation. Overall improvements to reactivity and durability were also made to the cylindrical extrude shape. The primary variables which were investigated during the program included iron oxide type, zinc oxide:iron oxide ratio, inorganic binder concentration, organic binder concentration, and induration conditions. The effects of some variables were small or inconclusive. Based on TGA studies and bench-scale tests, induration conditions were found to be very significant.

  5. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    SciTech Connect

    John G. Verkade

    1997-08-31

    Remarkably mild conditions have been discovered for quantitative sulfur removal from dibenzothiophene and other organosulfur systems using relatively cheap elemental sodium. The project objectives are: (1) Optimize the coal desulfurization reaction with respect to time, temperature, coal type and the R groups (including R = H), and also on extraction, impregnation and sonication conditions; (2) Optimize the conditions for the HDS reaction (which allows the PR{sub 3} to function as an HDS catalyst for coal) with respect to R group, temperature, pressure, H{sub 2} gas flow rate and inert solvent presence; (3) Determine the product(s) and the pathway of the novel redox reaction that appears to quantitatively remove sulfur from dibenzothiophene (DBT) when R = Bu when FeCl{sub 3} is used as a catalyst; (4) Impregnate sulfur-laden coals with Fe{sup 3+} to ascertain if the PR{sub 3} desulfurization rate increases; (5) Determine the nature of the presently unextractable phosphorus compounds formed in solid coals by PR{sub 3}; (6) Explore the efficacy of PR{sub 3}/Fe{sup 3+} in removing sulfur from petroleum feedstocks, heavy ends (whether solid or liquid), coal tar and discarded tire rubber; (7) Explore the possibility of using water-soluble PR{sub 3} compounds and Fe{sup 3+} to remove sulfur from petroleum feedstocks and heavy ends in order to remove the SPR{sub 3} (and Fe{sup 3+} catalyst) by water extraction (for subsequent HDS of the SPR{sub 3}); and (8) Explore the possibility of using solid-supported PR{sub 3} compounds (plus Fe{sup 3+} catalyst) to remove sulfur from petroleum feedstocks and heavy ends in order to keep the oil and the SPR{sub 3} (formed in the reaction) in easily separable phases.

  6. Biocatalytic potential of vanillin aminotransferase from Capsicum chinense

    PubMed Central

    2014-01-01

    Background The conversion of vanillin to vanillylamine is a key step in the biosynthetic route towards capsaicinoids in pungent cultivars of Capsicum sp. The reaction has previously been annotated to be catalysed by PAMT (putative aminotransferase; [GenBank: AAC78480.1, Swiss-Prot: O82521]), however, the enzyme has previously not been biochemically characterised in vitro. Results The biochemical activity of the transaminase was confirmed by direct measurement of the reaction with purified recombinant enzyme. The enzyme accepted pyruvate, and oxaloacetate but not 2-oxoglutarate as co-substrate, which is in accordance with other characterised transaminases from the plant kingdom. The enzyme was also able to convert (S)-1-phenylethylamine into acetophenone with high stereo-selectivity. Additionally, it was shown to be active at a broad pH range. Conclusions We suggest PAMT to be renamed to VAMT (vanillin aminotransferase, abbreviation used in this study) as formation of vanillin from vanillylamine could be demonstrated. Furthermore, due to high stereoselectivity and activity at physiological pH, VAMT is a suitable candidate for biocatalytic transamination in a recombinant whole-cell system. PMID:24712445

  7. Effectiveness Factors and Conversion in a Biocatalytic Membrane Reactor.

    PubMed

    Godongwana, Buntu

    2016-01-01

    Analytical expressions of the effectiveness factor of a biocatalytic membrane reactor, and its asymptote as the Thiele modulus becomes large, are presented. The evaluation of the effectiveness factor is based on the solution of the governing equations for solute transport in the two regions of the reactor, i.e. the lumen and the matrix (with the biofilm immobilized in the matrix). The lumen solution accounts for both axial diffusion and radial convective flow, while the matrix solution is based on Robin-type boundary conditions. The effectiveness factor is shown to be a function of the Thiele modulus, the partition coefficient, the Sherwood number, the Peclet number, and membrane thickness. Three regions of Thiele moduli are defined in the effectiveness factor graphs. These correspond with reaction rate limited, internal-diffusion limited, and external mass transfer limited solute transport. Radial convective flows were shown to only improve the effectiveness factor in the region of internal diffusion limitation. The assumption of first order kinetics is shown to be applicable only in the Thiele modulus regions of internal and external mass transfer limitation. An iteration scheme is also presented for estimating the effectiveness factor when the solute fractional conversion is known. The model is validated with experimental data from a membrane gradostat reactor immobilised with Phanerochaete chrysosporium for the production of lignin and manganese peroxidases. The developed model and experimental data allow for the determination of the Thiele modulus at which the effectiveness factor and fractional conversion are optimal.

  8. Effectiveness Factors and Conversion in a Biocatalytic Membrane Reactor

    PubMed Central

    Godongwana, Buntu

    2016-01-01

    Analytical expressions of the effectiveness factor of a biocatalytic membrane reactor, and its asymptote as the Thiele modulus becomes large, are presented. The evaluation of the effectiveness factor is based on the solution of the governing equations for solute transport in the two regions of the reactor, i.e. the lumen and the matrix (with the biofilm immobilized in the matrix). The lumen solution accounts for both axial diffusion and radial convective flow, while the matrix solution is based on Robin-type boundary conditions. The effectiveness factor is shown to be a function of the Thiele modulus, the partition coefficient, the Sherwood number, the Peclet number, and membrane thickness. Three regions of Thiele moduli are defined in the effectiveness factor graphs. These correspond with reaction rate limited, internal-diffusion limited, and external mass transfer limited solute transport. Radial convective flows were shown to only improve the effectiveness factor in the region of internal diffusion limitation. The assumption of first order kinetics is shown to be applicable only in the Thiele modulus regions of internal and external mass transfer limitation. An iteration scheme is also presented for estimating the effectiveness factor when the solute fractional conversion is known. The model is validated with experimental data from a membrane gradostat reactor immobilised with Phanerochaete chrysosporium for the production of lignin and manganese peroxidases. The developed model and experimental data allow for the determination of the Thiele modulus at which the effectiveness factor and fractional conversion are optimal. PMID:27104954

  9. Biocatalytic nerve agent detoxification in fire fighting foams.

    PubMed

    LeJeune, K E; Russell, A J

    1999-03-20

    Current events across the globe necessitate rapid technological advances to combat the epidemic of nerve agent chemical weapons. Biocatalysis has emerged as a viable tool in the detoxification of organophosphorus neurotoxins, such as the chemical weapons VX and sarin. Efficient detoxification of contaminated equipment, machinery, and soils are of principal concern. This study describes the incorporation of a biocatalyst (organophosphorus hydrolase, E.C. 3.1.8.1) into conventional formulations of fire fighting foam. The capacity of fire fighting foams to decrease volatilization of contained contaminants, increase surface wettability, and control the rate of enzyme delivery to large areas makes them useful vehicles for enzyme application at surfaces. The performance of enzyme containing foams has been shown to be not only reproducible but also predictable. An empirical model provides reasonable estimations for the amounts of achievable surface decontamination as a function of the important parameters of the system. Theoretical modeling illustrates that the enzyme-containing foam is capable of extracting agent from the surface and is catalytically active at the foam-surface interface and throughout the foam itself. Biocatalytic foam has proven to be an effective, "environmentally friendly" means of surface and soil decontamination.

  10. Chitosan-based biocatalytic nanoparticles for pollutant removal from wastewater.

    PubMed

    Alarcón-Payán, Dulce A; Koyani, Rina D; Vazquez-Duhalt, Rafael

    2017-05-01

    Chitosan, a renewable biopolymer has the prospective applications in different fields due to its gelation capacity. Nanoconfiguration of chitosan through ionotropic gelation to encapsulate enzymatic activity offers numerous potential applications. In the present study, the preparation and characterization of chitosan nanoparticles loaded with versatile peroxidase are reported. Their performance in bioremediation process and the resistance enhancement against natural microbial biodegradation were studied. The average diameter of enzymatic nanoparticles was 120nm and showed a high enzyme loading capacity. The kinetic parameters of nanoparticles exhibited a slightly lower catalytic activity (kcat), similar affinity constant (Km) for hydrogen peroxide and higher Km value for the phenolic compound when compared with the free enzyme. The enzymatic nanoparticles showed higher thermostability and the same pH activity profile than those from free enzyme. Ten phenolic compounds, including pesticides, halogenated compounds, endocrine disruptors and antibacterials were transformed by the enzymatic nanoparticles. The transformation rate was lower than those obtained with free enzyme suggesting mass transfer limitations. But very importantly, the enzymatic nanoparticles showed a significant increase of the operational stability in real conditions of wastewater treatment process. Moreover, chemical modification of nanoparticles with different aldehydes still enhanced the operational stability of nanoparticulated enzymes. This enhancement of stability in real conditions and the potential use of biocatalytic nanoparticles in bioremediation processes are discussed.

  11. Flue gas desulfurization gypsum agricultural network alabama (cotton)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flue gas desulfurization gypsum (FGDG) is an excellent source of gypsum (CaSO4•2H2O) that can be beneficially used in agriculture. Research was conducted as part of the Flue Gas Desulfurization Gypsum Agricultural Network program sponsored by the Electric Power Research Institute in collaboration wi...

  12. [A method of desulfurization with calcium sulfite and it's mechanism].

    PubMed

    Tong, Z; Chen, Z; Peng, Z

    2001-09-01

    Directing to the scaling problem lying in wet desulfurization with lime slurry, a method of desulfurization with calcium sulfite was proposed. Reaction mechanism and the effects of different conditions on desulfurization efficiency were studied. The optimum conditions were obtained, i.e. air velocity of 2.75 m/s in empty tower, L/G = 3.0 L/m3, solid content 6.7%, air temperature 31 degrees C, concentration inlet of SO2 1500 x 10(-6) and inlet suspension pH of 8.0. Under the conditions, the desulfurization efficiency was about 87%. The presented method theoretically and practically solved the scaling problems, which is a novel indirect lime-method with Ca-contained material as desulfurization agent.

  13. Bench-scale development of mild gasification char desulfurization; [Quarterly] report, September 1--November 30, 1993

    SciTech Connect

    Knight, R.A.

    1994-03-01

    This goal of this project is to scale up a process, developed under a previous ICCI grant, for desulfurization of mild gasification char by treatment with hydrogen-rich process-derived fuel gas at 650{degree}--760{degree}C and 7-15 atm. The char can be converted into a low-sulfur metallurgical form coke. In the prior study, IBC-105 coal with 4.0 wt % sulfur was converted to chars with less than 1.0 wt % sulfur in a laboratory-scale batch reactor. The susceptibility of the char to desulfurization was correlated with physicochemical char properties and mild gasification conditions. Acid pretreatment of the coal prior to mild gasification was also shown to significantly enhance subsequent sulfur removal. In this study, IGT is conducting continuous bench-scale tests in a 1-lb/h fluidized-bed reactor to determine the preferred process conditions and obtain steady-state data necessary for process design and scale-up. The desulfurized chars are to be used to produce low-sulfur form coke, which will be evaluated for density, reactivity, and strength properties relevant to utilization in blast furnaces. During the first quarter, 180 lb (82 kg) of IBC-105 coal was obtained and subjected to crushing, and sizing to prepare 49 lb (22 kg) of material for test operation.

  14. Sorbent for use in hot gas desulfurization

    DOEpatents

    Gasper-Galvin, Lee D.; Atimtay, Aysel T.

    1993-01-01

    A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.

  15. Flue gas desulfurization wastewater treatment primer

    SciTech Connect

    Higgins, T.E.; Sandy, A.T.; Givens, S.W.

    2009-03-15

    Purge water from a typical wet flue gas desulfurization system contains myriad chemical constituents and heavy metals whose mixture is determined by the fuel source and combustion products as well as the stack gas treatment process. A well-designed water treatment system can tolerate upstream fuel and sorbent arranged in just the right order to produce wastewater acceptable for discharge. This article presents state-of-the-art technologies for treating the waste water that is generated by wet FGD systems. 11 figs., 3 tabs.

  16. Biocatalytic Conversion of Avermectin to 4"-Oxo-Avermectin: Characterization of Biocatalytically Active Bacterial Strains and of Cytochrome P450 Monooxygenase Enzymes and Their Genes

    PubMed Central

    Jungmann, Volker; Molnár, István; Hammer, Philip E.; Hill, D. Steven; Zirkle, Ross; Buckel, Thomas G.; Buckel, Dagmar; Ligon, James M.; Pachlatko, J. Paul

    2005-01-01

    4"-Oxo-avermectin is a key intermediate in the manufacture of the agriculturally important insecticide emamectin benzoate from the natural product avermectin. Seventeen biocatalytically active Streptomyces strains with the ability to oxidize avermectin to 4"-oxo-avermectin in a regioselective manner have been discovered in a screen of 3,334 microorganisms. The enzymes responsible for this oxidation reaction in these biocatalytically active strains were found to be cytochrome P450 monooxygenases (CYPs) and were termed Ema1 to Ema17. The genes for Ema1 to Ema17 have been cloned, sequenced, and compared to reveal a new subfamily of CYPs. Ema1 to Ema16 have been overexpressed in Escherichia coli and purified as His-tagged recombinant proteins, and their basic enzyme kinetic parameters have been determined. PMID:16269732

  17. Gas suspension absorption demonstrated for flue gas desulfurization

    SciTech Connect

    1994-03-01

    The first U.S. demonstration of gas suspension absorption (GSA), a flue gas desulfurization (FGD) technology developed in Europe, has been conducted at the Tennessee Valley Authority`s National Center for Emissions Research (NCER) in Paducah, Kentucky. The technology was developed by the Danish company FLS miljo a/s. GSA is an attractive FGD candidate technology because, unlike conventional wet scrubbing, GSA requires no chemical analyses as part of its routine operation and maintenance. The 10-MW GSA demonstration plant was constructed by AirPol, Inc. (Teterboro, New Jersey), a U.S. subsidiary of FLS miljo a/s. The project was partially funded by the U.S. Department of Energy (DOE) through its clean coal technology program. GSA technology and results of the demonstration project are discussed in this paper in brief. The factorial tests conducted on the GSA demonstration plant at NCER showed that, using a modest Ca/S ratio, the system can achieve high SO{sub 2} removal efficiencies, low particulate emissions, and a low-moisture solid waste by-product. 1 ref., 3 figs., 1 tab.

  18. Process for desulfurizing combustion exhaust gases

    SciTech Connect

    Kumagai, T.; Matsuda, S.; Mori, T.; Nishimura, T.; Nishimura, Y.

    1982-05-04

    An improved process for desulfurizing combustion exhaust gases of mainly coal containing sulfur oxides, Hf and dust containing Al is provided, which process consists of four steps; a first step of contacting the gases with calcium carbonate or hydroxide in the form of slurry to convert the sulfur oxides into caso3; a second step of contacting O2 with the resulting slurry to convert CaSo3 into caso4; a third step of separating caso4 and mother liquor from the resulting slurry; and a fourth step of preparing a slurry of calcium carbonate or hydroxide to be employed in the first step, from the mother liquor, the pHs of the slurry and the mother liquor in the first and fourth steps being adjusted to 5 or higher by adding alkali such as sodium carbonate. According to the present process, it is possible to prevent hindrance of hf and al contained in dust to the reaction of so2absorbent (CaCO3 or Ca(OH)2) with SO2 gas, and thereby improve percentage desulfurization and also obtain a high quality gypsum.

  19. Selenium speciation in flue desulfurization residues.

    PubMed

    Zhong, Liping; Cao, Yan; Li, Wenying; Xie, Kechang; Pan, Wei-Ping

    2011-01-01

    Flue gas from coal combustion contains significant amounts of volatile selenium (Se). The capture of Se in the flue gas desulfurization (FGD) scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se(IV), Se(VI) and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry (AFS). It has been determined that Se(IV), Se(VI) and organic Se can be accurately determined with detection limits (DL) of 0.05, 0.06 and 0.06 microg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite (Se(IV)). The toxicity of Se(IV) is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.

  20. Thermostabilization of desulfurization enzymes from Rhodococcos sp. IGTS8. Final technical report

    SciTech Connect

    John J. Kilbane II

    2000-12-15

    The objective of this project was to develop thermophilic cultures capable of expressing the desulfurization (dsz) operon of Rhodococcus sp. IGTS8. The approaches taken in this project included the development of plasmid and integrative expression vectors that function well in Thermus thermophilus, the cloning of Rhodococcus dsz genes in Thermus expression vectors, and the isolation of bacterial cultures that express the dsz operon at thermophilic temperatures. This project has resulted in the development of plasmid and integrative expression vectors for use in T. thermophilus. The dsz genes have been expressed at moderately thermophilic temperatures (52 C) in Mycobacterium phlei and at temperatures as high as 72 C in T. thermophilus. The tools and methods developed in this project will be generally useful for the expression of heterologous genes in Thermus. Key developments in the project have been the isolation of a Mycobacterium phlei culture capable of expressing the desulfurization operon at 52 C, development of plasmid and integrative expression vectors for Thermus thermophilus, and the development of a host-vector system based on the malate dehydrogenase gene that allows plasmids to be stably maintained in T. thermophilus and provides a convenient reporter gene for the accurate quantification of gene expression. Publications have been prepared regarding each of these topics; these preprints are included.

  1. Shawnee flue gas desulfurization computer model users manual

    SciTech Connect

    Sudhoff, F.A.; Torstrick, R.L.

    1985-03-01

    In conjunction with the US Enviromental Protection Agency sponsored Shawnee test program, Bechtel National, Inc., and the Tennessee Valley Authority jointly developed a computer model capable of projecting preliminary design and economics for lime- and limestone-scrubbing flue gas desulfurization systems. The model is capable of projecting relative economics for spray tower, turbulent contact absorber, and venturi-spray tower scrubbing options. It may be used to project the effect on system design and economics of variations in required SO/sub 2/ removal, scrubber operating parameters (gas velocity, liquid-to-gas (L/G) ration, alkali stoichiometry, liquor hold time in slurry recirculation tanks), reheat temperature, and scrubber bypass. It may also be used to evaluate alternative waste disposal methods or additives (MgO or adipic acid) on costs for the selected process. Although the model is not intended to project the economics of an individual system to a high degree of accuracy, it allows prospective users to quickly project comparative design and costs for limestone and lime case variations on a common design and cost basis. The users manual provides a general descripton of the Shawnee FGD computer model and detailed instructions for its use. It describes and explains the user-supplied input data which are required such as boiler size, coal characteristics, and SO/sub 2/ removal requirments. Output includes a material balance, equipment list, and detailed capital investment and annual revenue requirements. The users manual provides information concerning the use of the overall model as well as sample runs to serve as a guide to prospective users in identifying applications. The FORTRAN-based model is maintained by TVA, from whom copies or individual runs are available. 25 refs., 3 figs., 36 tabs.

  2. Environmental significance of biocatalytic conversion of low grade oils

    SciTech Connect

    Lin, M.S.; Premuzic, E.T.; Lian, H.; Zhou, W.M.; Yablon, J.

    1996-09-01

    Studies dealing with the interactions between extremophilic microorganisms and crude oils have led to the identification of biocatalysts which through multiple biochemical reactions catalyze desulfurization, denitrogenation, and demetalation reactions in oils. Concurrently, the oils are also converted to lighter oils. These complex biochemical reactions have served as models in the development of the crude oil bioconversion technology to be applied prior to the treatment of oils by conventional chemical processes. In practical terms, this means that the efficiency of the existing technology is being enhanced. For example, the recently introduced additional regulation for the emission of nitrogen oxides in some states restricts further the kinds of oils that may be used in burners. The biocatalysts being developed in this laboratory selectively interact with nitrogen compounds, i.e. basic and neutral types present in the oil and, hence, affect the fuel NOx production. This, in turn, has a cost-efficient influence on the processed oils and their consumption. In this paper, these cost-efficient and beneficial effects will be discussed in terms of produced oils, the lowering of sulfur and nitrogen contents, and the effect on products, as well as the longevity of catalysts due to the removal of heteroatoms and metal containing compounds found in crudes.

  3. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2003-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeOn (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD analysis showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit full desulfurization testing. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that may be exposed to low concentrations of H{sub 2}S are constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time is determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations (<{approx}10 ppmv) and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, have been obtained. Much of the work during year 02 consisted of

  4. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Anirban Mukherjee; Elizabeth J. Podlaha; Douglas P. Harrison

    2004-03-01

    Mixed metal oxides containing ceria and zirconia have been studied as high temperature desulfurization sorbents with the objective of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S in the product gas. The research was justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeOn (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and was postulated to have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} mixtures was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD analysis showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit desulfurization testing. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that were exposed to low concentrations of H{sub 2}S were constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time was determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations from approximately 0.1 to 10 ppmv, and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, were obtained

  5. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2002-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeO{sub n} (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit full testing in our desulfurization reactor. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that may be exposed to low concentrations of H{sub 2}S are constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time is determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations ({approx}< 10 ppmv) and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, have been obtained. Characterization and desulfurization

  6. Plane flame furnace combustion tests on JPL desulfurized coal

    NASA Technical Reports Server (NTRS)

    Reuther, J. J.; Kim, H. T.; Lima, J. G. H.

    1982-01-01

    The combustion characteristics of three raw bituminous (PSOC-282 and 276) and subbituminous (PSOC-230) coals, the raw coals partially desulfurized (ca -60%) by JPL chlorinolysis, and the chlorinated coals more completely desulfurized (ca -75%) by JPL hydrodesulfurization were determined. The extent to which the combustion characteristics of the untreated coals were altered upon JPL sulfur removal was examined. Combustion conditions typical of utility boilers were simulated in the plane flame furnace. Upon decreasing the parent coal voltaile matter generically by 80% and the sulfur by 75% via the JPL desulfurization process, ignition time was delayed 70 fold, burning velocity was retarded 1.5 fold, and burnout time was prolonged 1.4 fold. Total flame residence time increased 2.3 fold. The JPL desulfurization process appears to show significant promise for producing technologically combustible and clean burning (low SO3) fuels.

  7. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Anirban Mukherjee; Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2001-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv of less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeO{sub n} (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} has been developed and the products have been characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} have been prepared. XRD showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Phase separation did not occur when the solid solutions were heat treated at 700 C. A flow reactor system constructed of quartz and teflon has been constructed, and a gas chromatograph equipped with a pulsed flame photometric detector (PFPD) suitable for measuring sub-ppmv levels of H{sub 2}S has been purchased with LSU matching funds. Preliminary desulfurization tests using commercial CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} in highly reducing gas compositions has confirmed that CeO{sub 2}-ZrO{sub 2} is more effective than CeO{sub 2} in removing H{sub 2}S. At 700 C the product H{sub 2}S concentration using CeO{sub 2}-ZrO{sub 2} sorbent was near the 0.1 ppmv PFPD detection limit during the prebreakthrough period.

  8. Pore structure and reactivity changes in hot coal gas desulfurization sorbents. Final report, September 1987--January 1991

    SciTech Connect

    Sotirchos, S.V.

    1991-05-01

    The primary objective of the project was the investigation of the pore structure and reactivity changes occurring in metal/metal oxide sorbents used for desulfurization of hot coal gas during sulfidation and regeneration, with particular emphasis placed on the effects of these changes on the sorptive capacity and efficiency of the sorbents. Commercially available zinc oxide sorbents were used as model solids in our experimental investigation of the sulfidation and regeneration processes.

  9. Olefins can limit desulfurization of reformer feedstock

    SciTech Connect

    Ali, S.A.; Anabtawi, J.A.

    1995-07-03

    Pilot plant studies have shown that the presence of even very small amounts of olefins may limit the desulfurization of reformer feedstocks to trace levels. Engineers at the Research Institute of King Fahd University of Petroleum and Minerals observed under typical industrial conditions the recombination reaction of olefins with hydrogen sulfide to form mercaptans. The results indicate that the advantage of using highly active (third generation) CoMo hydrotreating catalysts can be masked by these reactions if the olefins are not saturated. The trend in naphtha reforming is to use high-rhenium, bimetallic catalysts that display less resistance to sulfur than do balanced Pt-Re catalysts. Due consideration, therefore, should be given to these undesirable recombination reactions while designing hydrotreaters and selecting hydrodesulfurization (HDS) and reforming catalysts. The paper discusses catalysts and feedstock tests, catalyst activity, temperature effects, space velocity, feedstock effect, catalyst performance, and recommendations.

  10. Flue gas desulfurization method and apparatus

    DOEpatents

    Madden, Deborah A.; Farthing, George A.

    1998-08-18

    A combined furnace limestone injection and dry scrubber flue gas desulfurization (FGD) system collects solids from the flue gas stream in first particulate collection device located downstream of an outlet of a convection pass of the furnace and upstream of the dry scrubber. The collected solids are diverted to the dry scrubber feed slurry preparation system to increase sulfur oxide species removal efficiency and sorbent utilization. The level of lime in the feed slurry provided to the dry scrubber is thus increased, which enhances removal of sulfur oxide species in the dry scrubber. The decreased particulate loading to the dry scrubber helps maintain a desired degree of free moisture in the flue gas stream entering the dry scrubber, which enhances sulfur oxide species removal both in the dry scrubber and downstream particulate collector, normally a baghouse.

  11. Flue gas desulfurization method and apparatus

    DOEpatents

    Madden, Deborah A.; Farthing, George A.

    1998-09-29

    A combined furnace limestone injection and dry scrubber flue gas desulfurization (FGD) system collects solids from the flue gas stream in first particulate collection device located downstream of an outlet of a convection pass of the furnace and upstream of the dry scrubber. The collected solids are diverted to the dry scrubber feed slurry preparation system to increase sulfur oxide species removal efficiency and sorbent utilization. The level of lime in the feed slurry provided to the dry scrubber is thus increased, which enhances removal of sulfur oxide species in the dry scrubber. The decreased particulate loading to the dry scrubber helps maintain a desired degree of free moisture in the flue gas stream entering the dry scrubber, which enhances sulfur oxide species removal both in the dry scrubber and downstream particulate collector, normally a baghouse.

  12. Flue gas desulfurization method and apparatus

    DOEpatents

    Madden, D.A.; Farthing, G.A.

    1998-08-18

    A combined furnace limestone injection and dry scrubber flue gas desulfurization (FGD) system collects solids from the flue gas stream in first particulate collection device located downstream of an outlet of a convection pass of the furnace and upstream of the dry scrubber. The collected solids are diverted to the dry scrubber feed slurry preparation system to increase sulfur oxide species removal efficiency and sorbent utilization. The level of lime in the feed slurry provided to the dry scrubber is thus increased, which enhances removal of sulfur oxide species in the dry scrubber. The decreased particulate loading to the dry scrubber helps maintain a desired degree of free moisture in the flue gas stream entering the dry scrubber, which enhances sulfur oxide species removal both in the dry scrubber and downstream particulate collector, normally a baghouse. 5 figs.

  13. Flue gas desulfurization method and apparatus

    DOEpatents

    Madden, D.A.; Farthing, G.A.

    1998-09-29

    A combined furnace limestone injection and dry scrubber flue gas desulfurization (FGD) system collects solids from the flue gas stream in first particulate collection device located downstream of an outlet of a convection pass of the furnace and upstream of the dry scrubber. The collected solids are diverted to the dry scrubber feed slurry preparation system to increase sulfur oxide species removal efficiency and sorbent utilization. The level of lime in the feed slurry provided to the dry scrubber is thus increased, which enhances removal of sulfur oxide species in the dry scrubber. The decreased particulate loading to the dry scrubber helps maintain a desired degree of free moisture in the flue gas stream entering the dry scrubber, which enhances sulfur oxide species removal both in the dry scrubber and downstream particulate collector, normally a baghouse. 5 figs.

  14. Limestone-gypsum flue gas desulfurization process

    SciTech Connect

    Kuroda, H.; Hashimoto, T.; Kanda, O.; Nishimura, M.; Nishimura, T.; Nozawa, S.

    1984-12-11

    A flue gas desulfurization process capable of producing a high purity gypsum and also making equipment employed as minimum as possible is provided, which process comprises the steps of cooling and dedusting flue gas containing SO /SUB x/ ; contacting the cooled gas with a slurry containing limestone to remove SO /SUB x/ by absorption and also form CaSO/sub 3/; controlling the pH of the resulting slurry and then blowing air therein to form gypsum; and separating gypsum from the resulting slurry. As a modification of the above process, the slurry of the above second absorption step is further fed to the above first cooling step where unreacted limestone and SO /SUB x/ are reacted to form CaSO/sub 3/.

  15. Ductwork: Materials of construction for flue gas desulfurization systems

    SciTech Connect

    O`Donnell, R.J.; Khederian, J.C.; Martin, J.E.; Watson, W.K.

    1995-09-01

    This paper identifies the ductwork materials required for the various service conditions in the wet limestone flue gas desulfurization system (FGDS) at Indianapolis Power and Light Company`s (IPL) Petersburg Units 1 and 2. This project was initiated by IPL in response to the Clean Air Act Amendments (CAAA) of 1990 and is intended to treat the flue gas from two base-loaded units with a combined capacity of approximately 700 MW gross electrical output. The flue gas conditions include hot unscrubbed gas (bypass), hot unscrubbed gas mixed with cool ambient air (normal), a mixing zone of gas only/air only associated with an open bypass system (no damper), and cool, wet scrubbed gas (outlet ducts). In addition, there are upset conditions associated with the loss of an air preheater. This system is somewhat unique, in that each unit has its own separate open or undampered bypass system, including separate stack liners. While a separate bypass system eliminates the extremely severe corrosion problems associated with mixing unscrubbed gas and scrubbed gas in a common bypass flue, it does create potential problems mixing cool ambient air with hot flue gas.

  16. DEVELOPMENT OF ADVANCED HOT-GAS DESULFURIZATION PROCESSES

    SciTech Connect

    K. Jothimurugesan; Santosh K. Gangwal

    2000-12-01

    The techniques employed in this project have successfully demonstrated the feasibility of preparing sorbents that achieve greater than 99% H{sub 2}S removal at temperatures 480 C and that retain their activity over 50 cycles. Fundamental understanding of phenomena leading to chemical deactivation and high regeneration light-off temperature has enabled us to successfully prepare and scale up a FHR-32 sorbent that showed no loss in reactivity and capacity over 50 cycles. This sorbent removed H{sub 2}S below 80 ppmv and lighted-off nicely at 480 C during regeneration. Overall the test is a success with potential for an optimized FHR-32 to be a candidate for Sierra-Pacific. An advanced attrition resistant hot-gas desulfurization sorbent that can eliminate the problematic SO{sub 2} tail gas and yield elemental sulfur directly has been developed. Attrition resistant Zn-Fe sorbent (AHI-2) formulations have been prepared that can remove H{sub 2}S to below 20 ppmv from coal gas and can be regenerated using SO{sub 2} to produce elemental sulfur.

  17. Economic assessment of advanced flue gas desulfurization processes. Final report

    SciTech Connect

    Bierman, G. R.; May, E. H.; Mirabelli, R. E.; Pow, C. N.; Scardino, C.; Wan, E. I.

    1981-09-01

    This report presents the results of a project sponsored by the Morgantown Energy Technology Center (METC). The purpose of the study was to perform an economic and market assessment of advanced flue gas desulfurization (FGD) processes for application to coal-fired electric utility plants. The time period considered in the study is 1981 through 1990, and costs are reported in 1980 dollars. The task was divided into the following four subtasks: (1) determine the factors affecting FGD cost evaluations; (2) select FGD processes to be cost-analyzed; (3) define the future electric utility FGD system market; and (4) perform cost analyses for the selected FGD processes. The study was initiated in September 1979, and separate reports were prepared for the first two subtasks. The results of the latter two subtasks appear only in this final reprot, since the end-date of those subtasks coincided with the end-date of the overall task. The Subtask 1 report, Criteria and Methods for Performing FGD Cost Evaluations, was completed in October 1980. A slightly modified and condensed version of that report appears as appendix B to this report. The Subtask 2 report, FGD Candidate Process Selection, was completed in January 1981, and the principal outputs of that subtask appear in Appendices C and D to this report.

  18. Developing clean fuels: Novel techniques for desulfurization

    NASA Astrophysics Data System (ADS)

    Nehlsen, James P.

    The removal of sulfur compounds from petroleum is crucial to producing clean burning fuels. Sulfur compounds poison emission control catalysts and are the source of acid rain. New federal regulations require the removal of sulfur in both gasoline and diesel to very low levels, forcing existing technologies to be pushed into inefficient operating regimes. New technology is required to efficiently produce low sulfur fuels. Two processes for the removal of sulfur compounds from petroleum have been developed: the removal of alkanethiols by heterogeneous reaction with metal oxides; and oxidative desulfurization of sulfides and thiophene by reaction with sulfuric acid. Alkanethiols, common in hydrotreated gasoline, can be selectively removed and recovered from a hydrocarbon stream by heterogeneous reaction with oxides of Pb, Hg(II), and Ba. The choice of reactive metal oxides may be predicted from simple thermodynamic considerations. The reaction is found to be autocatalytic, first order in water, and zero order in thiol in the presence of excess oxide. The thiols are recovered by reactive extraction with dilute oxidizing acid. The potential for using polymer membrane hydrogenation reactors (PEMHRs) to perform hydrogenation reactions such as hydrodesulfurization is explored by hydrogenating ketones and olefins over Pt and Au group metals. The dependence of reaction rate on current density suggests that the first hydrogen addition to the olefin is the rate limiting step, rather than the adsorption of hydrogen, for all of the metals tested. PEMHRs proved unsuccessful in hydrogenating sulfur compounds to perform HDS. For the removal of sulfides, a two-phase reactor is used in which concentrated sulfuric acid oxidizes aromatic and aliphatic sulfides present in a hydrocarbon solvent, generating sulfoxides and other sulfonated species. The polar oxidized species are extracted into the acid phase, effectively desulfurizing the hydrocarbon. A reaction scheme is proposed for this

  19. High Contacting Efficience Carrier Structures & Porcesses for Liquid Phase Regenerable Desulfurization of Logistic Fuels

    DTIC Science & Technology

    2011-02-21

    Phase Regenerable Desulfurization of Logistic Fuels 5a. CONTRACT NUMBER Sb. GRANT NUMBER N00014-06-1-1165 6c. PROGRAM ELEMENT NUMBER 6. AUTHOR...developed and characterized. The adsorbent’s formulation, preparation procedure, desulfurization conditions and regeneration procedure have established and...enables novel process design for the logistic fuel desulfurization . 15. SUBJECT TERMS desulfurization , liquid fuel, silver, titania 16. SECURITY

  20. Spectroscopic and biocatalytic properties of a chlorophyll-containing extract in silica gel

    NASA Astrophysics Data System (ADS)

    Lipke, Agnieszka; Trytek, Mariusz; Fiedurek, Jan; Majdan, Marek; Janik, Ewa

    2013-11-01

    UV-Vis absorption and fluorescence spectra of chlorophyll a (in the form of spinach extract) in acetone solution and in silica gel showed a predominance of pigment dimers in its overall concentration and an evident transformation of chlorophyll a to pheophytin with time. The dimerization constant of chlorophyll a in acetone was log Kdim = 2.14, whereas the constants for chlorophyll a and pheophytin a in alcogel were log Kdim = 4.70 and log Kdim = 5.22, respectively. Biocatalytic experiments indicated the possibility of using the pigment embedded in silica gel, i.e. mainly its dimeric form, for biotransformation of α-pinene to pinocarveyl hydroperoxide, trans-pinocarveol, pinocarvone and myrtenal. The advantage of a heterogeneous biocatalytic system (composed of a solvent and silica gel) over a homogeneous system (single phase of chloroform) is the possibility of reusing the biocatalyst with about 10% preservation of its activity.

  1. Biocatalytic Synthesis of Chiral Alcohols and Amino Acids for Development of Pharmaceuticals

    PubMed Central

    Patel, Ramesh N.

    2013-01-01

    Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates and drugs has become increasingly important in the pharmaceutical industry. There has been an increasing awareness of the enormous potential of microorganisms and enzymes derived there from for the transformation of synthetic chemicals with high chemo-, regio- and enatioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral alcohols and unntural aminoacids for pharmaceuticals. PMID:24970190

  2. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS

    SciTech Connect

    G. Blythe; B. Marsh; S. Miller; C. Richardson; M. Richardson

    2001-06-01

    The U.S. Department of Energy and EPRI have co-funded this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project investigated catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems and to future FGD installations. Field tests have been conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit has been used to test the activity of four different catalyst materials for a period of up to six months at each of three utility sites. Catalyst testing was completed at the first site, which fires Texas lignite, in December 1998 and at the second test site, which fires a Powder River Basin subbituminous coal in the fall of 1999. Testing at the third site, which fires a medium- to high-sulfur bituminous coal, began in June 2000 and was completed at the end of January 2001. This Topical Reports includes results from Site 3; results from Sites 1 and 2 were reported previously. At Site 3, catalysts were tested in two forms, including powders dispersed in sand bed reactors and in a commercially available form as a coated honeycomb structure. Field testing has been supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and methods for regenerating spent catalysts. Laboratory results related to the Site 3 field effort are also included and discussed in this Topical Report.

  3. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS

    SciTech Connect

    Unknown

    2001-06-01

    The U.S. Department of Energy and EPRI co-funded this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project has investigated catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems, and to future FGD installations. Field tests were conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit was used to test the activity of four different catalyst materials for a period of up to six months each at three utility sites. Catalyst testing was completed at the first site, which fires Texas lignite, in December 1998; at the second test site, which fires a Powder River Basin subbituminous coal, in November 1999; and at the third site, which fires a medium- to high-sulfur bituminous coal, in January 2001. Results of testing at each of the three sites were reported in previous technical notes. At Site 1, catalysts were tested only as powders dispersed in sand bed reactors. At Sites 2 and 3, catalysts were tested in two forms, including powders dispersed in sand and in commercially available forms such as extruded pellets and coated honeycomb structures. This final report summarizes and presents results from all three sites, for the various catalyst forms tested. Field testing was supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and methods for regenerating spent catalysts. Laboratory results are also summarized and discussed in this report.

  4. Recent achievements in developing the biocatalytic toolbox for chiral amine synthesis.

    PubMed

    Kohls, Hannes; Steffen-Munsberg, Fabian; Höhne, Matthias

    2014-04-01

    Novel enzyme activities and chemoenzymatic reaction concepts have considerably expanded the biocatalytic toolbox for chiral amine synthesis. Creating new activities or extending the scope of existing enzymes by protein engineering is a common trend in biocatalysis and in chiral amine synthesis specifically. For instance, an amine dehydrogenase that allows for the direct asymmetric amination of ketones with ammonia was created by mutagenesis of an l-amino acid dehydrogenase. Another trend in chiral amine chemistry is the development of strategies allowing for the synthesis of secondary amines. For example the smart choice of substrates for amine transaminases provided access to secondary amines by chemoenzymatic reactions. Furthermore novel biocatalysts for the synthesis of secondary amines such as imine reductases and Pictet-Spenglerases have been identified and applied. Recent examples showed that the biocatalytic amine synthesis is emerging from simple model reactions towards industrial scale preparation of pharmaceutical relevant substances, for instance, as shown in the synthesis of a Janus kinase 2 inhibitor using an amine transaminase. A comparison of important process parameters such as turnover number and space-time yield demonstrates that biocatalytic strategies for asymmetric reductive amination are maturing and can already compete with established chemical methods.

  5. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    SciTech Connect

    John G. Verkade

    2001-11-01

    Column chromatographic separation of the S=PBu{sub 3}/PBu{sub 3} product mixture followed by weighing the S=PBu{sub 3}, and by vacuum distillation of S=PBu{sub 3}/PBu{sub 3}mixture followed by gas chromatographic analysis are described. Effects of coal mesh size, pre-treatment with methanol Coal (S) + excess PR{sub 3} {yields} Coal + S=PR{sub 3}/PBu{sub 3} and sonication on sulfur removal by PBu{sub 3} revealed that particle size was not observed to affect desulfurization efficiency in a consistent manner. Coal pretreatment with methanol to induce swelling or the addition of a filter aid such as Celite reduced desulfurization efficiency of the PBu{sub 3} and sonication was no more effective than heating. A rationale is put forth for the lack of efficacy of methanol pretreatment of the coal in desulfurization runs with PBu{sub 3}. Coal desulfurization with PBu{sub 3} was not improved in the presence of miniscule beads of molten lithium or sodium as a desulfurizing reagent for SPBu{sub 3} in a strategy aimed at regenerating PBu{sub 3} inside coal pores. Although desulfurization of coals did occur in sodium solutions in liquid ammonia, substantial loss of coal mass was also observed. Of particular concern is the mass balance in the above reaction, a problem which is described in some detail. In an effort to solve this difficulty, a specially designed apparatus is described which we believe can solve this problem reasonably effectively. Elemental sodium was found to remove sulfur quantitatively from a variety of polycyclic organosulfur compounds including dibenzothiophene and benzothiophene under relatively mild conditions (150 C) in a hydrocarbon solvent without requiring the addition of a hydrogen donor. Lithium facilitates the same reaction at a higher temperature (254 C). Mechanistic pathways are proposed for these transformations. Curiously, dibenzothiophene and its corresponding sulfone was virtually quantitatively desulfurized in sodium solutions in liquid

  6. Flue gas desulfurization: Physicochemical and biotechnological approaches

    SciTech Connect

    Pandey, R.A.; Biswas, R.; Chakrabarti, T.; Devotta, S.

    2005-07-01

    Various flue gas desulfurization processes - physicochemical, biological, and chemobiological - for the reduction of emission of SO{sub 2} with recovery of an economic by-product have been reviewed. The physicochemical processes have been categorized as 'once-through' and 'regenerable.' The prominent once-through technologies include wet and dry scrubbing. The wet scrubbing technologies include wet limestone, lime-inhibited oxidation, limestone forced oxidation, and magnesium-enhanced lime and sodium scrubbing. The dry scrubbing constitutes lime spray drying, furnace sorbent injection, economizer sorbent injection, duct sorbent injection, HYPAS sorbent injection, and circulating fluidized bed treatment process. The regenerable wet and dry processes include the Wellman Lord's process, citrate process, sodium carbonate eutectic process, magnesium oxide process, amine process, aqueous ammonia process, Berglau Forchung's process, and Shell's process. Besides these, the recently developed technologies such as the COBRA process, the OSCAR process, and the emerging biotechnological and chemobiological processes are also discussed. A detailed outline of the chemistry, the advantages and disadvantages, and the future research and development needs for each of these commercially viable processes is also discussed.

  7. Method for operating a flue gas desulfurization

    SciTech Connect

    Karger, R.; Weinzierl, K.

    1983-02-01

    A method of operating a flue gas desulfurization with a steam power plant heated with fossil fuels. The sulfur dioxide contained in the flue gas is removed in a wash tower by means of an excess of milk of lime or limestone, and the resulting sulfite is oxidized with air at a low ph-value into calcium sulfate. The non-converted milk of lime or limestone is neutralized at least partially by an addition of acid waste waters from a complete desalination plant for the supply water, and/or by an addition of acid condensate from the flue or chimney of the steam power plant. An installation for carrying out the method of the present invention includes a wash tower having flue gas flowing therethrough, an oxidation tower having air flowing therethrough, milk of lime or limestone supply into the wash tower, and a delivery device for the wash liquid in the wash tower and in the oxidation tower, with the device having a pump for liquid drawn off from the sump of the wash tower. The sump of the wash tower is connected with a supply line for acid waste water from a complete desalination plant, and/or with a supply line for acid condensate from the chimney or flue of the steam power plant.

  8. Coal desulfurization by low temperature chlorinolysis, phase 3

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Rohatgi, N. K.; Ernest, J.

    1981-01-01

    Laboratory scale, bench scale batch reactor, and minipilot plant tests were conducted on 22 bituminous, subbituminous, and lignite coals. Chemical pretreatment and post treatment of coals relative to the chlorination were tried as a means of enhancing desulfurization by the chlorinolysis process. Elevated temperature (500-700 C) hydrogen treatment of chlorinolysis-processed coal at atmospheric pressure was found to substantially increase coal desulfurization up to 90 percent. Sulfur forms, proximate and ultimate analyses of the processed coal are included. Minipilot plant operation indicates that the continuous flow reactor provides coal desulfurization results comparable to those obtained in the batch reactor. Seven runs were conducted at coal feed rates of 1.5 to 8.8 kg per hour using water and methylchloroform solvents, gaseous chlorine feed of 3 to 31.4 SCFH at 21 to 70 C, and atmospheric pressure for retention times of 20 to 120 minutes.

  9. Ultrasonic coal-wash for de-sulfurization.

    PubMed

    Ambedkar, B; Nagarajan, R; Jayanti, S

    2011-05-01

    Coal is the one of the world's most abundant fossil fuel resources. It is not a clean fuel, as it contains ash and sulfur. SOx as a pollutant are a real threat to both the ecosystem and to human health. There are numerous de-sulfurization methods to control SO(2) emissions. Nowadays, online flue gas de-sulfurization is being used as one such method to remove sulfur from coal during combustion. The biggest disadvantage associated with this method is formation of by-products (FGD gypsum). A way for effective usage of FGD gypsum has not yet been found. This will lead to acute and chronic effects to humans as well as plants. Power ultrasound can be used for the beneficiation of coal by the removal of sulfur from coal prior to coal combustion. The main effects of ultrasound in liquid medium are acoustic cavitation and acoustic streaming. The process of formation, growth and implosion of bubbles is called cavitation. Bulk fluid motion due to sound energy absorption is known as acoustic streaming. In addition, coupling of an acoustic field to water produces OH radicals, H(2)O(2), O(2), ozone and HO(2) that are strong oxidizing agents. Oxidation that occurs due to ultrasound is called Advanced Oxidation Process (AOP). It converts sulfur from coal to water-soluble sulphates. Conventional chemical-based soaking and stirring methods are compared here to ultrasonic methods of de-sulfurization. The main advantages of ultrasonic de-sulfurization over conventional methods, the mechanism involved in ultrasonic de-sulfurization and the difference between aqueous-based and solvent-based (2N HNO(3), 3-volume percentage H(2)O(2)) de-sulfurization are investigated experimentally.

  10. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

    Jha, M.C.; Baltich, L.K.

    1987-02-23

    AMAX Research Development Center (AMAX R D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such As size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  11. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

    Silaban, A.; Harrison, D.P. . Dept. of Chemical Engineering)

    1989-05-02

    AMAX Research Development Center (AMAX R D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such as size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  12. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

    Jha, M.C.; Berggren, M.H.

    1989-05-02

    AMAX Research Development Center (AMAX R D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such As size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  13. Control of thiosulfate in wet desulfurization process solutions

    SciTech Connect

    Castrantas, H.M.

    1983-01-04

    A method for controlling the concentration of dissolved thiosulfate byproduct which forms in a wet desulfurization process, by introducing a peroxygen chemical into its recirculating aqueous absorption medium. A peroxygen chemical such as aqueous hydrogen peroxide is introduced into the recirculating aqueous alkaline absorption medium, preferably after its regeneration, in an amount sufficient to maintain the concentration of thiosulfate byproduct below a saturation concentration. The method is applicable to cyclic wet desulfurization processes, used to recover elemental sulfur from H/sub 2/S-containing gas streams, in which the absorption medium contains a regenerable oxidizing agent and is subject to thiosulfate byproduct buildup.

  14. NON-EQUAL REACTIVITY MODEL FOR BIOCATALYTIC POLYTRANSESTERIFICATION. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  15. Bench-scale demonstration of hot-gas desulfurization technology. Quarterly report, October 1 - December 31, 1995

    SciTech Connect

    1995-12-31

    The US Department of Energy (DOE) Morgantown Energy Technology Center (METC) is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal gas) streams of integrated gasification combined-cycle (IGCC) power systems. The programs focus on hot-gas particulate removal and desulfurization technologies that match or nearly match the temperatures and pressures of the gasifier, cleanup system, and power generator. The work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs. The goal of this project is to continue further development of the zinc titanate desulfurization and direct sulfur recovery process (DSRP) technologies by (1) scaling up the zinc titanate reactor system; (2) developing an integrated skid-mounted zinc titanate desulfurization-DSRP reactor system; (3) testing the integrated system over an extended period with real coal-gas from an operating gasifier to quantify the degradative effect, if any, of the trace contaminants present in coal gas; (4) developing an engineering database suitable for system scaleup; and (5) designing, fabricating and commissioning a larger DSRP reactor system capable of operating on a six-fold greater volume of gas than the DSRP reactor used in the bench-scale field test. The work performed during the October 1 through December 31, 1995 is described.

  16. Enhanced durability of high-temperature desulfurization sorbents for fluidized-bed applications. [Zinc titanate

    SciTech Connect

    Gupta, R.P.; Gangwal, S.K.

    1992-01-01

    The objectives of this project are to identify and demonstrate methods for enhancing long-term chemical reactivity and attrition resistance of zinc ferrite and zinc titanate sorbents to be employed for desulfurization of hot coal-derived gases in a high-temperature, high-pressure (HTHP) fluid-bed reactor. The sorbent formulation specified for study during the base period of this project was zinc ferrite. Zinc titanate sorbents are being studied under two options to the base contract. Specific objectives of the zinc titanate sorbent development work are the following: The effect of following process variables was investigated o the performance of zinc titanate sorbents: Method of sorbent preparation, Composition of fuel gas, Zn to Ti ratio of the sorbent, Sulfidation temperature, and Superficial gas velocity. The effect of first three variables has been covered in RTI's 1991 paper (Gupta and Gangwal, 1991b), while the effect of temperature and superficial gas velocity is described here.

  17. Enhanced durability of high-temperature desulfurization sorbents for fluidized-bed applications

    SciTech Connect

    Gupta, R.P.; Gangwal, S.K.

    1992-11-01

    The objectives of this project are to identify and demonstrate methods for enhancing long-term chemical reactivity and attrition resistance of zinc ferrite and zinc titanate sorbents to be employed for desulfurization of hot coal-derived gases in a high-temperature, high-pressure (HTHP) fluid-bed reactor. The sorbent formulation specified for study during the base period of this project was zinc ferrite. Zinc titanate sorbents are being studied under two options to the base contract. Specific objectives of the zinc titanate sorbent development work are the following: The effect of following process variables was investigated o the performance of zinc titanate sorbents: Method of sorbent preparation, Composition of fuel gas, Zn to Ti ratio of the sorbent, Sulfidation temperature, and Superficial gas velocity. The effect of first three variables has been covered in RTI`s 1991 paper (Gupta and Gangwal, 1991b), while the effect of temperature and superficial gas velocity is described here.

  18. Desulfurization of coal by microbial column flotation.

    PubMed

    Ohmura, N; Saiki, H

    1994-06-05

    Twenty-three strains capable of oxidizing iron were isolated from coal and ore storage sites as well as coal and ore mines, volcanic areas, and hot spring. Four strains were found to have high iron-oxidizing activity. One strain (T-4) was selected for this experiment since the strain showed the fastest leaching rate of iron and sulfate from pyrite among the four strains. The T-4 strain was assigned for Thiobacillus ferrooxidans from its cultural and morphological characteristics.Bacterial treatment was applied to column flotation. An increase of cell density in the microbial column flotation resulted in the increase of pyrite removal from a coal-pyrite mixture (high sulfur imitated coal) with corresponding decrease of coal recovery. The addition of kerosene into the microbial column flotation increased the recovery of the imitated coal from 55% (without kerosene) to 81% (with 50 microL/L kerosene) with the reduction of pyrite sulfur content from 11% (feed coal) to 3.9% (product coal). The kerosene addition could reduce the pyritic sulfur content by collecting the coal in the recovery. However, the addition could not enhance separation of pyrite from the coal-pyrite mixture, since pyrite rejection was not affected by the increase of the kerosene addition. An excellent separation was obtained by the microbial flotation using a long column which had a length-diameter (L/D) ratio of 12.7. The long column flotation reduced the pyritic sulfur content from 11% (feed coal) to 1.8% (product coal) when 80% of the feed coal was recovered without the kerosene addition. The long column flotation not only attained an excellent separation but also reduced the amount of cells for desulfurization to as little as one-tenth of the reported amount.

  19. Flue gas desulfurization by rotating beds

    SciTech Connect

    Gardner, N.; Keyvani, M.; Coskundeniz, A.

    1992-01-01

    The operating and mass transfer characteristics of rotating foam metal beds were studied to determine the potential for flue gas desulfurization. This is a final technical report on the work supported by DOE [number sign]FG22-87-PC79924. The report is divided into two sections, Part 1 deals primarily with the operating characteristics of rotating beds, and Part 2 covers the mass transfer characteristics of S0[sub 2] absorption in water-lime slurries. Rotating foam metal beds are in essence packed towers operated in high gravitational fields. The foam metal bed is in the form of a cylindrical donut, or torus, and is rotated to produced the high centrifugal forces. The liquid phase enters the bed at the inner surface of the torus and is pulled by the field through the bed. Gas flows countercurrent to the liquid. The bed packing can have a very large specific surface areas and not flood. Possible benefits include much smaller height of a transfer unit resulting in smaller equipment and supporting structures, reduced solvent inventory, faster response with improved process control, reduced pressure drop, and shorter startup and shut-down times. This work is concerned broadly with the operating characteristics of rotating beds, the objectives being to (1) determine the pressure drop through the rotating bed; (2) determine the power required to operate the beds, (3) investigate the residence time distribution of the liquid phase in the beds; and (4) determine the mass transfer coefficients of S0[sub 2] absorption. Three packings of differing specific surface areas were studied, with areas ranging from 656 to 2952 m[sub 2]/m[sub 3]. Liquid flow rates to 36 kg/s*m[sub 2], gas flow rate to 2.2 kg/s*m[sub 2], and gravitational fields to 300 g were covered in this study.

  20. IHI in-line type flue gas desulfurization system

    SciTech Connect

    Yamaguchi, F.; Kanamori, A.; Fujino, Y.

    1995-06-01

    Desulfurization systems are indispensable for reducing air pollution caused by flue gas from power plants. It is essential that the cost for constructing and operating such systems is low. IHI has developed such a system based on its expertise gathered over the years. The test results and outline of the system are presented in this paper.

  1. Effect of Flue Gas Desulfurization Waste on Corn Plants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flue gas desulfurization gypsum (FGDG) is a by-product of conversion of sulfur dioxide into solid waste from coal combustion power generation plant. This by-product is rich in calcium, magnesium, and contains various other essential plant nutrients. The beneficial use of application of this waste as...

  2. FLUE GAS DESULFURIZATION: THE STATE OF THE ART

    EPA Science Inventory

    The paper gives results of a review of commercially available flue gas desulfurization (FGD) technologies that have an established record of full-scale performance. (NOTE: Sulfur dioxide (SO2) scrubbers may be used by coal-fired electrcity generating units to meet the requiremen...

  3. CURRENT STATUS OF ADVACATE PROCESS FOR FLUE GAS DESULFURIZATION

    EPA Science Inventory

    The following report discusses current bench- and pilot-plant advances in preparation of ADVAnced siliCATE (ADVACATE) calcium silicate sorbentsfor flue gas desulfurization. It also discusses current bench- and pilot-plant advances in sorbent preparation. Fly ash was ground in a l...

  4. Core-in-shell sorbent for hot coal gas desulfurization

    DOEpatents

    Wheelock, Thomas D.; Akiti, Jr., Tetteh T.

    2004-02-10

    A core-in-shell sorbent is described herein. The core is reactive to the compounds of interest, and is preferably calcium-based, such as limestone for hot gas desulfurization. The shell is a porous protective layer, preferably inert, which allows the reactive core to remove the desired compounds while maintaining the desired physical characteristics to withstand the conditions of use.

  5. Workshop on sulfur chemistry in flue gas desulfurization

    SciTech Connect

    Wallace, W.E. Jr.

    1980-05-01

    The Flue Gas Desulfurization Workshop was held at Morgantown, West Virginia, June 7-8, 1979. The presentations dealt with the chemistry of sulfur and calcium compounds in scrubbers. DOE and EPRI programs in this area are described. Ten papers have been entered individually into EDB and ERA. (LTN)

  6. Fluorescent signaling of oxone by desulfurization of thioamide.

    PubMed

    Eor, Suyoung; Hwang, Jiyoung; Choi, Myung Gil; Chang, Suk-Kyu

    2011-02-04

    The chemosignaling of the oxidant Oxone by selective desulfurization of a thioamide was investigated. Pyrene-thioamide was efficiently converted to its amide analogue by reaction with Oxone, resulting in a pronounced fluorescent turn-on type signaling. Selective signaling of Oxone in aqueous solution was possible in the presence of representative alkali and alkaline earth metal ions, as well as common anions.

  7. Effect of operating parameters and reactor structure on moderate temperature dry desulfurization

    SciTech Connect

    Jie Zhang; Changfu You; Haiying Qi; Bo Hou; Changhe Chen; Xuchang Xu

    2006-07-01

    A moderate temperature dry desulfurization process at 600-800 C was studied in a pilot-scale circulating fluidized bed flue gas desulfurization (CFB-FGD) experimental facility. The desulfurization efficiency was investigated for various operating parameters. Structural improvements in key parts of the CFB-FGD system, i.e., the cyclone separator and the distributor, were made to improve the desulfurization efficiency and flow resistance. The experimental results show that the desulfurization efficiency increased rapidly with increasing temperature above 600 C due to enhanced gas diffusion and the shift of the equilibrium for the carbonate reaction. The sorbent sulfated gradually after quick carbonation of the sorbent with a long particle residence time necessary to realize a high desulfurization ratio. A reduced solids concentration in the bed reduced the particle residence time and the desulfurization efficiency. A single-stage cyclone separator produced no improvement in the desulfurization efficiency compared with a two-stage cyclone separator. Compared with a wind cap distributor, a large hole distributor reduced the flow resistance which reduced the desulfurization efficiency due to the reduced bed pressure drop and worsened bed fluidization. The desulfurization efficiency can be improved by increasing the collection efficiency of fine particles to prolong their residence time and by improving the solids concentration distribution to increase the gas-solid contact surface area. 16 refs., 9 figs.

  8. Effect of operating parameters and reactor structure on moderate temperature dry desulfurization.

    PubMed

    Zhang, Jie; You, Changfu; Qi, Haiying; Hou, Bo; Chen, Changhe; Xu, Xuchang

    2006-07-01

    A moderate temperature dry desulfurization process at 600-800 degrees C was studied in a pilot-scale circulating fluidized bed flue gas desulfurization (CFB-FGD) experimental facility. The desulfurization efficiency was investigated for various operating parameters, such as bed temperature, CO2 concentration, and solids concentration. In addition, structural improvements in key parts of the CFB-FGD system, i.e., the cyclone separator and the distributor, were made to improve the desulfurization efficiency and flow resistance. The experimental results show that the desulfurization efficiency increased rapidly with increasing temperature above 600 degrees C due to enhanced gas diffusion and the shift of the equilibrium for the carbonate reaction. The sorbent sulfated gradually after quick carbonation of the sorbent with a long particle residence time necessary to realize a high desulfurization ratio. A reduced solids concentration in the bed reduced the particle residence time and the desulfurization efficiency. A single-stage cyclone separator produced no improvement in the desulfurization efficiency compared with a two-stage cyclone separator. Compared with a wind cap distributor, a large hole distributor reduced the flow resistance which reduced the desulfurization efficiency due to the reduced bed pressure drop and worsened bed fluidization. The desulfurization efficiency can be improved by increasing the collection efficiency of fine particles to prolong their residence time and by improving the solids concentration distribution to increase the gas-solid contact surface area.

  9. Bioinformatic analysis of a PLP-dependent enzyme superfamily suitable for biocatalytic applications.

    PubMed

    Steffen-Munsberg, Fabian; Vickers, Clare; Kohls, Hannes; Land, Henrik; Mallin, Hendrik; Nobili, Alberto; Skalden, Lilly; van den Bergh, Tom; Joosten, Henk-Jan; Berglund, Per; Höhne, Matthias; Bornscheuer, Uwe T

    2015-01-01

    In this review we analyse structure/sequence-function relationships for the superfamily of PLP-dependent enzymes with special emphasis on class III transaminases. Amine transaminases are highly important for applications in biocatalysis in the synthesis of chiral amines. In addition, other enzyme activities such as racemases or decarboxylases are also discussed. The substrate scope and the ability to accept chemically different types of substrates are shown to be reflected in conserved patterns of amino acids around the active site. These findings are condensed in a sequence-function matrix, which facilitates annotation and identification of biocatalytically relevant enzymes and protein engineering thereof.

  10. Chemotherapy pro-drug activation by biocatalytic virus-like nanoparticles containing cytochrome P450.

    PubMed

    Sánchez-Sánchez, Lorena; Cadena-Nava, Rubén D; Palomares, Laura A; Ruiz-Garcia, Jaime; Koay, Melissa S T; Cornelissen, Jeroen J M T; Vazquez-Duhalt, Rafael

    2014-06-10

    This work shows, for the first time, the encapsulation of a highly relevant protein in the biomedical field into virus-like particles (VLPs). A bacterial CYP variant was effectively encapsulated in VLPs constituted of coat protein from cowpea chlorotic mottle virus (CCMV). The catalytic VLPs are able to transform the chemotherapeutic pro-drug, tamoxifen, and the emerging pro-drug resveratrol. The chemical nature of the products was identified, confirming similar active products than those obtained with human CYP. The enzymatic VLPs remain stable after the catalytic reaction. The potential use of these biocatalytic nanoparticles as targeted CYP carriers for the activation of chemotherapy drugs is discussed.

  11. DEEP DESULFURIZATION OF DIESEL FUELS BY A NOVEL INTEGRATED APPROACH

    SciTech Connect

    Xiaoliang Ma; Michael Sprague; Lu Sun; Chunshan Song

    2002-10-01

    In order to reduce the sulfur level in liquid hydrocarbon fuels for environmental protection and fuel cell applications, deep desulfurization of a model diesel fuel and a real diesel fuel was conducted by our SARS (selective adsorption for removing sulfur) process using the adsorbent A-2. Effect of temperature on the desulfurization process was examined. Adsorption desulfurization at ambient temperature, 24 h{sup -1} of LHSV over A-2 is efficient to remove dibenzothiophene (DBT) in the model diesel fuel, but difficult to remove 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT). Adsorption desulfurization at 150 C over A-2 can efficiently remove DBT, 4-MDBT and 4,6-DMDBT in the model diesel fuel. The sulfur content in the model diesel fuel can be reduced to less than 1 ppmw at 150 C without using hydrogen gas. The adsorption capacity corresponding to the break-through point is 6.9 milligram of sulfur per gram of A-2 (mg-S/g-A-2), and the saturate capacity is 13.7 mg-S/g-A-2. Adsorption desulfurization of a commercial diesel fuel with a total sulfur level of 47 ppmw was also performed at ambient temperature and 24 h{sup -1} of LHSV over the adsorbent A-2. The results show that only part of the sulfur compounds existing in the low sulfur diesel can be removed by adsorption over A-2 at such operating conditions, because (1) the all sulfur compounds in the low sulfur diesel are the refractory sulfur compounds that have one or two alkyl groups at the 4- and/or 6-positions of DBT, which inhibit the approach of the sulfur atom to the adsorption site; (2) some compounds coexisting in the commercial low sulfur diesel probably inhibit the interaction between the sulfur compounds and the adsorbent. Further work in determining the optimum operating conditions and screening better adsorbent is desired.

  12. Desulfurization ability of refining slag with medium basicity

    NASA Astrophysics Data System (ADS)

    Yu, Hui-xiang; Wang, Xin-hua; Wang, Mao; Wang, Wan-jun

    2014-12-01

    The desulfurization ability of refining slag with relative lower basicity ( B) and Al2O3 content ( B = 3.5-5.0; 20wt%-25wt% Al2O3) was studied. Firstly, the component activities and sulfide capacity ( C S) of the slag were calculated. Then slag-metal equilibrium experiments were carried out to measure the equilibrium sulfur distribution ( L S). Based on the laboratorial experiments, slag composition was optimized for a better desulfurization ability, which was verified by industrial trials in a steel plant. The obtained results indicated that an MgO-saturated CaO-Al2O3-SiO2-MgO system with the basicity of about 3.5-5.0 and the Al2O3 content in the range of 20wt%-25wt% has high activity of CaO ( a CaO), with no deterioration of C S compared with conventional desulfurization slag. The measured L S between high-strength low-alloyed (HSLA) steel and slag with a basicity of about 3.5 and an Al2O3 content of about 20wt% and between HSLA steel and slag with a basicity of about 5.0 and an Al2O3 content of about 25wt% is 350 and 275, respectively. The new slag with a basicity of about 3.5-5.0 and an Al2O3 content of about 20wt% has strong desulfurization ability. In particular, the key for high-efficiency desulfurization is to keep oxygen potential in the reaction system as low as possible, which was also verified by industrial trials.

  13. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    PubMed

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  14. Biocatalytic virus capsid as nanovehicle for enzymatic activation of Tamoxifen in tumor cells.

    PubMed

    Tapia-Moreno, Alejandro; Juarez-Moreno, Karla; Gonzalez-Davis, Oscar; Cadena-Nava, Ruben D; Vazquez-Duhalt, Rafael

    2017-04-03

    Most of the drugs used in chemotherapy should be activated by a transformation catalyzed by cytochrome P450 (CYP) enzymes. In this work, bacteriophage P22 virus-like particles (VLPs) containing CYP activity, immunologically inert and functionalized in order to be recognized by human cervix carcinoma cells and human breast adenocarcinoma cells were designed. The CYP was encapsulated inside the virus capsid obtained from the bacteriophage P22. CYP and coat protein were both heterologously expressed in E. coli. The VLPs with enzymatic activity were covered with polyethylene glycol that was functionalized in its distal end with folic acid in order to be recognized by folate receptors exhibited on tumor cells. The capacity of biocatalytic VLPs to be recognized and internalized into tumor cells is demonstrated. The VLP-treated cells showed enhanced capacity for the transformation of the pro-drug tamoxifen, which resulted in an increase of the cell sensitivity to this oncological drug. In this work, the potential use of biocatalytic VLPs vehicles as a delivery system of medical relevant enzymes is clearly demonstrated. In addition to cancer treatment, this technology also offers an interesting platform as nano-bioreactors for intracellular delivery of enzymatic activity for other diseases originated by the lack of enzymatic activity.

  15. A robust methodology for kinetic model parameter estimation for biocatalytic reactions.

    PubMed

    Al-Haque, Naweed; Santacoloma, Paloma A; Neto, Watson; Tufvesson, Pär; Gani, Rafiqul; Woodley, John M

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches. The parameter estimation problem is decomposed into five hierarchical steps, where the solution of each of the steps becomes the input for the subsequent step to achieve the final model with the corresponding regressed parameters. The model is further used for validating its performance and determining the correlation of the parameters. The final model with the fitted parameters is able to describe both initial rate and dynamic experiments. Application of the methodology is illustrated with a case study using the ω-transaminase catalyzed synthesis of 1-phenylethylamine from acetophenone and 2-propylamine.

  16. Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin-Catalyzed Doyle-Kirmse Reaction.

    PubMed

    Tyagi, Vikas; Sreenilayam, Gopeekrishnan; Bajaj, Priyanka; Tinoco, Antonio; Fasan, Rudi

    2016-10-17

    The first example of a biocatalytic [2,3]-sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle-Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C-C bond-forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl-, benzyl-, and alkyl-substituted allylic sulfides) and α-diazo esters. Moreover, the scope of this myoglobin-mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active-site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle-Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon-carbon bonds.

  17. Sequential lignin depolymerization by combination of biocatalytic and formic acid/formate treatment steps.

    PubMed

    Gasser, Christoph A; Čvančarová, Monika; Ammann, Erik M; Schäffer, Andreas; Shahgaldian, Patrick; Corvini, Philippe F-X

    2017-03-01

    Lignin, a complex three-dimensional amorphous polymer, is considered to be a potential natural renewable resource for the production of low-molecular-weight aromatic compounds. In the present study, a novel sequential lignin treatment method consisting of a biocatalytic oxidation step followed by a formic acid-induced lignin depolymerization step was developed and optimized using response surface methodology. The biocatalytic step employed a laccase mediator system using the redox mediator 1-hydroxybenzotriazole. Laccases were immobilized on superparamagnetic nanoparticles using a sorption-assisted surface conjugation method allowing easy separation and reuse of the biocatalysts after treatment. Under optimized conditions, as much as 45 wt% of lignin could be solubilized either in aqueous solution after the first treatment or in ethyl acetate after the second (chemical) treatment. The solubilized products were found to be mainly low-molecular-weight aromatic monomers and oligomers. The process might be used for the production of low-molecular-weight soluble aromatic products that can be purified and/or upgraded applying further downstream processes.

  18. Recent advances on halohydrin dehalogenases-from enzyme identification to novel biocatalytic applications.

    PubMed

    Schallmey, Anett; Schallmey, Marcus

    2016-09-01

    Halohydrin dehalogenases are industrially relevant enzymes that catalyze the reversible dehalogenation of vicinal haloalcohols with formation of the corresponding epoxides. In the reverse reaction, also other negatively charged nucleophiles such as azide, cyanide, or nitrite are accepted besides halides to open the epoxide ring. Thus, novel C-N, C-C, or C-O bonds can be formed by halohydrin dehalogenases, which makes them attractive biocatalysts for the production of various β-substituted alcohols. Despite the fact that only five individual halohydrin dehalogenase enzyme sequences have been known until recently enabling their heterologous production, a large number of different biocatalytic applications have been reported using these enzymes. The recent characterization of specific sequence motifs has facilitated the identification of novel halohydrin dehalogenase sequences available in public databases and has largely increased the number of recombinantly available enzymes. These will help to extend the biocatalytic repertoire of this enzyme family and to foster novel biotechnological applications and developments in the future. This review gives a general overview on the halohydrin dehalogenase enzyme family and their biochemical properties and further focuses on recent developments in halohydrin dehalogenase biocatalysis and protein engineering.

  19. Mechanistic and kinetic studies of high-temperature coal gas desulfurization sorbents

    SciTech Connect

    Lew, S.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

    1991-10-01

    The overall objective of this project was to investigate the properties of and evaluate mixed oxides of zinc and titanium for hot fuel gas desulfurization. Uncombined ZnO was also investigated as a base case. Detailed investigation of the reduction and sulfidation reactions of Zn-Ti-O sorbents was performed. The intrinsic kinetics and the product layer diffusion rates in reduction and sulfidation were determined. Kinetic experiments with sorbents containing various Zn/Ti atomic ratios were performed. Chemical phase and structural transformations were followed by various methods. The results were compared to similar experiments performed with ZnO. The purpose of these experiments was to determine how the presence of titanium dioxide affects the reduction and sulfidation of ZnO. This information would be used to identify and select the sorbent composition that gives the best combination of low reduction rate and acceptable sulfidation performance at temperatures exceeding 600{degree}C. (VC)

  20. Analysis of Flue Gas Desulfurization (FGD) Processes for Potential Use on Army Coal-Fired Boilers

    DTIC Science & Technology

    1980-09-01

    TECHNICAL REPORT N-93 September 1980 ANALYSIS OF FLUE GAS DESULFURIZATION (FGD) PROCESSES FOR POTENTIAL USE ON ARMY COAL-FIRED BOILERS TECHNICAL LIBRARY...REFERENCE: Technical Report N-93, Analysis of Flue Gas Desulfurization (FGD) Ppooesses for Potential Use on Army Coal-Fired Boilers Please take a few...REPORT DOCUMENTATION PAGE 1. REPORT NUMBER CERL-TR-N-93 2. GOVT ACCESSION NO «. TITLE (end Subtitle) ANALYSIS OF FLUE GAS DESULFURIZATION (FGD

  1. Bench-scale demonstration of hot-gas desulfurization technology. Quarterly technical progress report, October 1--December 31, 1993

    SciTech Connect

    Not Available

    1994-04-01

    Research Triangle Institute (RTI) with DOE/METC sponsorship has been developing zinc titanate sorbent technology since 1986. In addition, RTI has been developing the Direct Sulfur Recovery Process (DSRP) with DOE/METC sponsorship since 1988. Fluidized-bed zinc titanate desulfurization coupled to the DSRP is currently the most advanced and attractive technology for sulfur removal/recovery for IGCC systems, and it has recently been proposed in a Clean Coal Technology project. The goal of this project is to continue further development of the zinc titanate desulfurization and DSRP technologies by: scaling up the zinc titanate reactor system; developing an integrated skid-mounted zinc titanate desulfurization-DSRP reactor system; testing the integrated system over an extended period with real coal-gas from an operating gasifier to quantify the degradative effect, if any, of the trace contaminants present in coal gas; developing an engineering database suitable for system scaleup; and designing, fabricating and commissioning a larger DSRP reactor system capable of operating on a six-fold greater volume of gas than the DSRP reactor used in the bench-scale field test. During this reporting period the Construction Permit Application was completed and approved by the Process Safety Committee, and a final revised Application has been submitted to DOE/METC. A draft Test Plan for the field test was formulated. Finally, progress was made in the reactor system fabrication with the submission of purchase orders for nearly all major equipment, and with the final design of the trailer (mobile laboratory).

  2. Unraveling heavy oil desulfurization chemistry: targeting clean fuels.

    PubMed

    Choudhary, Tushar V; Parrott, Stephen; Johnson, Byron

    2008-03-15

    The sulfur removal chemistry of heavy oils has been unraveled by systematically investigating several heavy oils with an extremely wide range of properties. The heavy oil feed and product properties have been characterized by advanced analytical methods, and these properties have been related to the sulfur conversion data observed in pilot hydrotreating units. These studies coupled with kinetic treatment of the data have revealed that the desulfurization chemistry of heavy oils is essentially controlled by the strongly inhibiting three and larger ring aromatic hydrocarbon content and surprisingly not by the content of the "hard-to-remove" sulfur compounds. Such enhanced understanding of the heavy oil sulfur removal is expected to open new avenues for catalyst/process optimization for heavy oil desulfurization and thereby assist the efficent production of clean transporation fuels.

  3. Exploring the Mechanism of Biocatalyst Inhibition in Microbial Desulfurization

    PubMed Central

    Abin-Fuentes, Andres; Mohamed, Magdy El-Said; Wang, Daniel I. C.

    2013-01-01

    Microbial desulfurization, or biodesulfurization (BDS), of fuels is a promising technology because it can desulfurize compounds that are recalcitrant to the current standard technology in the oil industry. One of the obstacles to the commercialization of BDS is the reduction in biocatalyst activity concomitant with the accumulation of the end product, 2-hydroxybiphenyl (HBP), during the process. BDS experiments were performed by incubating Rhodococcus erythropolis IGTS8 resting-cell suspensions with hexadecane at 0.50 (vol/vol) containing 10 mM dibenzothiophene. The resin Dowex Optipore SD-2 was added to the BDS experiments at resin concentrations of 0, 10, or 50 g resin/liter total volume. The HBP concentration within the cytoplasm was estimated to decrease from 1,100 to 260 μM with increasing resin concentration. Despite this finding, productivity did not increase with the resin concentration. This led us to focus on the susceptibility of the desulfurization enzymes toward HBP. Dose-response experiments were performed to identify major inhibitory interactions in the most common BDS pathway, the 4S pathway. HBP was responsible for three of the four major inhibitory interactions identified. The concentrations of HBP that led to a 50% reduction in the enzymes' activities (IC50s) for DszA, DszB, and DszC were measured to be 60 ± 5 μM, 110 ± 10 μM, and 50 ± 5 μM, respectively. The fact that the IC50s for HBP are all significantly lower than the cytoplasmic HBP concentration suggests that the inhibition of the desulfurization enzymes by HBP is responsible for the observed reduction in biocatalyst activity concomitant with HBP generation. PMID:24096431

  4. Mass Transfer Model of Desulfurization in the Electroslag Remelting Process

    NASA Astrophysics Data System (ADS)

    Hou, Dong; Jiang, Zhou-Hua; Dong, Yan-Wu; Li, Yang; Gong, Wei; Liu, Fu-Bin

    2017-02-01

    Experimental and theoretical studies have been carried out to investigate the effects of the slag on desulfurization during the electroslag remelting (ESR) process with a focus of developing a mass transfer model to understand the mechanism of desulfurization. Stainless steel 1Cr21Ni5Ti was used as the electrode and remelted with two different kinds of slags using a 50-kg ESR furnace. The contents of sulfur along the axial direction of product ingots were analyzed. It was found that the sulfur content of 350 ppm in the electrode is reduced to 71 to 95 ppm in the ingot by remelting with the slag containing 5 wt pct of CaO, and lowered more to 47 to 59 ppm with another slag having 20 wt pct CaO. On the basis of the penetration and film theories, the theoretical model developed in this work well elucidates the kinetics of desulfurization revealing the mechanism of sulfur transfer during the ESR process. The calculation results obtained from the model agree well with the experimental results. The model indicates that when sulfur content in electrode is given, there is a corresponding minimum value of sulfur content in the ingot due to the kinetics limit. This lowest sulfur content cannot be further reduced even with increasing L S (sulfur distribution coefficient between metal and slag phases) or decreasing sulfur content in the slag. Constant addition of extra amount of CaO to the molten slag with the increase of sulfur content in the slag during the remelting process can improve the macrosegregation of sulfur distributed along the axial direction of ESR ingots. Since the rate-determining steps of the sulfur mass transfer lie in the metal phase, adding calcium as deoxidizer can change mass transfer of sulfur and thus promote desulfurization further during the ESR process.

  5. Numerical simulation of flow in the wet scrubber for desulfurization

    NASA Astrophysics Data System (ADS)

    Novosád, Jan; Vít, Tomáš

    2015-05-01

    This article deals with numerical simulation of flow and chemical reactions in absorber for desulfurization of flue-gas. The objective of the work is the investigation of effect of different nozzles types and their placement in spray layers. These nozzles distribute lime suspension into flue gas stream. The research includes two types of nozzles and four different arrangements of nozzles and spray layers. Conclusion describes the effect of nozzle types and their arrangements on the suspension concentration in absorber.

  6. Unusual chemical compounds in flue gas desulfurization systems

    SciTech Connect

    Dille, E.R.

    1996-08-01

    Flue gas desulfurization (FGD) systems continue to have deposits formed on internal surfaces of the materials of which the FGD systems are fabricated. These compounds contribute to crevice corrosion of the alloys of which some of the FGD systems are made. In the process of performing the failure analysis of the FGD fabrication materials, new compounds were discovered. This paper discusses two corrosion failure analysis case histories and the new compounds that were discovered and the chemical environment in which they were discovered.

  7. The mechanism of coal gas desulfurization by iron oxide sorbents.

    PubMed

    Lin, Yi-Hsing; Chen, Yen-Chiao; Chu, Hsin

    2015-02-01

    This study aims to understand the roles of hydrogen and carbon monoxide during the desulfurization process in a coal gasification system that H2S of the syngas was removed by Fe2O3/SiO2 sorbents. The Fe2O3/SiO2 sorbents were prepared by incipient wetness impregnation. Through the breakthrough experiments and Fourier transform infrared spectroscopy analyses, the overall desulfurization mechanism of the Fe2O3/SiO2 sorbents was proposed in this study. The results show that the major reaction route is that Fe2O3 reacts with H2S to form FeS, and the existence of CO and H2 in the simulated gas significantly affects equilibrium concentrations of H2S and COS. The formation of COS occurs when the feeding gas is blended with CO and H2S, or CO2 and H2S. The pathways in the formation of products from the desulfurization process by the reaction of Fe2O3 with H2S have been successfully established.

  8. Molecular biological enhancement of coal desulfurization. Final report

    SciTech Connect

    Krawiec, S.

    1994-12-31

    During the period from 1986 through 1993 the prospect of bacterial desulfurization of fossil fuel was transformed from a theoretically appealing concept to a demonstrable laboratory phenomenon. Results from several laboratories confirmed that there was not one but, rather, several metabolic bases of selectively removing sulfur from the carbon frame of sulfur-containing organic compounds characteristic of fossil fuels. Results in this report relate solely to the so-called ``4S`` pathway (named for the four sulfur-containing compounds in the sequence: (l) dibenzothiophene [DBT] {yields} (2) dibenzothiophene sulfoxide [DBTO] {yields} (3) dibenzosulfone [DBTO{sup 2}] {yields} (4) dibenzosulfonate {yields} monohydroxybiphenyl [OH-BP] + SO{sub 4}{sup =}. [An additional desulfurized product, biphenyl, has been hypothesized and another, o,o{prime}-biphenyl, observed.]) The following subjects are discussed: isolating bacteria with a DbtS{sup +} phenotype; confirming the production of a desulfurized product; determining the identity of the isolates; determining the growth characteristics of the isolates in batch and continuous cultures; determining the kinetics and yields of product in batch and continuous cultures.

  9. Two-stage coal gasification and desulfurization apparatus

    DOEpatents

    Bissett, Larry A.; Strickland, Larry D.

    1991-01-01

    The present invention is directed to a system which effectively integrates a two-stage, fixed-bed coal gasification arrangement with hot fuel gas desulfurization of a first stream of fuel gas from a lower stage of the two-stage gasifier and the removal of sulfur from the sulfur sorbent regeneration gas utilized in the fuel-gas desulfurization process by burning a second stream of fuel gas from the upper stage of the gasifier in a combustion device in the presence of calcium-containing material. The second stream of fuel gas is taken from above the fixed bed in the coal gasifier and is laden with ammonia, tar and sulfur values. This second stream of fuel gas is burned in the presence of excess air to provide heat energy sufficient to effect a calcium-sulfur compound forming reaction between the calcium-containing material and sulfur values carried by the regeneration gas and the second stream of fuel gas. Any ammonia values present in the fuel gas are decomposed during the combustion of the fuel gas in the combustion chamber. The substantially sulfur-free products of combustion may then be combined with the desulfurized fuel gas for providing a combustible fluid utilized for driving a prime mover.

  10. Biocatalytic self-assembly of nanostructured peptide microparticles using droplet microfluidics.

    PubMed

    Bai, Shuo; Debnath, Sisir; Gibson, Kirsty; Schlicht, Barbara; Bayne, Lauren; Zagnoni, Michele; Ulijn, Rein V

    2014-01-29

    Uniformly-sized, nanostructured peptide microparticles are generated by exploiting the ability of enzymes to serve (i) as catalysts, to control self-assembly within monodisperse, surfactant-stabilized water-in-oil microdroplets, and (ii) as destabilizers of emulsion interfaces, to enable facile transfer of the produced microparticles to water. This approach combines the advantages of biocatalytic self-assembly with the compartmentalization properties enabled by droplet microfluidics. Firstly, using microfluidic techniques, precursors of self-assembling peptide derivatives and enzymes are mixed in the microdroplets which upon catalytic conversion undergo molecular self-assembly into peptide particles, depending on the chemical nature of the precursors. Due to their amphiphilic nature, enzymes adsorb at the water-surfactant-oil interface of the droplets, inducing the transfer of peptide microparticles from the oil to the aqueous phase. Ultimately, through washing steps, enzymes can be removed from the microparticles which results in uniformely-sized particles composed of nanostructured aromatic peptide amphiphiles.

  11. Biocatalytic Characterization of Human FMO5: Unearthing Baeyer-Villiger Reactions in Humans.

    PubMed

    Fiorentini, Filippo; Geier, Martina; Binda, Claudia; Winkler, Margit; Faber, Kurt; Hall, Mélanie; Mattevi, Andrea

    2016-04-15

    Flavin-containing mono-oxygenases are known as potent drug-metabolizing enzymes, providing complementary functions to the well-investigated cytochrome P450 mono-oxygenases. While human FMO isoforms are typically involved in the oxidation of soft nucleophiles, the biocatalytic activity of human FMO5 (along its physiological role) has long remained unexplored. In this study, we demonstrate the atypical in vitro activity of human FMO5 as a Baeyer-Villiger mono-oxygenase on a broad range of substrates, revealing the first example to date of a human protein catalyzing such reactions. The isolated and purified protein was active on diverse carbonyl compounds, whereas soft nucleophiles were mostly non- or poorly reactive. The absence of the typical characteristic sequence motifs sets human FMO5 apart from all characterized Baeyer-Villiger mono-oxygenases so far. These findings open new perspectives in human oxidative metabolism.

  12. Bubble-Free Propulsion of Ultrasmall Tubular Nanojets Powered by Biocatalytic Reactions

    PubMed Central

    2016-01-01

    The motion of self-propelled tubular micro- and nanojets has so far been achieved by bubble propulsion, e.g., O2 bubbles formed by catalytic decomposition of H2O2, which renders future biomedical applications inviable. An alternative self-propulsion mechanism for tubular engines on the nanometer scale is still missing. Here, we report the fabrication and characterization of bubble-free propelled tubular nanojets (as small as 220 nm diameter), powered by an enzyme-triggered biocatalytic reaction using urea as fuel. We studied the translational and rotational dynamics of the nanojets as functions of the length and location of the enzymes. Introducing tracer nanoparticles into the system, we demonstrated the presence of an internal flow that extends into the external fluid via the cavity opening, leading to the self-propulsion. One-dimensional nanosize, longitudinal self-propulsion, and biocompatibility make the tubular nanojets promising for future biomedical applications. PMID:27718566

  13. Bubble-Free Propulsion of Ultrasmall Tubular Nanojets Powered by Biocatalytic Reactions.

    PubMed

    Ma, Xing; Hortelao, Ana C; Miguel-López, Albert; Sánchez, Samuel

    2016-10-26

    The motion of self-propelled tubular micro- and nanojets has so far been achieved by bubble propulsion, e.g., O2 bubbles formed by catalytic decomposition of H2O2, which renders future biomedical applications inviable. An alternative self-propulsion mechanism for tubular engines on the nanometer scale is still missing. Here, we report the fabrication and characterization of bubble-free propelled tubular nanojets (as small as 220 nm diameter), powered by an enzyme-triggered biocatalytic reaction using urea as fuel. We studied the translational and rotational dynamics of the nanojets as functions of the length and location of the enzymes. Introducing tracer nanoparticles into the system, we demonstrated the presence of an internal flow that extends into the external fluid via the cavity opening, leading to the self-propulsion. One-dimensional nanosize, longitudinal self-propulsion, and biocompatibility make the tubular nanojets promising for future biomedical applications.

  14. Biocatalytic synthesis of acrylates in supercritical fluids: tuning enzyme activity by changing pressure.

    PubMed Central

    Kamat, S V; Iwaskewycz, B; Beckman, E J; Russell, A J

    1993-01-01

    Supercritical fluids are a unique class of nonaqueous media in which biocatalytic reactions can occur. The physical properties of supercritical fluids, which include gas-like diffusivities and liquid-like densities, can be predictably controlled with changing pressure. This paper describes how adjustment of pressure, with the subsequent predictable changes of the dielectric constant and Hildebrand solubility parameter for fluoroform, ethane, sulfur hexafluoride, and propane, can be used to manipulate the activity of lipase in the transesterification of methylmethacrylate with 2-ethyl-1-hexanol. Of particular interest is that the dielectric constant of supercritical fluoroform can be tuned from approximately 1 to 8, merely by increasing pressure from 850 to 4000 psi (from 5.9 to 28 MPa). The possibility now exists to predictably alter both the selectivity and the activity of a biocatalyst merely by changing pressure. Images Fig. 6 PMID:8464910

  15. Biocatalytic asymmetric synthesis of chiral amines from ketones applied to sitagliptin manufacture.

    PubMed

    Savile, Christopher K; Janey, Jacob M; Mundorff, Emily C; Moore, Jeffrey C; Tam, Sarena; Jarvis, William R; Colbeck, Jeffrey C; Krebber, Anke; Fleitz, Fred J; Brands, Jos; Devine, Paul N; Huisman, Gjalt W; Hughes, Gregory J

    2010-07-16

    Pharmaceutical synthesis can benefit greatly from the selectivity gains associated with enzymatic catalysis. Here, we report an efficient biocatalytic process to replace a recently implemented rhodium-catalyzed asymmetric enamine hydrogenation for the large-scale manufacture of the antidiabetic compound sitagliptin. Starting from an enzyme that had the catalytic machinery to perform the desired chemistry but lacked any activity toward the prositagliptin ketone, we applied a substrate walking, modeling, and mutation approach to create a transaminase with marginal activity for the synthesis of the chiral amine; this variant was then further engineered via directed evolution for practical application in a manufacturing setting. The resultant biocatalysts showed broad applicability toward the synthesis of chiral amines that previously were accessible only via resolution. This work underscores the maturation of biocatalysis to enable efficient, economical, and environmentally benign processes for the manufacture of pharmaceuticals.

  16. Use of Flue Gas Desulfurization (FGD) Gypsum as a Heavy Metal Stabilizer in Contaminated Soils

    EPA Science Inventory

    Flue Gas Desulfurization (FGD) gypsum is a synthetic by-product generated from the flue gas desulfurization process in coal power plants. It has several beneficial applications such as an ingredient in cement production, wallboard production and in agricultural practice as a soil...

  17. Molecular biological enhancement of coal desulfurization

    SciTech Connect

    Litchfield, J.H.; Fry, I.; Wyza, R.E.; Palmer, D.T.; Zupancic, T.J.; Conkle, H.N. ); Delgado, O.; Tuovinen, O.H. )

    1990-09-14

    The objective of this project is to produce one or more microorganisms capable of removing the organic and inorganic sulfur in coal. The specific technical objectives of the project are to: clone and characterize the genes encoding the enzymes of the 4S'' pathway (sulfoxide/sulfone/sulfonate/sulfate) for release of organic sulfur from coal; return multiple copies of genes to the original host to enhance the biodesulfurization activity of that organism; transfer this pathway into a fast-growing chemolithotrophic bacterium; and conduct a batch-mode optimization/analysis of scale-up variables. This report presents the results of research at Battelle during the 5th Quarterly Report period beginning on June 15, 1990. 1 ref., 6 figs., 4 tabs.

  18. Rational Improvement of Simvastatin Synthase Solubility in Escherichia coli Leads to Higher Whole-cell Biocatalytic Activity

    PubMed Central

    Xie, Xinkai; Pashkov, Inna; Gao, Xue; Guerrero, Jennifer L.; Yeates, Todd O.; Tang, Yi

    2014-01-01

    Simvastatin is the active pharmaceutical ingredient of the blockbuster cholesterol lowering drug Zocor. We have previously developed an Escherichia coli based whole-cell biocatalytic platform towards the synthesis of simvastatin sodium salt (SS) starting from the precursor monacolin J sodium salt (MJSS). The centerpiece of the biocatalytic approach is the simvastatin synthase LovD, which is highly prone to misfolding and aggregation when overexpressed from E. coli. Increasing the solubility of LovD without decreasing its catalytic activity can therefore elevate the performance of the whole-cell biocatalyst. Using a combination of homology structural prediction and site-directed mutagenesis, we identified two cysteine residues in LovD that are responsible for nonspecific intermolecular crosslinking, which leads to oligomer formation and protein aggregation. Replacement of Cys40 and Cys60 with alanine residues resulted in marked gain in both protein solubility and whole-cell biocatalytic activities. Further mutagenesis experiments converting these two residues to small or polar natural amino acids showed that C40A and C60N are the most beneficial, affording 27% and 26% increase in whole cell activities, respectively. The double mutant C40A/C60N combines the individual improvements and displayed ~50% increase in protein solubility and whole-cell activity. Optimized fed-batch high-cell-density fermentation of the double mutant in an E. coli strain engineered for simvastatin production quantitatively (>99%) converted 45 mM MJSS to SS within 18 hours, which represents a significant improvement over the performance of wild type LovD under identical conditions. The high efficiency of the improved whole-cell platform renders the biocatalytic synthesis of SS an attractive substitute over the existing semisynthetic routes. PMID:18988191

  19. Molecular biological enhancement of coal desulfurization. Final report

    SciTech Connect

    Krawiec, S.

    1995-01-01

    Fresh isolates of bacteria presumptively identified as R. erythropolis unequivocally have a DbtS{sup +} phenotype. The production of OH-BP from either DBT or DBTO{sub 2} was confirmed by difference spectroscopy, HPLC, and mass spectrometry. The temperature, pH, and means of supplying the thiophenic or sulfonic sole source of sulfur were optimized. The maximal rate of growth of the organism, its affinity for sulfone, and the extent to which substrate was converted to product were determined by using batch, fed batch, and continuous cultures. For strain N1-36, the maximum specific growth rate was 0.235 hr{sup -1} which corresponds to a minimal generation time of 2.95 hr. The K{sub s} was estimated to be 0.39 {mu}M. With 100 {mu}M DBT as the sole sulfur source, approximately 40 {mu}M OH-BP are produced (after 40 hr of growth); with 100 {mu}M DBTO{sub 2} as the sole sulfur source, approximately 70 {mu}M OH-BP are produced (after 40 hr of growth). The desulfurization activity is repressed by SO{sub 4}{sup =} OH-BP does not serve as a carbon source. The DbtS{sup +} phenotype of the R. erythropolis isolates is stable and discrete. The isolates selectively remove sulfur from DBT, a compound which models a refractory form of organic sulfur in compounds characteristic of fossil fuels. The desulfurization occurs with no oxidation of carbon-carbon bonds. The stability and specificity (along with genetic regulation) indicate that microbial desulfurization in a real phenomenon in which a noxious element is removed without significantly affecting the calorific value of the substrate. Additional characterization (and optimization) would provide the basis of a very important form of fossil fuel beneficiation.

  20. Coal desulfurization in a rotary kiln combustor

    SciTech Connect

    Cobb, J.T. Jr.

    1992-09-11

    The purpose of this project was to demonstrate the combustion of coal and coal wastes in a rotary kiln reactor with limestone addition for sulfur control. The rationale for the project was the perception that rotary systems could bring several advantages to combustion of these fuels, and may thus offer an alternative to fluid-bed boilers. Towards this end, an existing wood pyrolysis kiln (the Humphrey Charcoal kiln) was to be suitably refurbished and retrofitted with a specially designed version of a patented air distributor provided by Universal Energy, Inc. (UEI). As the project progressed beyond the initial stages, a number of issues were raised regarding the feasibility and the possible advantages of burning coals in a rotary kiln combustor and, in particular, the suitability of the Humphrey Charcoal kiln as a combustor. Instead, an opportunity arose to conduct combustion tests in the PEDCO Rotary Cascading-Bed Boiler (RCBB) commercial demonstration unit at the North American Rayon CO. (NARCO) in Elizabethton, TN. The tests focused on anthracite culm and had two objectives: (a) determine the feasibility of burning anthracite culms in a rotary kiln boiler and (b) obtain input for any further work involving the Humphrey Charcoal kiln combustor. A number of tests were conducted at the PEDCO unit. The last one was conducted on anthracite culm procured directly from the feed bin of a commercial circulating fluid-bed boiler. The results were disappointing; it was difficult to maintain sustained combustion even when large quantities of supplemental fuel were used. Combustion efficiency was poor, around 60 percent. The results suggest that the rotary kiln boiler, as designed, is ill-suited with respect to low-grade, hard to burn solid fuels, such as anthracite culm. Indeed, data from combustion of bituminous coal in the PEDCO unit suggest that with respect to coal in general, the rotary kiln boiler appears inferior to the circulating fluid bed boiler.

  1. Evaluation of performance and stability of biocatalytic redox films constructed with different copper oxygenases and osmium-based redox polymers.

    PubMed

    Jenkins, Peter A; Boland, Susan; Kavanagh, Paul; Leech, Dónal

    2009-09-01

    We are interested in investigating the applications of biocatalytic mediated reduction of oxygen by oxygenases in films on electrode surfaces, as such reactions can form the basis for biosensors or biocatalytic fuel cell development. Here we present approaches aimed at improving the stability and signal output of such films. These include selection of oxygen reducing biocatalysts which are active under physiological conditions and development of redox mediators which offer the opportunity to tailor the mediator to each enzyme. It was found that for each enzyme Melanocarpus albomyces laccase (MaL), Trametes hirsutus laccase (ThL) or bilirubin oxidase (MvBOD) it was the biocatalytic films mediated by Os(2,2'-bipyridine)(2)Cl.PVI that not only generated the highest current densities compared to Os(4,4'-dimethyl-2,2'-bipyridine)(2)Cl.PVI and Os(4,4'-dichloro-2,2'-bipyridine)(2)Cl.PVI, but also proved to be the most stable over 48 h. Under physiological conditions electrodes constructed from MvBOD generated the highest initial current densities for each of the osmium redox polymers, however these films proved to be the least stable over 48 h. Stability could be improved using surface pre-treatment.

  2. Efficiency Analysis and Mechanism Insight of that Whole-Cell Biocatalytic Production of Melibiose from Raffinose with Saccharomyces cerevisiae.

    PubMed

    Zhou, Yingbiao; Zhu, Yueming; Dai, Longhai; Men, Yan; Wu, Jinhai; Zhang, Juankun; Sun, Yuanxia

    2017-01-01

    Melibiose is widely used as a functional carbohydrate. Whole-cell biocatalytic production of melibiose from raffinose could reduce its cost. However, characteristics of strains for whole-cell biocatalysis and mechanism of such process are unclear. We compared three different Saccharomyces cerevisiae strains (liquor, wine, and baker's yeasts) in terms of concentration variations of substrate (raffinose), target product (melibiose), and by-products (fructose and galactose) in whole-cell biocatalysis process. Distinct difference was observed in whole-cell catalytic efficiency among three strains. Furthermore, activities of key enzymes (invertase, α-galactosidase, and fructose transporter) involved in process and expression levels of their coding genes (suc2, mel1, and fsy1) were investigated. Conservation of key genes in S. cerevisiae strains was also evaluated. Results show that whole-cell catalytic efficiency of S. cerevisiae in the raffinose substrate was closely related to activity of key enzymes and expression of their coding genes. Finally, we summarized characteristics of producing strain that offered advantages, as well as contributions of key genes to excellent strains. Furthermore, we presented a dynamic mechanism model to achieve some mechanism insight for this whole-cell biocatalytic process. This pioneering study should contribute to improvement of whole-cell biocatalytic production of melibiose from raffinose.

  3. Use of a Ceramic Membrane to Improve the Performance of Two-Separate-Phase Biocatalytic Membrane Reactor.

    PubMed

    Ranieri, Giuseppe; Mazzei, Rosalinda; Wu, Zhentao; Li, Kang; Giorno, Lidietta

    2016-03-14

    Biocatalytic membrane reactors (BMR) combining reaction and separation within the same unit have many advantages over conventional reactor designs. Ceramic membranes are an attractive alternative to polymeric membranes in membrane biotechnology due to their high chemical, thermal and mechanical resistance. Another important use is their potential application in a biphasic membrane system, where support solvent resistance is highly needed. In this work, the preparation of asymmetric ceramic hollow fibre membranes and their use in a two-separate-phase biocatalytic membrane reactor will be described. The asymmetric ceramic hollow fibre membranes were prepared using a combined phase inversion and sintering technique. The prepared fibres were then used as support for lipase covalent immobilization in order to develop a two-separate-phase biocatalytic membrane reactor. A functionalization method was proposed in order to increase the density of the reactive hydroxyl groups on the surface of ceramic membranes, which were then amino-activated and treated with a crosslinker. The performance and the stability of the immobilized lipase were investigated as a function of the amount of the immobilized biocatalytst. Results showed that it is possible to immobilize lipase on a ceramic membrane without altering its catalytic performance (initial residual specific activity 93%), which remains constant after 6 reaction cycles.

  4. Biocatalytic polymer coatings: on-demand drug synthesis and localized therapeutic effect under dynamic cell culture conditions.

    PubMed

    Fejerskov, Betina; Jensen, Najah B S; Teo, Boon M; Städler, Brigitte; Zelikin, Alexander N

    2014-04-09

    Biocatalytic surface coatings are prepared herein for localized synthesis of drugs and their on-demand, site-specific delivery to adhering cells. This novel approach is based on the incorporation of an enzyme into multilayered polymer coatings to accomplish enzyme-prodrug therapy (EPT). The build-up of enzyme-containing multilayered coatings is characterized and correlations are drawn between the multilayer film assembly conditions and the enzymatic activity of the resulting coatings. Therapeutic effect elicited by the substrate mediated EPT (SMEPT) strategy is investigated using a prodrug for an anticancer agent, SN-38. The performance of biocatalytic coatings under flow conditions is investigated and it is demonstrated that EPT allows synthesizing the drugs on-demand, at the time desired and in a controllable amount to suit particular applications. Finally, using cells cultured in sequentially connected flow chambers, it is demonstrated that SMEPT affords a site-specific drug delivery, that is, exerts a higher therapeutic effect in cells adhering directly to the biocatalytic coatings than in the cells cultured "downstream". Taken together, these data illustrate biomedical opportunities made possible by engineering tools of EPT into multilayered polymer coatings and present a novel, highly versatile tool for surface mediated drug delivery.

  5. Desulfurization of hot fuel gas produced from high-chlorine Illinois coals. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect

    O`Brien, W.S.; Gupta, R.P.

    1992-12-31

    In this project, simulated gasifier-product streams were contacted with the zinc titanate desulfurization sorbent in a bench-scale atmospheric fluidized-bed reactor at temperatures ranging from 538 to 750 {degree}C (1000 to 1382 {degree}F). The first set of experiments involved treating a medium-Btu fuel gas (simulating that of a ``Texaco`` oxygen-blown, entrained-bed gasifier) containing 1.4 percent H{sub 2}S and HCl concentrations of 0, 200, and 1500 ppmv. The second experimental set evaluated hot-gas desulfurization of a low-Btu fuel gas (simulating the product of the ``U-Gas`` air-blown gasifier), with HCl concentrations of 0, 200, and 800 ppmv. These operating conditions were typical of the gas-treatment requirements of gasifiers fueled by Illinois basin coals containing up to 0.6 percent chlorine. The results of the experiments at 538 and 650 {degree}C at all the HCl concentrations revealed no deleterious effects on the capability of the sorbent to remove H{sub 2}S from the fuel gas mixtures. In most cases, the presence of the HCl significantly enhanced the desulfurization reaction rate. Some zinc loss, however, was encountered in certain situations at 750 {degree}C when low-steam operating conditions were present. Also of interest, a portion of the incoming HCl was removed from the gas stream and was retained permanently by the sorbent. This behavior was examined in more detail in a limited set of experiments aimed at identifying ways to modify the sorbents composition so that the sorbent could act as a simultaneous desulfurization and dechlorination agent in the hot-gas cleanup process.

  6. Methods, systems, and devices for deep desulfurization of fuel gases

    DOEpatents

    Li, Liyu [Richland, WA; King, David L [Richland, WA; Liu, Jun [Richland, WA; Huo, Qisheng [Richland, WA

    2012-04-17

    A highly effective and regenerable method, system and device that enables the desulfurization of warm fuel gases by passing these warm gasses over metal-based sorbents arranged in a mesoporous substrate. This technology will protect Fischer-Tropsch synthesis catalysts and other sulfur sensitive catalysts, without drastic cooling of the fuel gases. This invention can be utilized in a process either alone or alongside other separation processes, and allows the total sulfur in such a gas to be reduced to less than 500 ppb and in some instances as low as 50 ppb.

  7. Cost effective materials for flue gas desulfurization (FGD)

    SciTech Connect

    Kelley, D.H.; Brady, B.

    1996-10-01

    Wet Flue Gas Desulfurization (FGD) is an effective way to remove sulfur dioxide from coal combustion processes and reduce the potential for acid rain. However, wet FGD processes often require highly corrosion resistant construction materials such as high alloys for adequate service life. An excellent material for wet FGD applications at about one half the cost of high alloys is fiberglass-reinforced plastic (FRP) based on epoxy vinyl ester resin. This paper discusses the background and improvements that have led to the use of some of the world`s largest composite structures in FGD service.

  8. Spray tower: the workhorse of flue-gas desulfurization

    SciTech Connect

    Saleem, A.

    1980-10-01

    A recently developed spray tower system for use in a utility flue gas desulfurization system is simple, durable, and capable of achieving very high sulfur dioxide removal efficiencies, possibly approaching 100%. The principles behind the design and operation of the spray tower are discussed. The quality of water used for washing, tower size limitations, construction materials liquid distribution, gas-inlet design, gas distribution, mass transfer, and operating characteristics are examined. Procedures to maintain the reliability and high performance of the spray tower are described. (5 diagrams, 5 photos, 12 references, 1 table)

  9. Synthesis of Neoglycoconjugates by the Desulfurative Rearrangement of Allylic Disulfides

    PubMed Central

    Crich, David; Yang, Fan

    2009-01-01

    Two series of neoglucosyl donors are prepared based on connection of the allylic disulfide motif to the anomeric center via either a simple O-glycosyl linkage or N-glycosyl amide unit. Conjugation of both sets of donors to cysteine in peptides is demonstrated through classical disulfide exchange followed by the phosphine-mediated desulfurative allylic rearrangement resulting in neoglycopeptides characterized by a simple thioether spacer. The conjugation reaction functions in the absence of protecting groups on both the neoglycosyl donor and peptide in aqueous media at room temperature. PMID:18729514

  10. Confined zone dispersion flue gas desulfurization demonstration

    SciTech Connect

    Not Available

    1993-01-15

    This is the sixth quarterly report for this project and it covers work performed on Phase 3a of the project from February 1, 1992 through April 30, 1992. Extension of the parametric test period through June 1992 provides an opportunity to regain most of the schedule slippage, but only if the modifications needed for continuous operation of the CZD system are installed concurrent with the extended test period. These modifications include automation of the lime preparation and transfer system, automatic injection control, and related instrumentation and controls as necessary to integrate the operation of the CZD system with Seward Station Boiler No. 15. Early installation of these modifications would permit testing, debugging and adjustment of the automatic control system during the parametric test period. Results of current testing indicate that considerable testing and adjustment will be required to optimize operation of the CZD system after it is automated for continuous operation. Therefore, we intend to incorporate in Phase 3a(parametric testing) the system modifications needed for continuous automatic operation that were originally included in Phase 3b. Phase 3b would then be limited only to the one-year continuous demonstration.

  11. Confined zone dispersion flue gas desulfurization demonstration

    SciTech Connect

    Not Available

    1992-12-31

    This is the fifth quarterly report for this project. This project is divided into three phases. Phase 1, which has been completed, involved design, engineering, and procurement for the CZD system, duct and facility modifications, and supporting equipment. Phase 2, also completed, included equipment acquisition and installation, facility construction, startup, and operator training for parametric testing. Phase 3 broadly covers testing, operation and disposition, but only a portion of Phase 3 was included in Budget Period 1. That portion was concerned with parametric testing of the CZD system to establish the optimum conditions for an extended, one-year, continuous demonstration. As of December 31, 1991, the following goals have been achieved. (1) Nozzle Selection - A modified Spraying Systems Company (SSC) atomizing nozzle has been selected for the one-year continuous CZD demonstration. (2) SO[sub 2] and NO[sub x] Reduction - Preliminary confirmation of 50% SO[sub 2] reduction has been achieved, but the NO[sub x] reduction target cannot be confirmed at this time. (3) Lime Selection - Testing indicated an injection rate of 40 to 50 gallons per minute with a lime slurry concentration of 8 to 10% to achieve 50% SO[sub 2] reduction. There has been no selection of the lime to be used in the one year demonstration. (4) ESP Optimization - Tests conducted to date have shown that lime injection has a very beneficial effect on ESP performance, and little adjustment may be necessary. (5) SO[sub 2] Removal Costs - Testing has not revealed any significant departure from the bases on which Bechtel's original cost estimates (capital and operating) were prepared. Therefore, SO[sub 2] removal costs are still expected to be in the range of $300/ton or less.

  12. Pyrite surface characterization and control for advanced fine coal desulfurization technologies

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Jiang, C.L.

    1992-01-01

    This is the 9th quarterly technical progress report for the project entitled Pyrite surface characterization and control for advanced fine coal desulfurization technologies'', DE-FG22-90PC90295. The work presented in this report was performed from September 1, 1992 to November 31, 1992. The objective of the project is to conduct extensive fundamental studies on the surface chemistry of pyrite oxidation and flotation and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the surface oxidation of pyrite in various electrolytes was investigated. It has been demonstrated, for the first time, that borate, a pH buffer and electrolyte used by many previous investigators in studying sulfide mineral oxidation, actively participates in the surface oxidation of pyrite. In borate solutions, the surface oxidation of pyrite is tronly enhanced. The anodic oxidation potential of pyrite is lowered by more than 0.4 volts. The initial reaction of the borate enhanced pyrite oxidation can be described by:FeS[sub 2] + B(OH)[sub 4][sup =] ------> [S[sub 2]Fe-B(OH)[sub 4

  13. Desulfurization of coal with hydroperoxides of vegetable oils. [Quarterly] report, September 1--November 30, 1994

    SciTech Connect

    Smith, G.V.; Gaston, R.D.; Song, Ruozhi; Cheng, Jianjun

    1994-12-31

    This project proposes a new method for removing organic sulfur from Illinois coals using readily available farm products. It proposes to use air and vegetable oils to disrupt the coal matrix, oxidize sulfur forms, increase volatiles, and desulfurize coal. This will be accomplished by impregnating coals with polyunsaturated oils, converting the oils to their hydroperoxides, and heating. Since these oils are relatively inexpensive and easily applied, this project could lead to a cost effective method for removing organic sulfur from coals. Moreover, the oils are environmentally safe; they will produce no noxious products and will improve burning qualities of the solid products. Preliminary experiments showed that EBC 104 coal catalyzes the formation of hydroperoxides in safflower oil and that more sulfur is extracted from the treated than untreated coal. During this first quarter the requirement of an added photosensitizer has been eliminated, the catalytic effect of coal has been confirmed, and the existence of a complex set of reactions revealed. These reactions between the oxygen, oil, hydroperoxides, and coal are hydroperoxide formation, which is catalyzed by the coal surface and by heat, an unknown coal-hydroperoxide reaction, and oil polymerization. Additionally, diffusion phenomena must be playing a role because oil polymerization occurs, but the importance of diffusion is difficult to assess because less polymerization occurs when coal is present. The first task has been completed and we are now ready to determine the ability of linseed oil hydroperoxides to oxidize organic sulfur in EBC 108 coal.

  14. Enhanced desulfurizing flotation of coal using sonoelectrochemical method.

    PubMed

    Zhang, Hong-Xi; Hou, Xiao-Yang; Xu, Shi-Xun; Li, Zhi-Long; Yu, Hai-Feng; Shen, Xue-Hua

    2013-09-01

    Enhanced desulfurizing flotation of low sulfur coal was investigated using sonoelectrochemical method. The supporting electrolyte used in this process was sodium chloride and the additive was anhydrous ethanol. The effects of treatment conditions on desulfurization were studied by a single-factor method. The conditions include anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature, sonoelectrolytic time and coal sample granulometry. The optimal experimental conditions achieved for anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature and sonoelectrolytic time are 1.7 mol L(-1), 5.1×10(-3) mol L(-1), 10 V, 70 °C, 50 min achieved for a -0.18 mm coal sample. Optimal conditions cause a sulfur reduction of up to 69.4%. The raw and treated coals were analyzed by infrared spectroscopy and a chemical method. Pyritic sulfur, organic sulfur, ash as well as moisture are partially removed. The combination of high sulfur reduction, high yield, as well as high ash reduction was obtained in the newly developed method of enhanced flotation by sonoelectrochemistry. Ultrasound irradiation promotes electron transfer efficiency and increases clean coal yield.

  15. Anion-exchange resin-based desulfurization process

    SciTech Connect

    Sheth, A.C.; Strevel, S.D.; Dharmapurikar, R.

    1992-01-01

    Under the current grant, the University of Tennessee Space Institute (UTSI) will carry out the bench scale evaluation and further development of the anion-exchange resin-based desulfurization concept to desulfurize alkali metal sulfates. This concept has been developed and patented by UTSI under US Patent No. 4,917,874. The developmental program proposed under this DOE grant includes screening of commercially available resins to select three candidate resins for further study. These three resins will undergo a series of experiments designed to test the resins' performance under different process conditions (including the use of spent MHD seed material). The best of these resins will be used in optimizing the regeneration step and in testing the effects of performance enhancers. The process schematic developed from the results will be used to estimate the related economics. During this reporting period, October 1, 1991 to September 30, 1992, analysis of batch mode screening experiments was completed to select three candidate resins for process variables study in the fixed-bed set-up. This setup was modified and the experiments were carded out to evaluate effects of major process variables. The analysis of fixed-bed experiments is going on and we have also started simple batch mode experiments to identify desirable conditions for resin regeneration step. We have also started simple process engineering type calculations to determine the trade-off between the solution concentration and the resulting evaporation/concentration load.

  16. BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    Unknown

    1999-07-01

    The U.S. Department of Energy (DOE), National Energy Technology Laboratory (NETL), is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal-derived fuel-gas) streams of integrated gasification combined-cycle (IGCC) power systems. The hot gas cleanup work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs. Hot-gas desulfurization research has focused on regenerable mixed-metal oxide sorbents that can reduce the sulfur in coal-derived fuel-gas to less than 20 ppmv and can be regenerated in a cyclic manner with air for multicycle operation. Zinc titanate (Zn{sub 2}TiO{sub 4} or ZnTiO{sub 3}), formed by a solid-state reaction of zinc oxide (ZnO) and titanium dioxide (TiO{sub 2}), is currently one of the leading sorbents. Overall chemical reactions with Zn{sub 2}TiO{sub 4} during the desulfurization (sulfidation)-regeneration cycle are shown. The sulfidation/regeneration cycle can be carried out in a fixed-bed, moving-bed, or fluidized-bed reactor configuration. The fluidized-bed reactor configuration is most attractive because of several potential advantages including faster kinetics and the ability to handle the highly exothermic regeneration to produce a regeneration offgas containing a constant concentration of SO{sub 2}.

  17. BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    Unknown

    2000-09-01

    The U.S. Department of Energy (DOE), National Energy Technology Laboratory (NETL), is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal-derived fuel-gas) streams of integrated gasification combined-cycle (IGCC) power systems. The hot gas cleanup work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs. Hot-gas desulfurization research has focused on regenerable mixed-metal oxide sorbents that can reduce the sulfur in coal-derived fuel-gas to less than 20 ppmv and can be regenerated in a cyclic manner with air for multicycle operation. Zinc titanate (Zn{sub 2}TiO{sub 4} or ZnTiO{sub 3}), formed by a solid-state reaction of zinc oxide (ZnO) and titanium dioxide (TiO{sub 2}), is currently one of the leading sorbents. Overall chemical reactions with Zn{sub 2}TiO{sub 4} during the desulfurization (sulfidation)-regeneration cycle are shown. The sulfidation/regeneration cycle can be carried out in a fixed-bed, moving-bed, or fluidized-bed reactor configuration. The fluidized-bed reactor configuration is most attractive because of several potential advantages including faster kinetics and the ability to handle the highly exothermic regeneration to produce a regeneration offgas containing a constant concentration of SO{sub 2}.

  18. An experimental study on desulfurization of high-sulfur coal slime with free jet flotation column

    SciTech Connect

    Xie Hua; Huang Bo; Xia Qing

    1998-12-31

    A free jet flotation column gives good selectivity and high separation efficiency in treating fine and ultra-fine coal. This paper reports test results of coal desulfurization with a free jet flotation column. Test results showed that when the coal sample from Zhong Liang Shan was processed its pyritic sulfur content was reduced from 3.08% to 0.84%, with 72.22% recovery of combustible matter in clean coal. The concept of Desulfurization Efficiency Index E(ds) for a comprehensive evaluation of desulfurization process is proposed, which is defined as the product of the ratio of sulfur content reduction and the recovery of combustible matters in clean coal.

  19. Method for enhancing the desulfurization of hot coal gas in a fluid-bed coal gasifier

    DOEpatents

    Grindley, Thomas

    1989-01-01

    A process and apparatus for providing additional desulfurization of the hot gas produced in a fluid-bed coal gasifier, within the gasifier. A fluid-bed of iron oxide is located inside the gasifier above the gasification bed in a fluid-bed coal gasifier in which in-bed desulfurization by lime/limestone takes place. The product gases leave the gasification bed typically at 1600.degree. to 1800.degree. F. and are partially quenched with water to 1000.degree. to 1200.degree. F. before entering the iron oxide bed. The iron oxide bed provides additional desulfurization beyond that provided by the lime/limestone.

  20. Coal desulfurization in a rotary kiln combustor

    SciTech Connect

    Cobb, J.T. Jr.

    1990-08-15

    BCR National Laboratory (BCRNL) has initiated a project aimed at evaluating the technical and economic feasibility of using a rotary kiln, suitably modified, to burn Pennsylvania anthracite wastes, co-fired with high-sulfur bituminous coal. Limestone will be injected into the kiln for sulfur control, to determine whether high sulfur capture levels can be achieved with high sorbent utilization. The principal objectives of this work are: (1) to prove the feasibility of burning anthracite refuse, with co-firing of high-sulfur bituminous coal and with limestone injection for sulfur emissions control, in a rotary kiln fitted with a Universal Energy International (UEI) air injector system; (2) to determine the emissions levels of SO{sub x} and NO{sub x} and specifically to identify the Ca/S ratios that are required to meet New Source Performance Standards; (3) to evaluate the technical and economic merits of a commercial rotary kiln combustor in comparison to fluidized bed combustors; and, (4) to ascertain the need for further work, including additional combustion tests, prior to commercial application, and to recommend accordingly a detailed program towards this end.

  1. Flue gas desulfurization gypsum and fly ash

    SciTech Connect

    Not Available

    1992-05-01

    The Cumberland Fossil Plant (CUF) is located in Stewart County, Tennessee, and began commercial operation in 1972. This is the Tennessee Valley Authority`s newest fossil (coal-burning) steam electric generating plant. Under current operating conditions, the plant burns approximately seven million tons of coal annually. By-products from the combustion of coal are fly ash, approximately 428,000 tons annually, and bottom ash, approximately 115,000 tons annually. Based on historical load and projected ash production rates, a study was initially undertaken to identify feasible alternatives for marketing, utilization and disposal of ash by-products. The preferred alternative to ensure that facilities are planned for all by-products which will potentially be generated at CUF is to plan facilities to handle wet FGD gypsum and dry fly ash. A number of different sites were evaluated for their suitability for development as FGD gypsum and ash storage facilities. LAW Engineering was contracted to conduct onsite explorations of sites to develop information on the general mature of subsurface soil, rock and groundwater conditions in the site areas. Surveys were also conducted on each site to assess the presence of endangered and threatened species, wetlands and floodplains, archaeological and cultural resources, prime farmland and other site characteristics which must be considered from an environmental perspective.

  2. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    PubMed

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

  3. Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede, Chamberlinius hualienensis

    PubMed Central

    Dadashipour, Mohammad; Ishida, Yuko; Yamamoto, Kazunori; Asano, Yasuhisa

    2015-01-01

    Hydroxynitrile lyase (HNL) catalyzes the degradation of cyanohydrins and causes the release of hydrogen cyanide (cyanogenesis). HNL can enantioselectively produce cyanohydrins, which are valuable building blocks for the synthesis of fine chemicals and pharmaceuticals, and is used as an important biocatalyst in industrial biotechnology. Currently, HNLs are isolated from plants and bacteria. Because industrial biotechnology requires more efficient and stable enzymes for sustainable development, we must continuously explore other potential enzyme sources for the desired HNLs. Despite the abundance of cyanogenic millipedes in the world, there has been no precise study of the HNLs from these arthropods. Here we report the isolation of HNL from the cyanide-emitting invasive millipede Chamberlinius hualienensis, along with its molecular properties and application in biocatalysis. The purified enzyme displays a very high specific activity in the synthesis of mandelonitrile. It is a glycosylated homodimer protein and shows no apparent sequence identity or homology with proteins in the known databases. It shows biocatalytic activity for the condensation of various aromatic aldehydes with potassium cyanide to produce cyanohydrins and has high stability over a wide range of temperatures and pH values. It catalyzes the synthesis of (R)-mandelonitrile from benzaldehyde with a 99% enantiomeric excess, without using any organic solvents. Arthropod fauna comprise 80% of terrestrial animals. We propose that these animals can be valuable resources for exploring not only HNLs but also diverse, efficient, and stable biocatalysts in industrial biotechnology. PMID:26261304

  4. Building carbon-carbon bonds using a biocatalytic methanol condensation cycle.

    PubMed

    Bogorad, Igor W; Chen, Chang-Ting; Theisen, Matthew K; Wu, Tung-Yun; Schlenz, Alicia R; Lam, Albert T; Liao, James C

    2014-11-11

    Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C-C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through (13)C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives.

  5. Microbiome and Biocatalytic Bacteria in Monkey Cup (Nepenthes Pitcher) Digestive Fluid.

    PubMed

    Chan, Xin-Yue; Hong, Kar-Wai; Yin, Wai-Fong; Chan, Kok-Gan

    2016-01-28

    Tropical carnivorous plant, Nepenthes, locally known as "monkey cup", utilises its pitcher as a passive trap to capture insects. It then secretes enzymes into the pitcher fluid to digest the insects for nutrients acquisition. However, little is known about the microbiota and their activity in its pitcher fluid. Eighteen bacteria phyla were detected from the metagenome study in the Nepenthes pitcher fluid. Proteobacteria, Bacteroidetes and Actinobacteria are the dominant phyla in the Nepenthes pitcher fluid. We also performed culturomics approach by isolating 18 bacteria from the Nepenthes pitcher fluid. Most of the bacterial isolates possess chitinolytic, proteolytic, amylolytic, and cellulolytic and xylanolytic activities. Fifteen putative chitinase genes were identified from the whole genome analysis on the genomes of the 18 bacteria isolated from Nepenthes pitcher fluid and expressed for chitinase assay. Of these, six clones possessed chitinase activity. In conclusion, our metagenome result shows that the Nepenthes pitcher fluid contains vast bacterial diversity and the culturomic studies confirmed the presence of biocatalytic bacteria within the Nepenthes pitcher juice which may act in symbiosis for the turn over of insects trapped in the Nepenthes pitcher fluid.

  6. Microbiome and Biocatalytic Bacteria in Monkey Cup (Nepenthes Pitcher) Digestive Fluid

    PubMed Central

    Chan, Xin-Yue; Hong, Kar-Wai; Yin, Wai-Fong; Chan, Kok-Gan

    2016-01-01

    Tropical carnivorous plant, Nepenthes, locally known as “monkey cup”, utilises its pitcher as a passive trap to capture insects. It then secretes enzymes into the pitcher fluid to digest the insects for nutrients acquisition. However, little is known about the microbiota and their activity in its pitcher fluid. Eighteen bacteria phyla were detected from the metagenome study in the Nepenthes pitcher fluid. Proteobacteria, Bacteroidetes and Actinobacteria are the dominant phyla in the Nepenthes pitcher fluid. We also performed culturomics approach by isolating 18 bacteria from the Nepenthes pitcher fluid. Most of the bacterial isolates possess chitinolytic, proteolytic, amylolytic, and cellulolytic and xylanolytic activities. Fifteen putative chitinase genes were identified from the whole genome analysis on the genomes of the 18 bacteria isolated from Nepenthes pitcher fluid and expressed for chitinase assay. Of these, six clones possessed chitinase activity. In conclusion, our metagenome result shows that the Nepenthes pitcher fluid contains vast bacterial diversity and the culturomic studies confirmed the presence of biocatalytic bacteria within the Nepenthes pitcher juice which may act in symbiosis for the turn over of insects trapped in the Nepenthes pitcher fluid. PMID:26817720

  7. Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede, Chamberlinius hualienensis.

    PubMed

    Dadashipour, Mohammad; Ishida, Yuko; Yamamoto, Kazunori; Asano, Yasuhisa

    2015-08-25

    Hydroxynitrile lyase (HNL) catalyzes the degradation of cyanohydrins and causes the release of hydrogen cyanide (cyanogenesis). HNL can enantioselectively produce cyanohydrins, which are valuable building blocks for the synthesis of fine chemicals and pharmaceuticals, and is used as an important biocatalyst in industrial biotechnology. Currently, HNLs are isolated from plants and bacteria. Because industrial biotechnology requires more efficient and stable enzymes for sustainable development, we must continuously explore other potential enzyme sources for the desired HNLs. Despite the abundance of cyanogenic millipedes in the world, there has been no precise study of the HNLs from these arthropods. Here we report the isolation of HNL from the cyanide-emitting invasive millipede Chamberlinius hualienensis, along with its molecular properties and application in biocatalysis. The purified enzyme displays a very high specific activity in the synthesis of mandelonitrile. It is a glycosylated homodimer protein and shows no apparent sequence identity or homology with proteins in the known databases. It shows biocatalytic activity for the condensation of various aromatic aldehydes with potassium cyanide to produce cyanohydrins and has high stability over a wide range of temperatures and pH values. It catalyzes the synthesis of (R)-mandelonitrile from benzaldehyde with a 99% enantiomeric excess, without using any organic solvents. Arthropod fauna comprise 80% of terrestrial animals. We propose that these animals can be valuable resources for exploring not only HNLs but also diverse, efficient, and stable biocatalysts in industrial biotechnology.

  8. Biocatalytic Production of Trehalose from Maltose by Using Whole Cells of Permeabilized Recombinant Escherichia coli

    PubMed Central

    Sun, Ye; Mei, Wending; Ouyang, Jia

    2015-01-01

    Trehalose is a non-reducing disaccharide, which can protect proteins, lipid membranes, and cells from desiccation, refrigeration, dehydration, and other harsh environments. Trehalose can be produced by different pathways and trehalose synthase pathway is a convenient, practical, and low-cost pathway for the industrial production of trehalose. In this study, 3 candidate treS genes were screened from genomic databases of Pseudomonas and expressed in Escherichia coli. One of them from P. stutzeri A1501 exhibited the best transformation ability from maltose into trehalose and the least byproduct. Thus, whole cells of this recombinant E. coli were used as biocatalyst for trehalose production. In order to improve the conversion rate of maltose to trehalose, optimization of the permeabilization and biotransformation were carried out. Under optimal conditions, 92.2 g/l trehalose was produced with a high productivity of 23.1 g/(l h). No increase of glucose was detected during the whole course. The biocatalytic process developed in this study might serve as a candidate for the large scale production of trehalose. PMID:26462117

  9. Two-Input Enzymatic Logic Gates Made Sigmoid by Modifications of the Biocatalytic Reaction Cascades

    SciTech Connect

    Zavalov, Oleksandr; Bocharova, Vera; Halamek, Jan; Halamkova, Lenka; Korkmaz, Sevim; Arugula, Mary; Chinnapareddy, Soujanya; Katz, Evgeny; Privman, Vladimir

    2012-01-01

    Computing based on biochemical processes is a newest rapidly developing field of unconventional information and signal processing. In this paper we present results of our research in the field of biochemical computing and summarize the obtained numerical and experimental data for implementations of the standard two-input OR and AND gates with double-sigmoid shape of the output signal. This form of response was obtained as a function of the two inputs in each of the realized biochemical systems. The enzymatic gate processes in the first system were activated with two chemical inputs and resulted in optically detected chromogen oxidation, which happens when either one or both of the inputs are present. In this case, the biochemical system is functioning as the OR gate. We demonstrate that the addition of a filtering biocatalytic process leads to a considerable reduction of the noise transmission factor and the resulting gate response has sigmoid shape in both inputs. The second system was developed for functioning as an AND gate, where the output signal was activated only by a simultaneous action of two enzymatic biomarkers. This response can be used as an indicator of liver damage, but only if both of these of the inputs are present at their elevated, pathophysiological values of concentrations. A kinetic numerical model was developed and used to estimate the range of parameters for which the experimentally realized logic gate is close to optimal. We also analyzed the system to evaluate its noise-handling properties.

  10. Characterisation of a Recombinant Patchoulol Synthase Variant for Biocatalytic Production of Terpenes.

    PubMed

    Frister, Thore; Hartwig, Steffen; Alemdar, Semra; Schnatz, Katharina; Thöns, Laura; Scheper, Thomas; Beutel, Sascha

    2015-08-01

    The patchoulol synthase (PTS) is a multi-product sesquiterpene synthases which is the central enzyme for biosynthesis of patchouli essential oil in the patchouli plant. Sesquiterpene synthases catalyse the formation of various complex carbon backbones difficult to approach by organic synthesis. Here, we report the characterisation of a recombinant patchoulol synthase complementary DNA (cDNA) variant (PTS var. 1), exhibiting significant amino acid exchanges compared to the native PTS. The product spectrum using the natural substrate E,E-farnesyl diphosphate (FDP) as well as terpenoid products resulting from conversions employing alternative substrates was analysed by GC-MS. In respect to a potential use as a biocatalyst, important enzymatic parameters such as the optimal reaction conditions, kinetic behaviour and the product selectivity were studied as well. Adjusting the reaction conditions, an increased patchoulol ratio in the recombinant essential oil was achieved. Nevertheless, the ratio remained lower than in plant-derived patchouli oil. As alternative substrates, several prenyl diposphates were accepted and converted in numerous compounds by the PTS var. 1, revealing its great biocatalytic potential.

  11. Techno-economic analysis of biocatalytic processes for production of alkene epoxides.

    PubMed

    Borole, Abhijeet P; Davison, Brian H

    2007-04-01

    A techno-economic analysis of two different bioprocesses was conducted, one for the conversion of propylene to propylene oxide (PO) and other for conversion of styrene to styrene epoxide (SO). The first process was a lipase-mediated chemo-enzymatic reaction, whereas the second one was a one-step enzymatic process using chloroperoxidase. The PO produced through the chemo-enzymatic process is a racemic product, whereas the latter process (based on chloroperoxidase) produces an enantio-pure product. The former process thus falls under the category of high-volume commodity chemical (PO); whereas the latter is a low-volume, high-value product (SO).A simulation of the process was conducted using the bioprocess engineering software SuperPro Designer v6.0 (Intelligen, Inc., Scotch Plains, NJ) to determine the economic feasibility of the process. The purpose of the exercise was to compare biocatalytic processes with existing chemical processes for production of alkene expoxides. The results show that further improvements are needed in improving biocatalyst stability to make these bioprocesses competitive with chemical processes.

  12. Cellulose digestion and metabolism induced biocatalytic transitions in anaerobic microbial ecosystems.

    PubMed

    Yamazawa, Akira; Iikura, Tomohiro; Morioka, Yusuke; Shino, Amiu; Ogata, Yoshiyuki; Date, Yasuhiro; Kikuchi, Jun

    2013-12-31

    Anaerobic digestion of highly polymerized biomass by microbial communities present in diverse microbial ecosystems is an indispensable metabolic process for biogeochemical cycling in nature and for industrial activities required to maintain a sustainable society. Therefore, the evaluation of the complicated microbial metabolomics presents a significant challenge. We here describe a comprehensive strategy for characterizing the degradation of highly crystallized bacterial cellulose (BC) that is accompanied by metabolite production for identifying the responsible biocatalysts, including microorganisms and their metabolic functions. To this end, we employed two-dimensional solid- and one-dimensional solution-state nuclear magnetic resonance (NMR) profiling combined with a metagenomic approach using stable isotope labeling. The key components of biocatalytic reactions determined using a metagenomic approach were correlated with cellulose degradation and metabolic products. The results indicate that BC degradation was mediated by cellulases that contain carbohydrate-binding modules and that belong to structural type A. The degradation reactions induced the metabolic dynamics of the microbial community and produced organic compounds, such as acetic acid and propionic acid, mainly metabolized by clostridial species. This combinatorial, functional and structural metagenomic approach is useful for the comprehensive characterization of biomass degradation, metabolic dynamics and their key components in diverse ecosystems.

  13. A continuous system for biocatalytic hydrogenation of CO2 to formate.

    PubMed

    Mourato, Cláudia; Martins, Mónica; da Silva, Sofia M; Pereira, Inês A C

    2017-03-20

    In this work a novel bioprocess for hydrogenation of CO2 to formate was developed, using whole cell catalysis by a sulfate-reducing bacterium. Three Desulfovibrio species were tested (D. vulgaris Hildenborough, D. alaskensis G20, and D. desulfuricans ATCC 27774), of which D. desulfuricans showed the highest activity, producing 12mM of formate in batch, with a production rate of 0.09mMh(-1). Gene expression analysis indicated that among the three formate dehydrogenases and five hydrogenases, the cytoplasmic FdhAB and the periplasmic [FeFe] HydAB are the main enzymes expressed in D. desulfuricans in these conditions. The new bioprocess for continuous formate production by D. desulfuricans had a maximum specific formate production rate of 14mMgdcw(-1)h(-1), and more than 45mM of formate were obtained with a production rate of 0.40mMh(-1). This is the first report of a continuous process for biocatalytic formate production.

  14. Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

    PubMed Central

    Bogorad, Igor W.; Chen, Chang-Ting; Theisen, Matthew K.; Wu, Tung-Yun; Schlenz, Alicia R.; Lam, Albert T.; Liao, James C.

    2014-01-01

    Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C–C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through 13C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives. PMID:25355907

  15. Separation, Immobilization, and Biocatalytic Utilization of Proteins by a Supramolecular Membrane

    PubMed Central

    Krieg, Elisha; Albeck, Shira; Weissman, Haim; Shimoni, Eyal; Rybtchinski, Boris

    2013-01-01

    Membrane separation of biomolecules and their application in biocatalysis is becoming increasingly important for biotechnology, demanding the development of new biocompatible materials with novel properties. In the present study, an entirely noncovalent water-based material is used as a membrane for size-selective separation, immobilization, and biocatalytic utilization of proteins. The membrane shows stable performance under physiological conditions, allowing filtration of protein mixtures with a 150 kDa molecular weight cutoff (∼8 nm hydrodynamic diameter cutoff). Due to the biocompatibility of the membrane, filtered proteins stay functionally active and retained proteins can be partially recovered. Upon filtration, large enzymes become immobilized within the membrane. They exhibit stable activity when subjected to a constant flux of substrates for prolonged periods of time, which can be used to carry out heterogeneous biocatalysis. The noncovalent membrane material can be easily disassembled, purified, reassembled, and reused, showing reproducible performance after recycling. The robustness, recyclability, versatility, and biocompatibility of the supramolecular membrane may open new avenues for manipulating biological systems. PMID:23675461

  16. Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.

    PubMed

    Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere

    2015-02-16

    The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology.

  17. Building Bridges: Biocatalytic C–C-Bond Formation toward Multifunctional Products

    PubMed Central

    2016-01-01

    Carbon–carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C–C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C–C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C–C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand. PMID:27398261

  18. Derivatization of single-walled carbon nanotubes with redox mediator for biocatalytic oxygen electrodes.

    PubMed

    Sadowska, K; Stolarczyk, K; Biernat, J F; Roberts, K P; Rogalski, J; Bilewicz, R

    2010-11-01

    Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected.

  19. Building Bridges: Biocatalytic C-C-Bond Formation toward Multifunctional Products.

    PubMed

    Schmidt, Nina G; Eger, Elisabeth; Kroutil, Wolfgang

    2016-07-01

    Carbon-carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C-C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C-C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C-C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand.

  20. Enzyme-Modified Particles for Selective Biocatalytic Hydrogenation by Hydrogen-Driven NADH Recycling

    PubMed Central

    Reeve, Holly A; Lauterbach, Lars; Lenz, Oliver; Vincent, Kylie A

    2015-01-01

    We describe a new approach to selective H2-driven hydrogenation that exploits a sequence of enzymes immobilised on carbon particles. We used a catalyst system that comprised alcohol dehydrogenase, hydrogenase and an NAD+ reductase on carbon black to demonstrate a greater than 98 % conversion of acetophenone to phenylethanol. Oxidation of H2 by the hydrogenase provides electrons through the carbon for NAD+ reduction to recycle the NADH cofactor required by the alcohol dehydrogenase. This biocatalytic system operates over the pH range 6–8 or in un-buffered water, and can function at low concentrations of the cofactor (10 μm NAD+) and at H2 partial pressures below 1 bar. Total turnover numbers >130 000 during acetophenone reduction indicate high enzyme stability, and the immobilised enzymes can be recovered by a simple centrifugation step and re-used several times. This offers a route to convenient, atom-efficient operation of NADH-dependent oxidoreductases for selective hydrogenation catalysis. PMID:26613009

  1. Biocatalytic Production of Trehalose from Maltose by Using Whole Cells of Permeabilized Recombinant Escherichia coli.

    PubMed

    Zheng, Zhaojuan; Xu, Ying; Sun, Ye; Mei, Wending; Ouyang, Jia

    2015-01-01

    Trehalose is a non-reducing disaccharide, which can protect proteins, lipid membranes, and cells from desiccation, refrigeration, dehydration, and other harsh environments. Trehalose can be produced by different pathways and trehalose synthase pathway is a convenient, practical, and low-cost pathway for the industrial production of trehalose. In this study, 3 candidate treS genes were screened from genomic databases of Pseudomonas and expressed in Escherichia coli. One of them from P. stutzeri A1501 exhibited the best transformation ability from maltose into trehalose and the least byproduct. Thus, whole cells of this recombinant E. coli were used as biocatalyst for trehalose production. In order to improve the conversion rate of maltose to trehalose, optimization of the permeabilization and biotransformation were carried out. Under optimal conditions, 92.2 g/l trehalose was produced with a high productivity of 23.1 g/(l h). No increase of glucose was detected during the whole course. The biocatalytic process developed in this study might serve as a candidate for the large scale production of trehalose.

  2. Limestone scrubbing for 2000 flue gas desulfurization system. Final report, October 1, 1993--April 1, 1997

    SciTech Connect

    1998-10-16

    As emission limits for sulfur dioxide from utility coal-fired boilers become lower due to increased regulation and environmental concern around the globe, power generating companies require increasingly cost-effective pollution control technology in order to maintain or reduce the cost of electricity to the end user. Limestone based wet flue gas desulfurization, or WFGD, is the preferred sulfur dioxide removal technology for utilities in the US and worldwide. This is a result of its extensive reference list, lower risks, and lower evaluated overall costs. For more than two decades ABB has supplied WFGD systems and currently has greater than 29,000 MWe of scrubbing capacity in operation. Given the industry`s ever-present need for lower costs, ABB funds a continuous research and development program focused on technology advancements that will reduce both capital and operating costs for its customers. As a result of this effort the LS-2 Concept WFGD System was developed through revolutionary design changes in every significant subprocess of conventional WFGD technology. To demonstrate the cumulative effects of all the individual advancements of the LS-2 Concept and to prove the process`s viability and cost-efficiency under representative US power plant conditions, the Limestone Scrubbing for 2000 project was initiated. This report is the final submittal to the Ohio Coal Development Office to document the results of this demonstrate project. The four-phase project execution, from the initial design and procurement through erection and extensive testing, proceeded as scheduled and on budget. The project resulted in a successful reference program that illustrates, in detail, the improved efficiencies and costs of the LS-2 advancements.

  3. Land application uses for dry flue gas desulfurization by-products. Executive summary

    SciTech Connect

    Dick, W.; Bigham, J.; Forster, R.; Hitzhusen, F.; Lal, R.; Stehouwer, R.; Traina, S.; Wolfe, W.; Haefner, R.; Rowe, G.

    1999-01-31

    Flue gas desulfurization (FGD) scrubbing technologies create several types of by-products. This project focused primarily on by-product materials obtained from what are commonly called ''dry scrubbers'' which produce a dry, solid material consisting of excess sorbent, reaction product that contains sulfate and sulfite, and coal fly ash. Prior to this project, dry FGD by-products were generally treated as solid wastes and disposed in landfills. However, landfill sites are becoming scarce and tipping fees are constantly increasing; The major objective of this project was to develop beneficial uses, via recycling, capable of providing economic benefits to both the producer and the end user of the FGD by-product. It is equally important, however, that the environmental impacts be carefully assessed so that the new uses developed are not only technically feasible but socially acceptable. Specific objectives developed for this project were derived over an 18-month period during extensive discussions with personnel from industry, regulatory agencies and research institutions. These were stated as follows: Objective 1: To characterize the material generated by dry FGD processes. Objective 2: To demonstrate the utilization of dry FGD by-product as a soil amendment on agricultural lands and on abandoned and active surface coal mines in Ohio. Objective 3: To demonstrate the use of dry FGD by-product as an engineering material for soil stabilization. Objective 4: To determine the quantities of dry FGD by-product that can be utilized in each of these applications. Objective 5. To determine the environmental and economic impacts of utilizing the material. Objective 6. To calibrate environmental, engineering, and economic models that can be used to determine the applicability and costs of utilizing these processes at other sites.

  4. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    SciTech Connect

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

    2015-05-15

    M{sub 2}(PcAN){sub 2} (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M{sub 2}(PcAN){sub 2}–W-HZSM-5) or the M{sub 2}(PcTN){sub 2} doping W-HZSM-5 (M{sub 2}(PcTN){sub 2}/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 and Cu{sub 2}(PcTN){sub 2}/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu{sub 2}(PcTN){sub 2}/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N{sub 2} adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed.

  5. Desulfurization of coal and petroleum. (Latest citations from the NTIS bibliographic database). Published Search

    SciTech Connect

    1996-04-01

    The bibliography contains citations concerning the desulfurization of coal, coal liquids, and crude oil. Flotation heap leaching, oxydesulfurization, metal oxide, microwave process, and chlorination are among the pre-combustion processes discussed. Coal liquefaction and gasification are only included if sulfur removal is stressed. Flue gas desulfurization and other post-combustion sulfur control processes are excluded. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

  6. Key factor in rice husk ash/CaO sorbent for high flue gas desulfurization activity

    SciTech Connect

    Irvan Dahlan; Keat Teong Lee; Azlina Harun Kamaruddin; Abdul Rahman Mohamed

    2006-10-01

    Siliceous materials such as rice husk ash (RHA) have potential to be utilized as high performance sorbents for the flue gas desulfurization process in small-scale industrial boilers. This study presents findings on identifying the key factor for high desulfurization activity in sorbents prepared from RHA. Initially, a systematic approach using central composite rotatable design was used to develop a mathematical model that correlates the sorbent preparation variables to the desulfurization activity of the sorbent. The sorbent preparation variables studied are hydration period, x{sub 1} (6-16 h), amount of RHA, x{sub 2} (5-15 g), amount of CaO, x{sub 3} (2-6 g), amount of water, x{sub 4} (90-110 mL), and hydration temperature, x{sub 5} (150-250{sup o}C). The mathematical model developed was subjected to statistical tests and the model is adequate for predicting the SO{sub 2} desulfurization activity of the sorbent within the range of the sorbent preparation variables studied. Based on the model, the amount of RHA, amount of CaO, and hydration period used in the preparation step significantly influenced the desulfurization activity of the sorbent. The ratio of RHA and CaO used in the preparation mixture was also a significant factor that influenced the desulfurization activity of the sorbent. A RHA to CaO ratio of 2.5 leads to the formation of specific reactive species in the sorbent that are believed to be the key factor responsible for high desulfurization activity in the sorbent. Other physical properties of the sorbent such as pore size distribution and surface morphology were found to have insignificant influence on the desulfurization activity of the sorbent. 31 refs., 5 figs., 3 tabs.

  7. Microbial reduction of SO{sub 2} and NO{sub x} as a means of by-product recovery/disposal from regenerable processes for the desulfurization of flue gas. Technical progress report, March 11, 1993--June 11, 1993

    SciTech Connect

    Sublette, K.L.

    1993-11-01

    There are two basic approaches to addressing the problem of SO{sub 2} and NO{sub x} emissions: (1) desulfurize (and denitrogenate) the feedstock prior to or during combustion; or (2) scrub the resultant SO{sub 2} and oxides of nitrogen from the boiler flue gases. The flue gas processing alternative has been addressed in this project via microbial reduction of SO{sub 2} and NO{sub x} by sulfate-reducing bacteria

  8. Full-scale utility FGD (flue gas desulfurization) system adipic acid demonstration program. Volume 1. Process results. Final report Jun 80-Nov 82

    SciTech Connect

    Hargrove, O.W. Jr; Colley, J.D.; Glover, R.L.; Owen, M.L.

    1983-06-01

    The report culminates a series of projects sponsored by the EPA, investigating the use of adipic acid as an additive to enhance SO/sub 2/ removal in aqueous flue gas desulfurization (FGD) systems, using limestone reagent. A 9-month program at the 194-MW Southwest Power Plant (SWPP) of City Utilities, Springfield, MO, demonstrated the effectiveness of adipic acid and dibasic acids (the latter, by-products of the production of adipic acid). The program examined the effect of adipic acid addition on a limestone FGD system under natural and forced-oxidation modes of operation.

  9. Full-scale utility FGD (flue gas desulfurization) system adipic acid demonstration program. Volume 2. Continuous emissions monitoring results. Final report Jun 80-Nov 82

    SciTech Connect

    Hargrove, O.W. Jr.; Colley, J.D.; Glover, R.L.; Owen, M.L.

    1983-06-01

    The report culminates a series of projects sponsored by the EPA, investigating the use of adipic acid as an additive to enhance SO/sub 2/ removal in aqueous flue gas desulfurization (FGD) systems, using limestone reagent. A 9-month program at the 194-MW Southwest Power Plant (SWPP) of City Utilities, Springfield, MO, demonstrated the effectiveness of adipic acid and dibasic acids (the latter, by-products of the production of adipic acid). The program examined the effect of adipic acid addition on a limestone FGD system under natural and forced-oxidation modes of operation.

  10. Mechanistic and kinetic studies of high-temperature coal gas desulfurization sorbents. Final report, July 1988--July 1991

    SciTech Connect

    Lew, S.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

    1991-10-01

    The overall objective of this project was to investigate the properties of and evaluate mixed oxides of zinc and titanium for hot fuel gas desulfurization. Uncombined ZnO was also investigated as a base case. Detailed investigation of the reduction and sulfidation reactions of Zn-Ti-O sorbents was performed. The intrinsic kinetics and the product layer diffusion rates in reduction and sulfidation were determined. Kinetic experiments with sorbents containing various Zn/Ti atomic ratios were performed. Chemical phase and structural transformations were followed by various methods. The results were compared to similar experiments performed with ZnO. The purpose of these experiments was to determine how the presence of titanium dioxide affects the reduction and sulfidation of ZnO. This information would be used to identify and select the sorbent composition that gives the best combination of low reduction rate and acceptable sulfidation performance at temperatures exceeding 600{degree}C. (VC)

  11. Agricultural use of a flue gas desulfurization by-product

    SciTech Connect

    Dick, W.; Chen, L.; Nelson, S. Jr.

    1998-12-31

    Few, if any, economical alternatives exist for operators of small coal-fired boilers that require a flue-gas desulfurization system which does not generate wastes. A new duct-injection technology called Fluesorbent has been developed to help fill this gap. Fluesorbent FGD was intentionally designed so that the saturated SO{sub 2}-sorbent materials would be valuable soil amendments for agricultural or turf-grass land. Agricultural and turf grass studies recently commenced using spent Fluesorbent materials from an FGD pilot program at an Ohio power plant. In the first year of testing, alfalfa yields on field plots with the FGD by-products were approximately 250% greater than on plots with no treatment, and about 40% greater than on plots treated with an equivalent amount of agricultural lime. Because the FGD by-products contained trace elements from included fly ash, the chemical composition of the alfalfa was significantly improved. Detailed yield and chemical data are presented.

  12. The durability of stabilized flue gas desulfurization sludge

    SciTech Connect

    Chen, X.; Wolfe, W.E.; Hargraves, M.D.

    1995-12-31

    The effects of freeze-thaw cycling on the strength and durability of samples of compacted, stabilized, wet flue gas desulfurization (FGD) by-products are reported. The results of laboratory tests show a clear relationship between higher water contents and increasing vulnerability to freeze-thaw effects. In the samples tested, water contents at or above 40% were characteristic of all the freeze-thaw specimens exhibiting low strengths. Lime content and curing time were also shown to have a marked influence on the durability of the FGD material. It was shown that samples can maintain good strength under freeze-thaw conditions provided 5% lime was added before compaction and the time from compaction to first freeze was at least 60 days.

  13. Washing tower for the desulfurization of flue gases

    SciTech Connect

    Stehning, W.

    1985-05-07

    A scrubber is provided with a grate in its sump through which oxygen is introduced to separate the oxidation zone above this grate from a reaction zone below the grate, a calcium containing additive being introduced into this reaction zone. Flue gas to be desulfurized is passed through a washing zone above the sump and there contacted with normally circulating scrubbing liquid containing the additive to absorb sulfur dioxide and sulfur trioxide. The sulfur dioxide is oxidized to sulfur trioxide and the additive induces precipitation of calcium sulfate in the sump. After a prolonged standstill, settled solids in the sump are induced into movement by drawing a portion of the sump liquid from an upper part thereof and injecting it into a lower part of the sump.

  14. Final report on agglomerate column flotation for cleaning and desulfurization of Ohio coal fines

    SciTech Connect

    Attia, Y.A.; El Zeky, M.; Yu, Mulong . Dept. of Materials Science and Engineering)

    1990-08-30

    The objective of this research program was investigate the feasibility of cleaning and desulfurization of Ohio coal by an agglomerate column flotation process, which integrates selective flocculation with conventional column flotation. It was concluded earlier on in the program that the conventional design of flotation column was not particularly efficient for pyrite rejection. A novel design for flotation column system was conceived and a prototype unit was manufactured and tested in the laboratory. Several design and operational parameters for the column and the agglomerate flotation process were briefly investigated to define proper design and working conditions for a satisfactory performance. The novel design was compared with conventional design of flotation column through laboratory tests and through published results. The role of selective flocculation of coal including selective depression of pyrite has been identified and tested with both novel and conventional design of flotation columns. The results of these brief investigations, which are summarized in this report, suggest that: (1) excellent performance ca n be obtained with agglomerate column flotation using the new design. For example, a raw coal containing 3.16% total sulfur, 2.11% pyritic sulfur, and 17% ash can be cleaned to 1.91 % ash, 0.42% pyritic sulfur, 1.32% total sulfur, while maintaining a projected Btu/coal recovery of 86% (mmmf basis). This is equivalent to 89% ash removal and 81% pyritic sulfur (58% total sulfur) rejection. (2) The novel design of flotation column is superior to conventional design particularly for pyrite rejection.

  15. Fixed bed testing of a molybdenum-promoted zinc titanate for hot gas desulfurization

    SciTech Connect

    Gasper-Galvin, L.D.; Mei, J.S.; Everitt, C.E.; Katta, S.

    1993-09-01

    The following conclusions were made, based upon this study of T-2535 molybdenum-promoted zinc titanate: (1) Results of the half-cycle sulfidation experiments showed that sorbent efficiency and capacity of this formulation of zinc titanate were weak functions of operating-bed temperature. Evidence of diffusion limitations on the sulfidation reaction were observed, particularly at superficial velocities greater than 30 cm/s (1 ft/s). Sorbent performance appeared to be affected by the concentration of reducing gases and/or water content of the simulated coal gas mixtures. Sorbent capacity and efficiency deteriorated during the first three cycles, but stabilized thereafter. (2) Sorbent spalling was observed and appeared to increase with sulfur loading. Possible causes of spalling may be attributed to the induced crystal lattice stresses due to the formation of ZnS and especially ZnSO{sub 4}, which have relative molar volumes that are approximately 1-1/2 and 3 times larger, respectively, than that of the original ZnO. (3) Based on these results, it is apparent that the molybdenum-promoted zinc titanate with Zn/Ti molar ratio of 1.91 may not be a suitable sorbent for hot gas desulfurization in the fixed bed reactor for the Pinon Pine project, due to problems with spalling and loss of reactivity during sulfidation/regeneration cycling.

  16. Cold-side desulfurization by humidification of fly ash in CFB boilers

    SciTech Connect

    Curran, R.A.; Tang, J.T.; Capan, S.F.; Fioriti, G.A.; Taylor, T.E.

    1995-12-31

    It is expected that sulfur emission regulations for fluidized bed boilers will continue to become more stringent. By capturing sulfur in-situ with furnace limestone injection, circulating fluidized bed (CFB) boilers have been quite successful in achieving capture efficiencies of up to 93%. However, CFB operating experience has shown that extending sulfur capture beyond this level results in a diminishing return relationship and requires a substantial increase in limestone consumption, especially for fuels with a relatively low (< 1.0%) sulfur content. Such an increase in limestone consumption can have numerous effects upon boiler design and performance, including: increased ash handling system requirements; higher operating cost of increased limestone consumption; increased NO{sub x} emissions; a detrimental effect upon SNCR performance, higher pH of ash leachate; and lower boiler efficiency. For future power generation projects, which are predicted to require increasingly higher sulfur capture efficiencies, the combination of the above listed conditions could result in a CFB boiler being cost-prohibitive in comparison to a pulverized coal boiler for a given coal. Clearly, CFB boilers will require a refined operating strategy, together with a consideration of auxiliary desulfurization technology, in order to remain competitive in the future energy equipment market.

  17. BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    Unknown

    1999-10-01

    The U.S. Department of Energy (DOE), Federal Energy Technology Center (FETC), is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal-derived fuel-gas) streams of integrated gasification combined-cycle (IGCC) power systems. The hot gas cleanup work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs. Hot-gas desulfurization research has focused on regenerable mixed-metal oxide sorbents that can reduce the sulfur in coal-derived fuel-gas to less than 20 ppmv and can be regenerated in a cyclic manner with air for multicycle operation. Zinc titanate (Zn{sub 2} TiO{sub 4} or ZnTiO{sub 3}), formed by a solid-state reaction of zinc oxide (ZnO) and titanium dioxide (TiO{sub 2}), is currently one of the leading sorbents. Overall chemical reactions with Zn{sub 2} TiO{sub 4} during the desulfurization (sulfidation)-regeneration cycle are shown below: Sulfidation: Zn{sub 2} TiO{sub 4} + 2H{sub 2}S {yields} 2ZnS + TiO{sub 2} + 2H{sub 2}O; Regeneration: 2ZnS + TiO{sub 2} + 3O{sub 2} {yields} Zn{sub 2} TiO{sub 4} + 2SO{sub 2} The sulfidation/regeneration cycle can be carried out in a fixed-bed, moving-bed, or fluidized-bed reactor configuration. The fluidized-bed reactor configuration is most attractive because of several potential advantages including faster kinetics and the ability to handle the highly exothermic regeneration to produce a regeneration offgas containing a constant concentration of SO{sub 2}.

  18. Biocatalytic Synthesis of Novel Partial Esters of a Bioactive Dihydroxy 4-Methylcoumarin by Rhizopus oryzae Lipase (ROL).

    PubMed

    Kumar, Vinod; Mathur, Divya; Srivastava, Smriti; Malhotra, Shashwat; Rana, Neha; Singh, Suraj K; Singh, Brajendra K; Prasad, Ashok K; Varma, Anjani J; Len, Christophe; Kuhad, Ramesh C; Saxena, Rajendra K; Parmar, Virinder S

    2016-11-09

    Highly regioselective acylation has been observed in 7,8-dihydroxy-4-methylcoumarin (DHMC) by the lipase from Rhizopus oryzae suspended in tetrahydrofuran (THF) at 45 °C using six different acid anhydrides as acylating agents. The acylation occurred regioselectively at one of the two hydroxy groups of the coumarin moiety resulting in the formation of 8-acyloxy-7-hydroxy-4-methylcoumarins, which are important bioactive molecules for studying biotansformations in animals, and are otherwise very difficult to obtain by only chemical steps. Six monoacylated, monohydroxy 4-methylcoumarins have been biocatalytically synthesised and identified on the basis of their spectral data and X-ray crystal analysis.

  19. Enzyme-functionalized polymer brush films on the inner wall of silicon-glass microreactors with tunable biocatalytic activity.

    PubMed

    Costantini, Francesca; Benetti, Edmondo M; Reinhoudt, David N; Huskens, Jurriaan; Vancso, G Julius; Verboom, Willem

    2010-12-21

    The lipase from Candida Rugosa was immobilized to a poly(methacrylic acid) polymer brush layer, grown on the inner wall of silicon-glass microreactors. The hydrolysis of 4-nitrophenyl acetate was used as a model reaction to study the activity of this biocatalytic system. The amount of bound lipase could be tuned by changing the polymerization time of the brush formation. The Michaelis-Menten constants and V(max) values, determined for immobilized and free lipase, are similar, demonstrating that the lipase's substrate affinity and its activity remain unchanged upon immobilization to the microchannel wall.

  20. Biocatalytic Asymmetric Alkene Reduction: Crystal Structure and Characterization of a Double Bond Reductase from Nicotiana tabacum

    PubMed Central

    2013-01-01

    The application of biocatalysis for the asymmetric reduction of activated C=C is a powerful tool for the manufacture of high-value chemical commodities. The biocatalytic potential of “-ene” reductases from the Old Yellow Enzyme (OYE) family of oxidoreductases is well-known; however, the specificity of these enzymes toward mainly small molecule substrates has highlighted the need to discover “-ene” reductases from different enzymatic classes to broaden industrial applicability. Here, we describe the characterization of a flavin-free double bond reductase from Nicotiana tabacum (NtDBR), which belongs to the leukotriene B4 dehydrogenase (LTD) subfamily of the zinc-independent, medium chain dehydrogenase/reductase superfamily of enzymes. Using steady-state kinetics and biotransformation reactions, we have demonstrated the regio- and stereospecificity of NtDBR against a variety of α,β-unsaturated activated alkenes. In addition to catalyzing the reduction of typical LTD substrates and several classical OYE-like substrates, NtDBR also exhibited complementary activity by reducing non-OYE substrates (i.e., reducing the exocyclic C=C double bond of (R)-pulegone) and in some cases showing an opposite stereopreference in comparison with the OYE family member pentaerythritol tetranitrate (PETN) reductase. This serves to augment classical OYE “-ene” reductase activity and, coupled with its aerobic stability, emphasizes the potential industrial value of NtDBR. Furthermore, we also report the X-ray crystal structures of the holo-, binary NADP(H)-bound, and ternary [NADP+ and 4-hydroxy-3-methoxycinnamaldehyde (9a)-bound] NtDBR complexes. These will underpin structure-driven site-saturated mutagenesis studies aimed at enhancing the reactivity, stereochemistry, and specificity of this enzyme. PMID:27547488

  1. [Experimental investigation of nano-TiO2 on combustion and desulfurization Catalysis].

    PubMed

    Wang, Shu-qin; Zhao, Yi; Tan, Qian; Xu, Pei-yao

    2008-02-01

    Experiment research of nanometer TiO2 catalytic combustion to CaO desulfurization was studied. Desulfurization effect was measured by the composition analysis of fly ash after combustion and the content of SO2 in flue gas. The effects of analytical grade CaO desulfurization by nanometer TiO2 addition, Ca/S molar ratio, nanometer TiO2 that was prepared at different conditions and combustion temperature were discussed. Desulfurization effects were compared with different coals and Ca-base agents by nanometer TiO2 addition. The reaction products wereanalyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) analysis. The combustion desulfurization mechanisms of CaO by nanometer TiO2 addition were discussed. The experiment results show that nanometer TiO2 has good catalytic effect to CaO combustion desulfurization. When nanometer TiO2 was added together with CaO, the optimal addition dosage of nanometer TiO2 is 8%, Ca/S molar ratio is 2 and the combustion temperature is 850 degrees C. The desulfurization efficiency of analytical and industrial grade CaO catalyzed by nanometer TiO2 can achieve to 87.8% and 60.3%, and it increased 13.4% and 29.6% than that without nanometer TiO2. The pore diameter and surface area of different coal ashes with nano-TiO2 addition increase because of the active centers of nano-TiO2 surface which are helpful to the diffusion of SO2 and reaction of SO2 to SO3 and increase the desulphurization efficiency of CaO.

  2. Peroxidase-active cell free extract from onion solid wastes: biocatalytic properties and putative pathway of ferulic acid oxidation.

    PubMed

    El Agha, Ayman; Makris, Dimitris P; Kefalas, Panagiotis

    2008-09-01

    The exploitation of food residuals can be a major contribution in reducing the polluting load of food industry waste and in developing novel added-value products. Plant food residues including trimmings and peels might contain a range of enzymes capable of transforming bioorganic molecules, and thus they may have potential uses in several biocatalytic processes, including green organic synthesis, modification of food physicochemical properties, bioremediation, etc. Although the use of bacterial and fungal enzymes has gained attention in studies pertaining to biocatalytic applications, plant enzymes have been given less consideration or even disregarded. Therefore, we investigated the use of a crude peroxidase preparation from solid onion by-products for oxidizing ferulic acid, a widespread phenolic acid, various derivatives of which may occur in food wastes. The highest enzyme activity was observed at a pH value of 4, but considerable activity was retained up to a pH value of 6. Favorable temperatures for increased activity varied between 20-40 degrees C, 30 degrees C being the optimal. Liquid chromatography-mass spectrometry analysis of a homogenate/H(2)O(2)-treated ferulic acid solution showed the formation of a dimer as a major oxidation product.

  3. Molecular biological enhancement of coal desulfurization: Cloning and expression of the sulfoxide/sulfone/sulfonate/sulfate genes in Pseudomonads and Thiobacillae. [Rhodococcus erythropolis, Thiobacillus acidophilus, Thiobacillus novellus

    SciTech Connect

    Krawiec, S.

    1992-01-01

    Research continues on desulfurization of coal using microorganisms. Topics reported on this quarter include: desulfurization with N1-36 (presumptively identified as Rhodochrous erythropolis), pulsed-field gel electrophoresis of chromosomal DNA's of Thiobacillus spp., and fresh isolates with the presumptive capacity to desulfurize dibenzothiophenes.

  4. Molecular biological enhancement of coal desulfurization: Cloning and expression of the sulfoxide/sulfone/sulfonate/sulfate genes in Pseudomonads and Thiobacillae. Eleventh quarterly report

    SciTech Connect

    Krawiec, S.

    1992-08-01

    Research continues on desulfurization of coal using microorganisms. Topics reported on this quarter include: desulfurization with N1-36 (presumptively identified as Rhodochrous erythropolis), pulsed-field gel electrophoresis of chromosomal DNA`s of Thiobacillus spp., and fresh isolates with the presumptive capacity to desulfurize dibenzothiophenes.

  5. Desulfurization of coal with hydroperoxides of vegetable oils. Technical progress report, March 1--May 31, 1995

    SciTech Connect

    Smith, G.V.; Gaston, R.D.; Song, R.; Cheng, J.; Shi, Feng; Gholson, K.L.

    1995-12-31

    This project proposes a new method for removing organic sulfur from Illinois coals using readily available farm products. It proposes to use air and vegetable oils to disrupt the coal matrix, oxidize sulfur forms, increase volatiles, and desulfurize coal. This will be accomplished by impregnating coals with polyunsaturated oils, converting the oils to their hydroperoxides, and heating. Since these oils are relatively inexpensive and easily applied, this project could lead to a cost effective method for removing organic sulfur from coals. Moreover, the oils are environmentally safe; they will produce no noxious products and will improve burning qualities of solid products. Preliminary experiments showed that IBC 104 coal catalyzes the formation of hydroperoxides in safflower oil and that more sulfur is extracted from the treated than untreated coal. During the first quarter the requirement of an added photosensitizer was eliminated, the catalytic effect of coal was confirmed, and the existence of a complex set of reactions was revealed. During the second quarter, working with IBC-108 coal (2.3% organic S, 0.4% pyrite S), the effects of different extraction solvents were examined. A new pretreatment which combines alkali with linseed oil was discovered. Best organic sulfur removal is approximately 26% using alkali pretreatment combined with linseed oil at 100[degrees]C. BTU loses can be kept to a minimum of 3% with proper use of solvents. During this third quarter the effects of different ratios of oil:coal, different temperatures, and different reaction times were completely examined. The effects of alkali on sulfur removal were further investigated. Best organic sulfur removal reaches 34% using ammonia pretreatment, then oil and finally aqNA2CO3 extraction.

  6. Advanced sulfur control concepts in hot-gas desulfurization technology. Quarterly report, April--June 1994

    SciTech Connect

    Harrison, D.P.

    1994-07-01

    The primary objective of this research project is the direct production of elemental sulfur during the regeneration of known high temperature desulfurization sorbents. The contract was awarded to LSU on April 12, 1994, and this quarterly report covers accomplishments during the first 2 1/2 months of the project. Effort during the initial 2 1/2 month period has been limited to Tasks 1 and 2, and involves a search of the literature to identify concepts for producing elemental sulfur during regeneration of known metal oxide sorbents and a thermodynamic evaluation of these concepts. While searching and evaluating the literature is a continuing process, concentrated effort on that phase is now complete and a detailed summary is included in this report. Three possible concepts for the direct production of elemental sulfur were identified in the LSU proposal, and the literature search has not uncovered any additional concepts. Thus, the three concepts being investigated involve: (1) regeneration with SO{sub 2}, (2) regeneration with mixtures Of 02 and H{sub 2}O, and (3) regeneration with H{sub 2}O. While concept (3) directly produces H{sub 2}S instead of elemental sulfur, the concept is included because the possibility exists for converting H{sub 2}S to elemental sulfur using the Claus process. Each of the concepts will ultimately be compared to the Direct Sulfur Recovery Process (DSRP) under development by RTI. DSRP involves initial sorbent regeneration to SO{sub 2}, and the inclusion of additional processing steps to reduce the SO{sub 2} to elemental sulfur.

  7. Simultaneous desulfurization and denitrification by microwave reactor with ammonium bicarbonate and zeolite.

    PubMed

    Wei, Zaishan; Lin, Zhehang; Niu, Hejingying; He, Haiming; Ji, Yongfeng

    2009-03-15

    Microwave reactor with ammonium bicarbonate (NH(4)HCO(3)) and zeolite was set up to study the simultaneous removal of sulfur dioxide (SO(2)) and nitrogen oxides (NO(x)) from flue gas. The results showed that the microwave reactor filled with NH(4)HCO(3) and zeolite could reduce SO(2) to sulfur with the best desulfurization efficiency of 99.1% and reduce NO(x) to nitrogen with the best NO(x) purifying efficiency of 86.5%. Microwave desulfurization and denitrification effect of the experiment using ammonium bicarbonate and zeolite together is much higher than that using ammonium bicarbonate or zeolite only. NO(x) concentration has little effect on denitrification but has no influence on desulfurization, SO(2) concentration has no effect on denitrification. The optimal microwave power and empty bed residence time (EBRT) on simultaneous desulfurization and dentrification are 211-280 W and 0.315 s, respectively. The mechanism for microwave reduced desulfurization and denitrification can be described as the microwave-induced catalytic reduction reaction between SO(2), NO(x) and ammonium bicarbonate with zeolite being the catalyst and microwave absorbent.

  8. Roles of Electrolyte Characterization on Bauxite Electrolysis Desulfurization with Regeneration and Recycling

    NASA Astrophysics Data System (ADS)

    Gong, Xuzhong; Wang, Zhi; Zhuang, Siyuan; Wang, Dong; Wang, Yuhua; Wang, Mingyong

    2017-02-01

    The recycling of NaCl used as supporting electrolyte for bauxite electrolysis was carried out in this study. The electrolyte was regenerated by adding anhydrous CaCl2 into the solution after filtration, and effects of electrolyte characterization on bauxite electrolysis were examined by observing the change in desulfurization ratio and cell voltage. The results indicated that the desulfurization ratio increased with increasing recycling times of electrolyte. In the meantime, the increase in recycling times has led to the decrease in pH value as well as the increase in Fe ion concentration in the electrolyte, which were the main reasons for the increase in the desulfurization ratio with increasing recycling of electrolyte. The pH value of electrolyte after second electrolysis was lower than 1.5, and the desulfurization ratio increased obviously due to the increase in Fe3+ concentration and suppression of jarosite formation. The increase in Ca2+ concentration did not apparently change desulfurization ratio and anode surface activity. However, with Ca2+ addition, the cathode surface was covered by CaSO4·nH2O, thus resulting in the increase of cell voltage.

  9. Engineering the microstructure and permeability of thin multilayer latex biocatalytic coatings containing E. coli.

    PubMed

    Lyngberg, O K; Ng, C P; Thiagarajan, V; Scriven, L E; Flickinger, M C

    2001-01-01

    The microstructure and permeability of rehydrated 20-100 microm thick partially coalesced (vinyl-actetate acrylic copolymer) SF091 latex coatings and a 118 microm thick model trilayer biocatalytic coating consisting of two sealant SF091 layers containing a middle layer of viable E. coli HB101 + latex were studied as delaminated films in a diffusion apparatus with KNO(3) as the diffussant. The permeability of the hydrated coatings is due to diffusive transport through the pore space between the partially coalesced SF091 latex particles. Coating microstructure was visualized by fast freeze cryogenic scanning electron microscopy (cryo-SEM). The effective diffusion coefficient of SF091 latex coatings (diffusive permeability/film thickness) was determined as the ratio of the effective diffusivity of KNO(3) to its diffusivity in water (D(eff)/D). Polymer particle coalescence was arrested by two methods to increase coating permeability. The first used glycerol with coating drying at 4 degrees C, near the glass transition temperature (T(g)). The second method used sucrose or trehalose as a filler to arrest coalescence; the filler was then dissolved away. D(eff)/D was measured as a function of film thickness; content of glycerol, sucrose, and trehalose; drying time; and rehydration time. D(eff)/D varied from 3 x 10(-4) for unmodified SF091 coatings to 6.8 x 10(-2) for coatings containing sucrose. D(eff)/D was reduced by the flattening of latex particles against the surface of the solid substrate, as well as by the presence of the colloid stabilizer hydroxyethylcellulose (HEC). When corrected for the flattened particle layer, D(eff)/D of HEC-free coatings was as high as 0.20, which agreed with the value predicted from analysis of cryo-SEM images of the coat surface. D(eff)/D decreased by one-half in approximately 5 days in rehydrated SF091 coatings, indicating that significant wet coalescence occurs after glycerol, sucrose, or trehalose are leached from the films. D

  10. Characteristics of pneumatically-emplaced dry flue gas desulfurization materials

    SciTech Connect

    Carter, S.D.; Rathbone, R.F.; Graham, U.M.; Robl, T.L.

    1996-12-31

    The University of Kentucky in collaboration with the Department of Energy, Addington, Inc. and Costain Coal is currently developing a commercial concept for the haul back of dry flue gas desulfurization materials (FGDM) into highwall mine adits. The University`s Center for Applied Energy Research (CAER) is investigating emplacement systems for a mine demonstration which is planned for the third quarter of 1996. A laboratory-scale transport system has been built at the CAER to evaluate the potential of pneumatic transport for FGDM emplacement. The system is modeled after shotcreting systems in which water is mixed with cement (FGDM) in a nozzle at the end of the pneumatic pipe. Solids travel approximately 70 ft in the lab-scale system at a rate of up to 6 lb FGDM/minute prior to impingement onto a sample collector. Prehydrated FGDM from a circulating fluidized bed combustor has been successfully emplaced onto vertically positioned sample surfaces without excessive dust liberation. The test program is focussed on determining the pneumatic conditions necessary to maximize the strength of the emplaced FGDM under anticipated mine curing conditions while minimizing dust formation. The mineralogy and strength of a pneumatically created sample are described following curing for 60 days.

  11. Coal desulfurization by a microwave process. Technical progress report

    SciTech Connect

    Zavitsanos, P.D.; Golden, J.A.; Bleiler, K.W.

    1982-01-01

    Desulfurization experiments have been carried out using the moving bed flow reactor to examine the following: (1) hardgrove grindability index of microwave treated coal compared with raw coal; (2) washability of microwave treated coal compared with raw coal; (3) the extent of sulfur and ash removal from alkali/coal treated samples. In the washability experiments, the following treatment sequence was carried out: expose raw coal (1-2'' size) to microwaves (2 kW power level, 120 to 240 sec exposure); crush (30 to 200 mesh); float/sink (1.6 S.G.). Sulfur, ash and CV measurements were made on the float fractions for comparison with similar measurements on raw coal float samples prepared in the same way as microwave treated samples. Table 2 is a summary of the sulfur, ash and calorific value analyses comparing washed with raw coal samples. These data were used to calculate percent energy recovery as shown in the table. It is not possible to conclude from the data taken to date whether there is beneficiation from microwave treated-washed coal since two coals showed increased energy recovery and two did not. Additional washability data will be taken to pursue this question.

  12. Microbial communities associated with wet flue gas desulfurization systems

    PubMed Central

    Brown, Bryan P.; Brown, Shannon R.; Senko, John M.

    2012-01-01

    Flue gas desulfurization (FGD) systems are employed to remove SOx gasses that are produced by the combustion of coal for electric power generation, and consequently limit acid rain associated with these activities. Wet FGDs represent a physicochemically extreme environment due to the high operating temperatures and total dissolved solids (TDS) of fluids in the interior of the FGD units. Despite the potential importance of microbial activities in the performance and operation of FGD systems, the microbial communities associated with them have not been evaluated. Microbial communities associated with distinct process points of FGD systems at several coal-fired electricity generation facilities were evaluated using culture-dependent and -independent approaches. Due to the high solute concentrations and temperatures in the FGD absorber units, culturable halothermophilic/tolerant bacteria were more abundant in samples collected from within the absorber units than in samples collected from the makeup waters that are used to replenish fluids inside the absorber units. Evaluation of bacterial 16S rRNA genes recovered from scale deposits on the walls of absorber units revealed that the microbial communities associated with these deposits are primarily composed of thermophilic bacterial lineages. These findings suggest that unique microbial communities develop in FGD systems in response to physicochemical characteristics of the different process points within the systems. The activities of the thermophilic microbial communities that develop within scale deposits could play a role in the corrosion of steel structures in FGD systems. PMID:23226147

  13. Enhanced durability of desulfurization sorbents for fluidized-bed applications

    SciTech Connect

    Gupta, R.P.; Gangwal, S.K.

    1991-06-01

    Advanced integrated gasification combined cycle (IGCC) power systems require the development of high-temperature desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier down to very low levels. The objective of this investigation was to identify and demonstrate methods for enhancing the long-term chemical reactivity and mechanical strength of zinc ferrite, a leading regenerable sorbent, for fluidized-bed applications. Fluidized sorbent beds offer significant potential in IGCC systems because of their ability to control the highly exothermic regeneration involved. However, fluidized beds require a durable, attrition-resistant sorbent in the 100--300 {mu}m size range. A bench-scale high-temperature, high- pressure (HTHP) fluidized-bed reactor (7.6-cm I.D.) system capable of operating up to 24 atm and 800{degree}C was designed, built and tested. A total of 175 sulfidation-regeneration cycles were carried out using KRW-type coal gas with various zinc ferrite formulations. A number of sorbent manufacturing techniques including spray drying, impregnation, crushing and screening, and granulation were investigated. While fluidizable sorbents prepared by crushing durable pellets and screening had acceptable sulfur capacity, they underwent excessive attrition during multicycle testing. The sorbent formulations prepared by a proprietary technique were found to have excellent attrition resistance and acceptable chemical reactivity during multicycle testing. However, zinc ferrite was found to be limited to 550{degree}C, beyond which excessive sorbent weakening due to chemical transformations, e.g., iron oxide reduction, was observed.

  14. Producing ammonium sulfate from flue gas desulfurization by-products

    USGS Publications Warehouse

    Chou, I.-Ming; Bruinius, J.A.; Benig, V.; Chou, S.-F.J.; Carty, R.H.

    2005-01-01

    Emission control technologies using flue gas desulfurization (FGD) have been widely adopted by utilities burning high-sulfur fuels. However, these technologies require additional equipment, greater operating expenses, and increased costs for landfill disposal of the solid by-products produced. The financial burdens would be reduced if successful high-volume commercial applications of the FGD solid by-products were developed. In this study, the technical feasibility of producing ammonium sulfate from FGD residues by allowing it to react with ammonium carbonate in an aqueous solution was preliminarily assessed. Reaction temperatures of 60, 70, and 80??C and residence times of 4 and 6 hours were tested to determine the optimal conversion condition and final product evaluations. High yields (up to 83%) of ammonium sulfate with up to 99% purity were achieved under relatively mild conditions. The optimal conversion condition was observed at 60??C and a 4-hour residence time. The results of this study indicate the technical feasibility of producing ammonium sulfate fertilizer from an FGD by-product. Copyright ?? Taylor & Francis Inc.

  15. Microbial communities associated with wet flue gas desulfurization systems.

    PubMed

    Brown, Bryan P; Brown, Shannon R; Senko, John M

    2012-01-01

    Flue gas desulfurization (FGD) systems are employed to remove SO(x) gasses that are produced by the combustion of coal for electric power generation, and consequently limit acid rain associated with these activities. Wet FGDs represent a physicochemically extreme environment due to the high operating temperatures and total dissolved solids (TDS) of fluids in the interior of the FGD units. Despite the potential importance of microbial activities in the performance and operation of FGD systems, the microbial communities associated with them have not been evaluated. Microbial communities associated with distinct process points of FGD systems at several coal-fired electricity generation facilities were evaluated using culture-dependent and -independent approaches. Due to the high solute concentrations and temperatures in the FGD absorber units, culturable halothermophilic/tolerant bacteria were more abundant in samples collected from within the absorber units than in samples collected from the makeup waters that are used to replenish fluids inside the absorber units. Evaluation of bacterial 16S rRNA genes recovered from scale deposits on the walls of absorber units revealed that the microbial communities associated with these deposits are primarily composed of thermophilic bacterial lineages. These findings suggest that unique microbial communities develop in FGD systems in response to physicochemical characteristics of the different process points within the systems. The activities of the thermophilic microbial communities that develop within scale deposits could play a role in the corrosion of steel structures in FGD systems.

  16. SCALE-UP OF ADVANCED HOT-GAS DESULFURIZATION SORBENTS

    SciTech Connect

    K. JOTHIMURUGESAN; S.K. GANGWAL

    1998-03-01

    The objective of this study was to develop advanced regenerable sorbents for hot gas desulfurization in IGCC systems. The specific objective was to develop durable advanced sorbents that demonstrate a strong resistance to attrition and chemical deactivation, and high sulfidation activity at temperatures as low as 343 C (650 F). Twenty sorbents were synthesized in this work. Details of the preparation technique and the formulations are proprietary, pending a patent application, thus no details regarding the technique are divulged in this report. Sulfidations were conducted with a simulated gas containing (vol %) 10 H{sub 2}, 15 CO, 5 CO{sub 2}, 0.4-1 H{sub 2}S, 15 H{sub 2}O, and balance N{sub 2} in the temperature range of 343-538 C. Regenerations were conducted at temperatures in the range of 400-600 C with air-N{sub 2} mixtures. To prevent sulfation, catalyst additives were investigated that promote regeneration at lower temperatures. Characterization were performed for fresh, sulfided and regenerated sorbents.

  17. Apparatus and method for the desulfurization of petroleum by bacteria

    DOEpatents

    Lizama, Hector M.; Scott, Timothy C.; Scott, Charles D.

    1995-01-01

    A method for treating petroleum with anaerobic microorganisms acting as biocatalysts that can remove sulfur atoms from hydrocarbon molecules, under anaerobic conditions, and then convert the sulfur atoms to hydrogen sulfide. The microorganisms utilized are from the family known as the "Sulfate Reducing Bacteria." These bacteria generate metabolic energy from the oxidation of organic compounds, but use oxidized forms of sulfur as an electron acceptor. Because the biocatalyst is present in the form of bacteria in an aqueous suspension, whereas the reacting substrate consists of hydrocarbon molecules in an organic phase, the actual desulfurization reaction takes place at the aqueous-organic interphase. To ensure adequate interfacial contacting and mass transfer, a biphasic electrostatic bioreactor system is utilized. The bioreactor is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the sulfur. High-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the sulfur to produce hydrogen sulfide which is then removed from the bioreactor. The organic liquid, now free of the sulfur, is ready for immediate use or further processing.

  18. Apparatus and method for the desulfurization of petroleum by bacteria

    DOEpatents

    Lizama, H.M.; Scott, T.C.; Scott, C.D.

    1995-10-17

    A method is described for treating petroleum with anaerobic microorganisms acting as biocatalysts that can remove sulfur atoms from hydrocarbon molecules, under anaerobic conditions, and then convert the sulfur atoms to hydrogen sulfide. The microorganisms utilized are from the family known as the ``Sulfate Reducing Bacteria``. These bacteria generate metabolic energy from the oxidation of organic compounds, but use oxidized forms of sulfur as an electron acceptor. Because the biocatalyst is present in the form of bacteria in an aqueous suspension, whereas the reacting substrate consists of hydrocarbon molecules in an organic phase, the actual desulfurization reaction takes place at the aqueous-organic interphase. To ensure adequate interfacial contacting and mass transfer, a biphasic electrostatic bioreactor system is utilized. The bioreactor is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the sulfur. High-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the sulfur to produce hydrogen sulfide which is then removed from the bioreactor. The organic liquid, now free of the sulfur, is ready for immediate use or further processing. 5 figs.

  19. Ultrasound-assisted oxidative desulfurization of bunker-C oil using tert-butyl hydroperoxide.

    PubMed

    Tang, Qiong; Lin, Song; Cheng, Ying; Liu, Sujun; Xiong, Jun-Ru

    2013-09-01

    This work investigated the ultrasonic assisted oxidative desulfurization of bunker-C oil with TBHP/MoO3 system. The operational parameters for the desulfurization procedure such as ultrasonic irradiation time, ultrasonic wave amplitude, catalyst initial concentration and oxidation agent initial concentration were studied. The experimental results show that the present oxidation system was very efficient for the desulfurization of bunker-C oil and ~35% sulfur was removed which was dependent on operational parameters. The application of ultrasonic irradiation allowed sulfur removal in a shorter time. The stronger the solvent polarity is, the higher the sulfur removal rate, but the recovery rate of oil is lower. The sulfur compounds in bunker-C oil reacted with TBHP to produce corresponding sulfoxide, and further oxidation produced the corresponding sulfone.

  20. Sulfur-selective desulfurization of dibenzothiophene and diesel oil by newly isolated Rhodococcus sp. strains.

    PubMed

    Castorena, Gladys; Suárez, Claudia; Valdez, Idania; Amador, Guadalupe; Fernández, Luis; Le Borgne, Sylvie

    2002-09-24

    New desulfurizing bacteria able to convert dibenzothiophene into 2-hydroxybiphenyl and sulfate were isolated from contaminated soils collected in Mexican refineries. Random amplified polymorphic DNA analysis showed they were different from previously reported Rhodococcus erythropolis desulfurizing strains. According to 16S rRNA gene sequencing and fatty acid analyses, these new isolates belonged to the genus Rhodococcus. These strains could desulfurize 4,6-dimethyldibenzothiophene which is one of the most difficult dibenzothiophene derivatives to remove by hydrodesulfurization. A deeply hydrodesulfurized diesel oil containing significant amounts of 4,6-dimethyldibenzothiophene was treated with Rhodococcus sp. IMP-S02 cells. Up to 60% of the total sulfur was removed and all the 4,6-dimethyldibenzothiophene disappeared as a result of this treatment.

  1. Identification and cloning of genes involved in specific desulfurization dibenzothiophene by Rhodococcus sp. strain IGTS8

    SciTech Connect

    Denome, S.A.; Young, K.D.; Olson, E.S. )

    1993-09-01

    The presence of sulfur in coal and petroleum contributes to corrosion of production and refining equipment and burning these high-sulfur products emits sulfur oxides to the atmosphere. Microorganisms that can enzymatically release organically bound sulfur from organic components of coal or petroleum or from dibenzothiophene (DBT) could reduce the sulfur content of high sulfur fuels without depleting their British thermal unit value. Two major pathways for microbial metabolism of DBT have been proposed. Some of the genes for the DPT degradative pathway have been isolated and characterized. However, no genes for the desulfurization pathway have been identified. This paper reports the isolation from Rhodoccus sp. strain IGTS8 pf a set of genes that confer a specific desulfurization phenotype to mutants and to a related organism, R. fascians D188-5, that is normally unable to desulfurize DBT. 38 refs., 2 figs., 1 tab.

  2. Molecular biology of coal bio-desulfurization. Quarterly technical progress report, January 1--March 31, 1992

    SciTech Connect

    Young, K.D.; Gallagher, J.R.

    1992-04-30

    Genes cloned from Rhodococcus rhodochrous IGTS8 can transfer the DBT desulfurization phenotype to a different species (R. Fascians). The product was identified as 2-phenylphenol by gas chromatography. This result parallels the results we have previously reported for the activity of these genes in a DBT-negative mutant of IGTS8. Thus, the evidence is strong that we have identified and cloned the entire set of genes that are responsible for this very specific desulfurization reaction. Sequencing of these genes has commenced. A genomic library was constructed from the bacterium, Besulfovibrio desulfuricans. Screening has not yet identified a clone that carries the desulfurization genes from that organism. Two open reading frames, doxH and doxJ, in the C18 DBT degradation pathway were mutated and are now believed to be dispensable to that pathway. Finally, progress was made toward beginning to sequence the DBT dixoygenase genes from strain A15.

  3. Molecular biology of coal bio-desulfurization. [Rhodococcus rhodochrous, Desulfovibrio desulfuricans

    SciTech Connect

    Young, K.D.; Gallagher, J.R.

    1992-04-30

    Genes cloned from Rhodococcus rhodochrous IGTS8 can transfer the DBT desulfurization phenotype to a different species (R. Fascians). The product was identified as 2-phenylphenol by gas chromatography. This result parallels the results we have previously reported for the activity of these genes in a DBT-negative mutant of IGTS8. Thus, the evidence is strong that we have identified and cloned the entire set of genes that are responsible for this very specific desulfurization reaction. Sequencing of these genes has commenced. A genomic library was constructed from the bacterium, Besulfovibrio desulfuricans. Screening has not yet identified a clone that carries the desulfurization genes from that organism. Two open reading frames, doxH and doxJ, in the C18 DBT degradation pathway were mutated and are now believed to be dispensable to that pathway. Finally, progress was made toward beginning to sequence the DBT dixoygenase genes from strain A15.

  4. Evaluation of sulfur-reducing microorganisms for organic desulfurization. [Pyrococcus furiosus

    SciTech Connect

    Miller, K.W.

    1991-01-01

    Because of substantial portion of the sulfur in Illinois coal is organic, microbial desulfurization of sulfidic and thiophenic functionalities could hold great potential for completing pyritic sulfur removal. We are testing the hypothesis that organic sulfur can be reductively removed as H{sub 2}S through the activities of anaerobic microorganisms. Our objectives for this year include the following: (1) To obtain cultures that will reductively desulfurize thiophenic model compounds. In addition to crude oil enrichments begun last year, we sampled municipal sewage sludge. (2) To continue to work toward optimizing the activity of the DBDS-reducing cultures obtained during the previous year. (3) To expand coal desulfurization work to include other coals including Illinois Basin Coal 101 and a North Dakota lignite, which might be more susceptible to the dibenzyldisulfide reducing cultures due to its lower rank. (4) To address the problem of sulfide sorption, by investigating the sorption capacity of coals in addition to Illinois Basin Coal 108.

  5. Development and testing of regenerable hot-coal-gas desulfurization sorbents

    SciTech Connect

    Grindley, T.; Steinfeld, G.

    1981-10-01

    Investigations over several years at the Morgantown Energy Technology Center have been concerned with the development of a regenerable metal oxide desulfurization sorbent which would function on hot coal-derived fuel gas. In the latest phase of testing, a combination of zinc oxide with iron oxide as zinc ferrite has produced a sorbent which has demonstrated regenerability and capability of removing sulfur from simulated hot coal gas to a level of 1 to 10 ppM by volume. The principal finding at this stage of the project is that the compound zinc ferrite and also iron oxide containing some zinc ferrite have hydrogen sulfide absorption performances very similar to those of zinc oxide. Extruded sorbents made from these compounds have been demonstrated to perform with varying ability in the temperature range 800/sup 0/F (427/sup 0/C) to 1400/sup 0/F (760/sup 0/C) at a space velocity of 2000 hourly and a hydrogen sulfide concentration of 2.7 percent. They have also been shown to be regenerable with a 50/50 percent v/v steam-air mixture at 1000/sup 0/F (538/sup 0/C) and 600 hourly space velocity with no loss of absorptive power. Both zinc ferrite and zinc oxide appear to perform optimally in the middle of the temperature range, where absorption capacity is greatest. Surprisingly, the experimental results indicate no trend to a lower degree of hydrogen sulfide removal with rise in temperature. Zinc ferrite appears to be superior to zinc oxide in terms of its absorption capacity and resistance to sintering at higher temperatures.

  6. Marketable products from gypsum, a coal combustion byproduct derived from a wet flue gas desulfurization process

    SciTech Connect

    Chou, M.I.M.; Ghiassi, K.; Lytle, J.M.; Chou, S.J.; Banerjee, D.D.

    1998-07-01

    For two years the authors have been developing a process to produce two marketable products, ammonium sulfate fertilizer and precipitated calcium carbonate (PCC), from wet limestone flue gas desulfurization (FGD) by-product gypsum. Phase 1 of the project focused on the process for converting FGD-gypsum to ammonium sulfate fertilizer with PCC produced as a by-product during the conversion. Early cost estimates suggested that the process was economically feasible when granular size ammonium sulfate crystals were produced. However, sale of the by-product PCC for high-value commercial application could further improve the economics of the process. The results of their evaluation of the market potential of the PCC by-product are reported in this paper. The most significant attributes of carbonate fillers that determine their usefulness in industry are particle size (i.e, fineness) and shape, whiteness (brightness), and mineralogical and chemical purity. The PCC produced from the FGD dypsum obtained from the Abbott Power Plant at the University of Illinois Urbana-Champaign campus are pure calcite with a CaCO{sub 3} content greater than 98%, 3% higher than the minimum requirement of 95%. However, the size, shape, and brightness of the PCC particles are suitable only for certain applications. Impurities in the gypsum from Abbott power plant influence the whiteness of the PCC products. Test results suggested that, to obtain gypsum that is pure enough to produce a high whiteness PCC for high value commercial applications, limestone with minimum color impurities should be used during the FGD process. Alternatively, purification procedures to obtain the desired whiteness of the FGD-gypsum can be used. Further improvement in the overall qualities of the PCC products should lead to a product that is adequate for high-value paper applications.

  7. Marketable products from gypsum, a coal combustion byproduct derived from a wet flue gas desulfurization process

    SciTech Connect

    Chou, M.I.M.; Ghiassi, K.; Lytle, J.M.; Chou, S.J.; Banerjee, D.D.

    1998-04-01

    For two years the authors have been developing a process to produce two marketable products, ammonium sulfate fertilizer and precipitated calcium carbonate (PCC), from wet limestone flue gas desulfurization (FGD) by-product gypsum. Phase I of the project focused on the process for converting FGD-gypsum to ammonium sulfate fertilizer with PCC produced as a by-product during the conversion. Early cost estimates suggested that the process was economically feasible when granular size ammonium sulfate crystals were produced. However, sale of the by-product PCC for high-value commercial application could further improve the economics of the process. The results of our evaluation of the market potential of the PCC by-product are reported in this paper. The most significant attributes of carbonate fillers that determine their usefulness in industry are particle size (i.e. fineness) and shape, whiteness (brightness), and mineralogical and chemical purity. The PCC produced from the FGD gypsum obtained from the Abbott Power Plant at the University of Illinois Urbana-Champaign campus are pure calcite with a CaCO{sub 3} content greater than 98%, 3% higher than the minimum requirement of 95%. However, the size, shape, and brightness of the PCC particles are suitable only for certain applications. Impurities in the gypsum from Abbott power plant influence the whiteness of the PCC products. Test results suggested that, to obtain gypsum that is pure enough to produce a high whiteness PCC for high value commercial applications, limestone with minimum color impurities should be used during the FGD process. Alternatively, purification procedures to obtain the desired whiteness of the FGD-gypsum can be used. Further improvement in the overall qualities of the PCC products should lead to a product that is adequate for high-value paper applications.

  8. Desulfurization with a modified limestone formulation in an industrial CFBC boiler

    SciTech Connect

    Young Goo Park; Seung Ho Kim

    2006-02-01

    This work presents a practical result of experimental investigation of the limestone particle size effect on de-SOx from a circulating fluidized bed combustion (CFBC) boiler that burns domestic anthracite and is the first industrial scale in Korea. Because of combustion problems such as clinker formation, fine limestone has not been used as a desulfurization agent. The present test, however, showed that higher content (up to 50%) of the particles under 0.1 mm did not entail any malfunction in a modern CFBC system. In addition, the desulfurization efficiency was found to be comparable to the old mode of limestone sorbents. 17 refs., 4 figs., 3 tabs.

  9. Effect of Slag Chemistry on the Desulfurization Kinetics in Secondary Refining Processes

    NASA Astrophysics Data System (ADS)

    Kang, Jin Gyu; Shin, Jae Hong; Chung, Yongsug; Park, Joo Hyun

    2017-03-01

    Desulfurization behavior was investigated based on a wide slag composition and working temperature range. Moreover, the rate-controlling step (RCS) for desulfurization with regard to the ladle-refining conditions and the transition of the RCS by changing the slag composition was systematically discussed. The desulfurization ratio reached an equilibrium value within approximately 15 minutes irrespective of the CaO/Al2O3 (=C/A = 1.3 to 1.9) and CaO/SiO2 (=C/S = 3.8 to 6.3) ratios. However, the desulfurization behavior of less basic slags (C/A = 1.1 or C/S = 1.9) exhibited a relatively sluggish [S]-decreasing rate as a function of time. The equilibrium S partition ratio increased with an increase in slag basicity (C/A and C/S ratio), not only due to an increase in sulfide capacity but also due to a decrease in oxygen activity in the molten steel. There was a good correlation between the calculated and measured S partition ratios at various slag compositions. However, the measured S partition ratio increased by adding 5 pct CaF2, followed by a constant value. Multiphase slag exhibited a relatively slow desulfurization rate compared to that of fully liquid slag, possibly due to a decrease in the effective liquid slag volume, interfacial reaction area, and a relatively slow slag initial melting rate due to a high melting point. The activation energy of the desulfurization process was estimated to be 58.7 kJ/mol, from which it was proposed that the desulfurization reaction of molten steel via CaO-Al2O3-SiO2-MgO-CaF2 ladle slag was generally controlled by the mass transfer of sulfur in the metal phase. However, there was a transitional period associated with the rate-controlling mechanism due to a change in the physicochemical properties of the slag. For slag with a viscosity greater than about 1.1 dPa·s and an equilibrium S partition ratio lower than about 400, the overall mass-transfer coefficient was affected by the slag properties. Hence, it was theoretically and

  10. Biocatalytic polymer thin films: optimization of the multilayered architecture towards in situ synthesis of anti-proliferative drugs

    NASA Astrophysics Data System (ADS)

    Andreasen, Sidsel Ø.; Fejerskov, Betina; Zelikin, Alexander N.

    2014-03-01

    We report on the assembly of multi-layered polyelectrolyte thin films containing an immobilized enzyme to perform conversion of externally administered prodrugs and achieve delivery of the resulting therapeutics to adhering cells. Towards this goal, multi-layered coatings were assembled using poly(sodium styrene sulfonate) and poly(allylamine hydrochloride). Activity of the incorporated enzyme was quantified as a function of the assembly conditions, position of the enzyme within the multi-layered architecture, concentration of the enzyme in the adsorption solution, and concentration of the administered prodrug. Biocatalytic coatings exhibited sustained levels of enzymatic activity over at least one week of incubation in physiological buffers without signs of loss of activity of the enzyme. Developed enzyme-containing polymer films afforded zero-order release of the in situ synthesized cargo with kinetics of synthesis (nM per hour) covering at least 3 orders of magnitude. Internalization of the synthesized product by adhering cells was visualized using a fluorogenic enzyme substrate. Therapeutic utility of biocatalytic coatings was demonstrated using a myoblast cell line and a prodrug for the anti-proliferative agent, 5-fluorouridine. Taken together, this work presents a novel approach to delivery of small molecule drugs using multi-layered polymer thin films with utility in surface-mediated drug delivery, assembly of therapeutic implantable devices, and tissue engineering.We report on the assembly of multi-layered polyelectrolyte thin films containing an immobilized enzyme to perform conversion of externally administered prodrugs and achieve delivery of the resulting therapeutics to adhering cells. Towards this goal, multi-layered coatings were assembled using poly(sodium styrene sulfonate) and poly(allylamine hydrochloride). Activity of the incorporated enzyme was quantified as a function of the assembly conditions, position of the enzyme within the multi

  11. A biocatalytic approach to capuramycin analogues by exploiting a substrate permissive N-transacylase CapW.

    PubMed

    Liu, Xiaodong; Jin, Yuanyuan; Cai, Wenlong; Green, Keith D; Goswami, Anwesha; Garneau-Tsodikova, Sylvie; Nonaka, Koichi; Baba, Satoshi; Funabashi, Masanori; Yang, Zhaoyong; Van Lanen, Steven G

    2016-04-28

    Using the ATP-independent transacylase CapW required for the biosynthesis of capuramycin-type antibiotics, we developed a biocatalytic approach for the synthesis of 43 analogues via a one-step aminolysis reaction from a methyl ester precursor as an acyl donor and various nonnative amines as acyl acceptors. Further examination of the donor substrate scope for CapW revealed that this enzyme can also catalyze a direct transamidation reaction using the major capuramycin congener as a semisynthetic precursor. Biological activity tests revealed that a few of the new capuramycin analogues have significantly improved antibiotic activity against Mycobacterium smegmatis MC2 155 and Mycobacterium tuberculosis H37Rv. Furthermore, most of the analogues are able to be covalently modified by the phosphotransferase CapP/Cpr17 involved in self resistance, providing critical insight for future studies regarding clinical development of the capuramycin antimycobacterial antibiotics.

  12. Enhancing the biocatalytic manufacture of the key intermediate of atorvastatin by focused directed evolution of halohydrin dehalogenase

    PubMed Central

    Luo, Yu; Chen, Yangzi; Ma, Hongmin; Tian, ZhenHua; Zhang, Yeqi; Zhang, Jian

    2017-01-01

    Halohydrin dehalogenases (HHDHs) are biocatalytically interesting enzymes due to their ability to form C-C, C-N, C-O, and C-S bonds. One of most important application of HHDH was the protein engineering of HheC (halohydrin dehalogenase from Agrobacterium radiobacter AD1) for the industrial manufacturing of ethyl (R)-4-cyano-3-hydroxybutanoate (HN), a key chiral synthon of a cholesterol-lowering drug of atorvastatin. During our development of an alternative, more efficient and economic route for chemo-enzymatic preparation of the intermediate of atorvastatin, we found that the HheC2360 previously reported for HN manufacture, had insufficient activity for the cyanolysis production of tert-butyl (3 R,5 S)-6-cyano-3,5-dihydroxyhexanoate (A7). Herein, we present the focused directed evolution of HheC2360 with higher activity and enhanced biocatalytic performance using active site mutagenesis. Through docking of the product, A7, into the crystal structure of HheC2360, 6 residues was selected for combined active sites testing (CASTing). After library screening, the variant V84G/W86F was identified to have a 15- fold increase in activity. Time course analysis of the cyanolysis reaction catalyzed by this variant, showed 2- fold increase in space time productivity compared with HheC2360. These results demonstrate the applicability of the variant V84G/W86F as a biocatalyst for the efficient and practical production of atorvastatin intermediate. PMID:28165015

  13. Flue gas desulfurization of high sulfur coals retrofit costs, lime consumption and removal efficiencies 10 Mwe DOE demonstrate plant

    SciTech Connect

    Goss, W.L.

    1993-12-31

    AirPol, with the assistance of the Tennessee Valley Authority (TVA), is demonstrating the Gas Suspension Absorption (GSA) technology in the Clean Coal Technology project entitled {open_quote}10 MW Demonstration of Gas Suspension Absorption.{close_quote} AirPol is performing this demonstration under a Cooperative Agreement awarded by the United States Department of Energy (DOE) in October 1990, in Round III of the Clean Coal Technology Program. This project will be the first North American demonstration of the GSA system in its application for flue gas desulfurization. This low-cost retrofit project seeks to demonstrate the GSA system which is expected to remove more than 90% of the sulfur dioxide (SO{sub 2}) from coal-fired flue gas, while achieving a high utilization of reagent lime. TVA has provided its National Center for Emissions Research (NCER) as the host site and will provide operation and testing services during the operations and testing phase. The TVA NCER is located at the TVA Shawnee Fossil Plant in West Paducah, Kentucky. This Clean Coal Technology project is designed to demonstrate the GSA system`s performance in a coal-fired boiler application, and its suitability for retrofit at existing boiler plants. Air foxics testing and operation and testing of a 1 Mwe fabric filter were added to the operation/testing phase of the project. The additional testing work will be conducted for the purpose of determining the GSA`s performance in removal of air toxics and the significance of replacing the electrostatic precipitator with a fabric filter. The experience gained by AirPol in designing, manufacturing, and constructing the GSA equipment through executing this project will be used for future commercialization of the GSA system. Results of the operation and testing phase will be used to further improve the GSA system design and operation.

  14. Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

    NASA Astrophysics Data System (ADS)

    Sundararaman, Ramanathan

    Conventional approaches to oxidative desulfurization of liquid hydrocarbons involve use of high-purity, expensive water soluble peroxide for oxidation of sulfur compounds followed by post-treatment for removal of oxidized sulfones by extraction. Both are associated with higher cost due to handling, storage of oxidants and yield loss with extraction and water separation, making the whole process more expensive. This thesis explores an oxidative desulfurization process using air as an oxidant followed by catalytic decomposition of sulfones thereby eliminating the aforementioned issues. Oxidation of sulfur compounds was realized by a two step process in which peroxides were first generated in-situ by catalytic air oxidation, followed by catalytic oxidation of S compounds using the peroxides generated in-situ completing the two step approach. By this technique it was feasible to oxidize over 90% of sulfur compounds present in real jet (520 ppmw S) and diesel (41 ppmw S) fuels. Screening of bulk and supported CuO based catalysts for peroxide generation using model aromatic compound representing diesel fuel showed that bulk CuO catalyst was more effective in producing peroxides with high yield and selectivity. Testing of three real diesel fuels obtained from different sources for air oxidation over bulk CuO catalyst showed different level of effectiveness for generating peroxides in-situ which was consistent with air oxidation of representative model aromatic compounds. Peroxides generated in-situ was then used as an oxidant to oxidize sulfur compounds present in the fuel over MoO3/SiO2 catalyst. 81% selectivity of peroxides for oxidation of sulfur compounds was observed on MoO3/SiO2 catalyst at 40 °C and under similar conditions MoO3/Al2O3 gave only 41% selectivity. This difference in selectivity might be related to the difference in the nature of active sites of MoO3 on SiO2 and Al2O 3 supports as suggested by H2-TPR and XRD analyses. Testing of supported and bulk Mg

  15. Chemical and physical properties of dry flue gas desulfurization products.

    PubMed

    Kost, David A; Bigham, Jerry M; Stehouwer, Richard C; Beeghly, Joel H; Fowler, Randy; Traina, Samuel J; Wolfe, William E; Dick, Warren A

    2005-01-01

    Beneficial and environmentally safe recycling of flue gas desulfurization (FGD) products requires detailed knowledge of their chemical and physical properties. We analyzed 59 dry FGD samples collected from 13 locations representing four major FGD scrubbing technologies. The chemistry of all samples was dominated by Ca, S, Al, Fe, and Si and strong preferential partitioning into the acid insoluble residue (i.e., coal ash residue) was observed for Al, Ba, Be, Cr, Fe, Li, K, Pb, Si, and V. Sulfur, Ca, and Mg occurred primarily in water- or acid-soluble forms associated with the sorbents or scrubber reaction products. Deionized water leachates (American Society for Testing and Materials [ASTM] method) and dilute acetic acid leachates (toxicity characteristic leaching procedure [TCLP] method) had mean pH values of >11.2 and high mean concentrations of S primarily as SO(2-)4 and Ca. Concentrations of Ag, As, Ba, Cd, Cr, Hg, Pb, and Se (except for ASTM Se in two samples) were below drinking water standards in both ASTM and TCLP leachates. Total toxicity equivalents (TEQ) of dioxins, for two FGD products used for mine reclamation, were 0.48 and 0.53 ng kg(-1). This was similar to the background level of the mine spoil (0.57 ng kg(-1)). The FGD materials were mostly uniform in particle size. Specific surface area (m2 g(-1)) was related to particle size and varied from 1.3 for bed ash to 9.5 for spray dryer material. Many of the chemical and physical properties of these FGD samples were associated with the quality of the coal rather than the combustion and SO2 scrubbing processes used.

  16. Flue gas desulfurization by rotating beds. Final technical report

    SciTech Connect

    Gardner, N.; Keyvani, M.; Coskundeniz, A.

    1992-12-01

    The operating and mass transfer characteristics of rotating foam metal beds were studied to determine the potential for flue gas desulfurization. This is a final technical report on the work supported by DOE {number_sign}FG22-87-PC79924. The report is divided into two sections, Part 1 deals primarily with the operating characteristics of rotating beds, and Part 2 covers the mass transfer characteristics of S0{sub 2} absorption in water-lime slurries. Rotating foam metal beds are in essence packed towers operated in high gravitational fields. The foam metal bed is in the form of a cylindrical donut, or torus, and is rotated to produced the high centrifugal forces. The liquid phase enters the bed at the inner surface of the torus and is pulled by the field through the bed. Gas flows countercurrent to the liquid. The bed packing can have a very large specific surface areas and not flood. Possible benefits include much smaller height of a transfer unit resulting in smaller equipment and supporting structures, reduced solvent inventory, faster response with improved process control, reduced pressure drop, and shorter startup and shut-down times. This work is concerned broadly with the operating characteristics of rotating beds, the objectives being to (1) determine the pressure drop through the rotating bed; (2) determine the power required to operate the beds, (3) investigate the residence time distribution of the liquid phase in the beds; and (4) determine the mass transfer coefficients of S0{sub 2} absorption. Three packings of differing specific surface areas were studied, with areas ranging from 656 to 2952 m{sub 2}/m{sub 3}. Liquid flow rates to 36 kg/s*m{sub 2}, gas flow rate to 2.2 kg/s*m{sub 2}, and gravitational fields to 300 g were covered in this study.

  17. Analytical chemistry of the citrate process for flue gas desulfurization

    SciTech Connect

    Marchant, W.N.; May, S.L.; Simpson, W.W.; Winter, J.K.; Beard, H.R.

    1980-01-01

    The citrate process for flue gas desulfurization (FGD) is a product of continuing research by the US Bureau of Mines to meet the goal of minimizing the objectionable effects of minerals industry operations upon the environment. The reduction of SO/sub 2/ in solution by H/sub 2/S to produce elemental sulfur by the citrate process is extremely complex and results in solutions that contain at least nine different sulfur species. Process solution analysis is essential to a clear understanding of process chemistry and its safe, efficient operation. The various chemical species, the approximate ranges of their concentrations in citrate process solutions, and the analytical methods evolved to determine them are hydrogen sulfide (approx. 0M to 0.06M) by specific ion electrode, polysulfides (unknown) by ultraviolet (uv) spectrophotometry, elemental sulfur (approx. 0M to approx. 0.001M dissolved, approx. 0M to approx. 0.1M suspended) by uv spectrophotometry, thiosulfate (approx. 0M to approx. 0.25M) by iodometry or high performance liquid chromatography (HPLC), polythionates (approx. 0M to approx. 0.01M) by thin layer chromatography (TLC), dithionite (searched for but not detected in process solutions) by polarography or TLC, bisulfite (approx. 0M to 0.2M) by iodometry, sulfate (approx. 0M to 1M) by a Bureau-developed gravimetric procedure, citric acid (approx. 0M to 0.5M) by titration or visible colorimetry, glycolic acid (approx. 0M to 1M) by HPLC, sodium (approx. 1.5M) by flame photometry, and chloride by argentometric titration.

  18. ENGINEERING EVALUATION OF HOT-GAS DESULFURIZATION WITH SULFUR RECOVERY

    SciTech Connect

    G.W. ROBERTS; J.W. PORTZER; S.C. KOZUP; S.K. GANGWAL

    1998-05-31

    Engineering evaluations and economic comparisons of two hot-gas desulfurization (HGD) processes with elemental sulfur recovery, being developed by Research Triangle Institute, are presented. In the first process, known as the Direct Sulfur Recovery Process (DSRP), the SO{sub 2} tail gas from air regeneration of zinc-based HGD sorbent is catalytically reduced to elemental sulfur with high selectivity using a small slipstream of coal gas. DSRP is a highly efficient first-generation process, promising sulfur recoveries as high as 99% in a single reaction stage. In the second process, known as the Advanced Hot Gas Process (AHGP), the zinc-based HGD sorbent is modified with iron so that the iron portion of the sorbent can be regenerated using SO{sub 2} . This is followed by air regeneration to fully regenerate the sorbent and provide the required SO{sub 2} for iron regeneration. This second-generation process uses less coal gas than DSRP. Commercial embodiments of both processes were developed. Process simulations with mass and energy balances were conducted using ASPEN Plus. Results show that AHGP is a more complex process to operate and may require more labor cost than the DSRP. Also capital costs for the AHGP are higher than those for the DSRP. However, annual operating costs for the AHGP appear to be considerably less than those for the DSRP with a potential break-even point between the two processes after just 2 years of operation for an integrated gasification combined cycle (IGCC) power plant using 3 to 5 wt% sulfur coal. Thus, despite its complexity, the potential savings with the AHGP encourage further development and scaleup of this advanced process.

  19. Desulfurization of dibenzothiophene (DBT) by a novel strain Lysinibacillus sphaericus DMT-7 isolated from diesel contaminated soil.

    PubMed

    Bahuguna, Ashutosh; Lily, Madhuri K; Munjal, Ashok; Singh, Ravindra N; Dangwal, Koushalya

    2011-01-01

    A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene (DBT) was isolated from diesel contaminated soil. The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7 (NCBI GenBank Accession No. GQ496620) using 16S rDNA gene sequence analysis. The desulfurized product of DBT, 2-hydroxybiphenyl (2HBP), was identified and confirmed by high performance liquid chromatography analysis and gas chromatography-mass spectroscopy analysis respectively. The desulfurization kinetics revealed that DMT-7 started desulfurization of DBT into 2HBP after the lag phase of 24 hr, exponentially increasing the accumulation of 2HBP up to 15 days leading to approximately 60% desulfurization of the DBT. However, further growth resulted into DBT degradation. The induced culture of DMT-7 showed shorter lag phase of 6 hr and early onset of stationary phase within 10 days for desulfurization as compared to that of non-induced culture clearly indicating the inducibility of the desulfurization pathway of DMT-7. In addition, Lysinibacillus sphaericus DMT-7 also possess the ability to utilize broad range of substrates as sole source of sulfur such as benzothiophene, 3,4-benzo DBT, 4,6-dimethyl DBT, and 4,6-dibutyl DBT. Therefore, Lysinibacillus sphaericus DMT-7 could serve as model system for efficient biodesulfurization of diesel and petrol.

  20. Biocatalytic strategies for the asymmetric synthesis of alpha-hydroxy ketones.

    PubMed

    Hoyos, Pilar; Sinisterra, Josep-Vicent; Molinari, Francesco; Alcántara, Andrés R; Domínguez de María, Pablo

    2010-02-16

    The development of efficient syntheses for enantiomerically enriched alpha-hydroxy ketones is an important research focus in the pharmaceutical industry. For example, alpha-hydroxy ketones are found in antidepressants, in selective inhibitors of amyloid-beta protein production (used in the treatment of Alzheimer's), in farnesyl transferase inhibitors (Kurasoin A and B), and in antitumor antibiotics (Olivomycin A and Chromomycin A3). Moreover, alpha-hydroxy ketones are of particular value as fine chemicals because of their utility as building blocks for the production of larger molecules. They can also be used in preparing many other important structures, such as amino alcohols, diols, and so forth. Several purely chemical synthetic approaches have been proposed to afford these compounds, together with some organocatalytic strategies (thiazolium-based carboligations, proline alpha-hydroxylations, and so forth). However, many of these chemical approaches are not straightforward, lack selectivity, or are economically unattractive because of the large number of chemical steps required (usually combined with low enantioselectivities). In this Account, we describe three different biocatalytic approaches that have been developed to efficiently produce alpha-hydroxy ketones: (i) The use of thiamine diphosphate-dependent lyases (ThDP-lyases) to catalyze the umpolung carboligation of aldehydes. Enantiopure alpha-hydroxy ketones are formed from inexpensive aldehydes with this method. Some lyases with a broad substrate spectrum have been successfully characterized. Furthermore, the use of biphasic media with recombinant whole cells overexpressing lyases leads to productivities of approximately 80-100 g/L with high enantiomeric excesses (up to >99%). (ii) The use of hydrolases to produce alpha-hydroxy ketones by means of (in situ) dynamic kinetic resolutions (DKRs). Lipases are able to successfully resolve racemates, and many outstanding examples have been reported. However

  1. Comprehensive report to Congress: Clean Coal Technology program: Confined zone dispersion low-NO sub x flue gas desulfurization demonstration

    SciTech Connect

    Not Available

    1990-09-01

    This report describes a project selected for funding under the US Clean Coal Technology Program. This project will demonstrate the removal of SO{sub 2} from the flue gas of a utility coal-fired boiler retrofitted with the confined zone dispersion-flue gas desulfurization (CZD-FGD) process. In the CZD-FGD process, a finely atomized slurry of a highly reactive pressure hydrated dolomitic lime is sprayed into the flue gas stream between the boiler air heater(s) and the particulate collection equipment. The lime slurry is injected into the center of the duct and the type and position of the spray nozzles are designed to produce a cone of fine spray. As the cone of spray moves nozzles are designed to produce a cone of fine spray. As the cone of spray moves downstream and expands, the gas within the cone cools and the SO{sub 2} is rapidly absorbed by the liquid droplets. This fast drying time precludes wet particle build-up in the duct and allows carry-over of the dry reaction products and the unreacted lime in the flue gas, which will be removed by the particulate collection equipment. 6 figs., 1 tab.

  2. Desulfurization of coal with hydroperoxides of vegetable oils. [Quarterly progress report], December 1, 1994--February 28, 1995

    SciTech Connect

    Smith, G.V.; Gaston, R.D.; Song, Ruozhi; Cheng, Jianjun; Shi, Feng; Gholson, K.L.; Ho, K.K.

    1995-12-31

    This project proposes a new method for removing organic sulfur from Illinois coals using readily available farm products. It proposes to use air and vegetable oils to disrupt the coal matrix, oxidize sulfur forms, increase volatiles, and desulfurize coal. This will be accomplished by impregnating coals with polyunsaturated oils, converting the oils to their hydroperoxides, and heating. Since these oils are relatively inexpensive and easily applied, this project could lead to a cost effective method for removing organic sulfur from coals. Moreover, the oils are environmentally safe; they will produce no noxious products and will improve burning qualities of the solid products. Preliminary experiments showed that IBC 104 coal catalyzes the formation of hydroperoxides in safflower oil and that more sulfur is extracted from the treated than untreated coal. During the first quarter the requirement of an added photosensitizer was eliminated, the catalytic effect of coal was confirmed, and the existence of a complex set of reactions was revealed. During this second quarter working with IBC-108 coal (2.3% organic S. 0.4% pyrite S), the effects of different ratios of oil:coal, different extraction solvents, and different temperatures were examined. A new pretreatment which combines alkali with linseed oil was discovered. Best organic sulfur removal is approximately 26% using alkali pretreatment combined with linseed oil at 1OO{degree}C. BTU loses can be kept to a minimum of 3% with proper use of solvents.

  3. Method and apparatus for enhancing the desulfurization of hot coal gas in a fluid-bed coal gasifier

    DOEpatents

    Grindley, T.

    1988-04-05

    A process and apparatus for providing additional desulfurization of the hot gas produced in a fluid-bed coal gasifier, within the gasifier is described. A fluid-bed of iron oxide is located inside the gasifier above the gasification bed in a fluid-bed coal gasifier in which in-bed desulfurization by lime/limestone takes place. The product gases leave the gasification bed typically at 1600 to 1800 F and are partially quenched with water to 1000 to 1200 F before entering the iron oxide bed. The iron oxide bed provides additional desulfurization beyond that provided by the lime /limestone. 1 fig.

  4. Field studies on the use of flue gas desulfurization (FGD) gypsum in agriculture

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flue gas desulfurization gypsum (FGDG) is a product of precipitation of sulfur from stack gases from coal-fired electric power plants. This material is produced in increasingly large quantities by electric power companies to meet clean air standards. We have evaluated this material for beneficial us...

  5. Synthesis, characterization, and application of 1-butyl-3-methylimidazolium thiocyanate for extractive desulfurization of liquid fuel.

    PubMed

    Dharaskar, Swapnil A; Wasewar, Kailas L; Varma, Mahesh N; Shende, Diwakar Z

    2016-05-01

    1-Butyl-3-methylimidazolium thiocyanate [BMIM]SCN has been presented on extractive desulfurization of liquid fuel. The FTIR, (1)H-NMR, and C-NMR have been discussed for the molecular confirmation of synthesized [BMIM]SCN. Further, thermal, conductivity, moisture content, viscosity, and solubility analyses of [BMIM]SCN were carried out. The effects of time, temperature, sulfur compounds, ultrasonication, and recycling of [BMIM]SCN on removal of dibenzothiophene from liquid fuel were also investigated. In extractive desulfurization, removal of dibenzothiophene in n-dodecane was 86.5 % for mass ratio of 1:1 in 30 min at 30 °C under the mild process conditions. [BMIM]SCN could be reused five times without a significant decrease in activity. Also, in the desulfurization of real fuels, multistage extraction was examined. The data and results provided in the present paper explore the significant insights of imidazolium-based ionic liquids as novel extractant for extractive desulfurization of liquid fuels.

  6. Coal desulfurization by chlorinolysis production and combustion test evaluation of product coals

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Daly, D.

    1982-01-01

    Laboratory-scale screening tests were carried out on coal from Harrison County, Ohio to establish chlorination and hydrodesulfurization conditions for the batch reactor production of chlorinolysis and chlorinolysis-hydrodesulfurized coals. In addition, three bituminous coals, were treated on the lab scale by the chlorinolysis process to provide 39 to 62% desulfurization. Two bituminous coals and one subbituminous coal were then produced in 11 to 15 pound lots as chlorinolysis and hydrodesulfurized coals. The chlorinolysis coals had a desulfurization of 29-69%, reductions in voltatiles and hydrogen. Hydrodesulfurization provided a much greater desulfurization (56-86%), reductions in volatiles and hydrogen. The three coals were combustion tested in the Penn State ""plane flame furnace'' to determine ignition and burning characteristics. All three coals burned well to completion as: raw coals, chlorinolysis processed coals, and hydrodesulfurized coals. The hydrodesulfurized coals experienced greater ignition delays and reduced burning rates than the other coals because of the reduced volatile content. It is thought that the increased open pore volume in the desulfurized-devolatilized coals compensates in part for the decreased volatiles effect on ignition and burning.

  7. High Temperature Flue Gas Desulfurization In Moving Beds With Regenerable Copper Based Sorbents

    SciTech Connect

    Cengiz, P.A.; Ho, K.K.; Abbasian, J.; Lau, F.S.

    2002-09-20

    The objective of this study was to develop new and improved regenerable copper based sorbent for high temperature flue gas desulfurization in a moving bed application. The targeted areas of sorbent improvement included higher effective capacity, strength and long-term durability for improved process control and economic utilization of the sorbent.

  8. Use of glass fiber-reinforced plastic as an absorber in limestone wet flue gas desulfurization.

    PubMed

    Lin, Haibo

    2008-10-01

    The choice of materials for the spraying and oxidation of pipes directly affect the operation in limestone wet flue gas desulfurization (FGD). There is reason to consider using glass fiber-reinforced plastic (FRP) instead of expensive high nickel alloy for the spraying and oxidation of pipes.

  9. COMPARISON OF WEST GERMAN AND U.S. FLUE GAS DESULFURIZATION AND SELECTIVE CATALYTIC REDUCTION COSTS

    EPA Science Inventory

    The report documents a comparison of the actual cost retrofitting flue gas desulfurization (FGD) and selective catalytic reduction (SCR) on Federal Republic of German (FRG) boilers to cost estimating procedures used in the U.S. to estimate the retrofit of these controls on U.S. b...

  10. Elemental sulfur-producing high-temperature fuel gas desulfurization process

    SciTech Connect

    Anderson, G.L.; Garrigan, P.C.; Berry, F.O.

    1980-01-01

    Preliminary studies have shown that certain materials when added to air-regenerable, high-temperature, fuel gas desulfurization sorbents, such as iron oxide or zinc oxide, significantly increase elemental sulfur formation during regeneration. Although the full range of conditions under which these materials can be applied remains to be determined, successful applications could eliminate a costly SO/sub 2/ reduction step.

  11. Investigation Of A Mercury Speciation Technique For Flue Gas Desulfurization Materials

    EPA Science Inventory

    Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to bene...

  12. Comparison of soil applied flue gas desulfurization (FGD) and agricultural gypsum on soil physical properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Gypsum can come from different sources. Agricultural gypsum is typically mined and used to supply calcium to crops. Flue gas desulfurization (FGD) gypsum is a by-product of coal power plants. Although their chemical formulas are the same, different trace elements and materials are present in them....

  13. Catalyst for Desulfurization of Industrial Waste Gases and Process for Preparing the Catalyst

    SciTech Connect

    Dupin, T.

    1983-12-27

    Industrial waste gases containing objectionable/polluting compounds of sulfur, e.g., H/sub 2/S, SO/sub 2/ and such organo-sulfur derivatives as COS, CS/sub 2/ and mercaptans, are catalytically desulfurized, e.g., by Claus process, employing an improved catalyst comprising titanium dioxide and calcium, barium, strontium or magnesium sulfate.

  14. Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

    NASA Astrophysics Data System (ADS)

    Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

    2012-09-01

    The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

  15. Flue gas desulfurization gypsum: Its effectiveness as an alternative bedding material for broiler production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flue gas desulfurization gypsum (FGDG) may be a viable low-cost alternative bedding material for broiler production. In order to evaluate FGD gypsum’s viability, three consecutive trials were conducted to determine its influence on live performance (body weight, feed consumption, feed efficiency, an...

  16. Decreasing phosphorus loss in tile-drained landscapes using flue gas desulfurization gypsum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Elevated phosphorus (P) loading from agricultural non-point source pollution continues to impair inland waterbodies throughout the world. The application of flue gas desulfurization (FGD) gypsum to agricultural fields has been suggested to decrease P loading because of its high calcium content and P...

  17. Characteristics and reactivity of rapidly hydrated sorbent for semidry flue gas desulfurization

    SciTech Connect

    Jie Zhang; Changfu You; Suwei Zhao; Changhe Chen; Haiying Qi

    2008-03-01

    The semidry flue gas desulfurization (FGD) process has many advantages over the wet FGD process for moving sulfur dioxide emissions from pulverized coal-fired power plants. Semidry FGD with a rapidly hydrated sorbent was studied in a pilot-scale circulating fluidized bed (CFB) experimental facility. The sorbent was made from lumps of lime and coal fly ash. The desulfurization efficiency was measured for various operating parameters, including the sorbent recirculation rate and the water spray method. The experimental results show that the desulfurization efficiencies of the rapidly hydrated sorbent were 1.5-3.0 times higher than a commonly used industrial sorbent for calcium to sulfur molar ratios from 1.2 to 3.0, mainly due to the higher specific surface area and pore volume. The Ca(OH){sub 2} content in the cyclone separator ash was about 2.9% for the rapidly hydrated sorbent and was about 0.1% for the commonly used industrial sorbent, due to the different adhesion between the fine Ca(OH){sub 2} particles and the fly ash particles, and the low cyclone separation efficiency for the fine Ca(OH){sub 2} particles that fell off the sorbent particles. Therefore the actual recirculation rates of the active sorbent with Ca(OH){sub 2} particles were higher for the rapidly hydrated sorbent, which also contributed to the higher desulfurization efficiency. The high fly ash content in the rapidly hydrated sorbent resulted in good operating stability. The desulfurization efficiency with upstream water spray was 10-15% higher than that with downstream water spray. 20 refs., 7 figs., 1 tab.

  18. Advanced sulfur control concepts for hot gas desulfurization technology. Quarterly report, January 1--March 31, 1997

    SciTech Connect

    1997-08-01

    Favorable results were achieved in the sulfidation of CeO{sub 2} by H{sub 2}S and the regeneration of Ce{sub 2}O{sub 2}S by SO{sub 2}. Successful removal of approximately 99% of the H{sub 2}S from the sulfidation gas to levels of about 100 ppmv (or lower), and the production of approximately 12% elemental sulfur (as S{sub 2}) in the regeneration product gas were highlights. Final effort in the preliminary phase included a ten-cycle test at standard sulfidation and regeneration conditions with little or no sorbent deterioration. In the initial test of the detailed experimental phase of the program, the authors investigated the effect of temperature on the regeneration reaction. Results of preliminary tests showed that the Ce{sub 2}O{sub 2}S-SO{sub 2} reaction did not occur at 350 C, and all subsequent regeneration tests were at 600 C where the reaction was rapid. Significant progress has been made on the process analysis effort during the quarter. Detailed process flow diagrams along with material and energy balance calculations for six design case studies were completed in the previous quarter. Two of the cases involved two-stage desulfurization with steam regeneration, three used two-stage desulfurization with SO{sub 2} regeneration, and the sixth was based on single-stage desulfurization with elemental sulfur recovery using the DSRP concept. In the present quarter, major process equipment was sized for each of the six cases. Preliminary annual operating and levelized total cost estimates were then completed for two design cases--one involving two-stage desulfurization with SO{sub 2} regeneration and the second based on single-stage desulfurization with DSRP.

  19. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS--SITE 2 RESULTS

    SciTech Connect

    G. Blythe; S. Miller; C. Richardson; K. Searcy

    2000-02-01

    The U.S. Department of Energy and EPRI are co-funding this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project is investigating catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems, and to future FGD installations. Field tests are being conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit is being used to test the activity of four different catalysts for a period of up to six months at each of three utility sites. Catalyst testing at the first site, which fires Texas lignite, was completed in December 1998. Testing at the second test site, which fires a Powder River Basin subbituminous coal, was completed in the fall of 1999, and testing at the third site, which fires a high-sulfur bituminous coal, will begin in early 2000. This technical note reports results from Site 2; results from Site 1 were reported in a previous technical note. At Site 2, catalysts were tested in several forms, including powders dispersed in sand bed reactors and in more commercially viable forms such as extruded beads and coated honeycomb structures. This technical note presents results from Site 2 for both the sand bed reactors and commercial catalyst forms. Site 3 results are not yet available, but should be available late in the year 2000. Field testing is being supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and to investigate methods for regenerating spent catalysts. Laboratory results related to the

  20. ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS--SITE 2 RESULTS

    SciTech Connect

    G. Blythe; S. Miller; C. Richardson; K. Searcy

    2000-06-01

    The U.S. Department of Energy and EPRI are co-funding this project to improve the control of mercury emissions from coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems. The project is investigating catalytic oxidation of vapor-phase elemental mercury to a form that is more effectively captured in wet FGD systems. If successfully developed, the process could be applicable to over 90,000 MW of utility generating capacity with existing FGD systems, and to future FGD installations. Field tests are being conducted to determine whether candidate catalyst materials remain active towards mercury oxidation after extended flue gas exposure. Catalyst life will have a large impact on the cost effectiveness of this potential process. A mobile catalyst test unit is being used to test the activity of four different catalysts for a period of up to six months at each of three utility sites. Catalyst testing at the first site, which fires Texas lignite, was completed in December 1998. Testing at the second test site, which fires a Powder River Basin subbituminous coal, was completed in the fall of 1999, and testing at the third site, which fires a high-sulfur bituminous coal, will begin in 2000. This technical note reports results from Site 2; results from Site 1 were reported in a previous technical note. At Site 2, catalysts were tested in several forms, including powders dispersed in sand bed reactors and in commercial forms such as extruded beads and coated honeycomb structures. This technical note presents results from Site 2 for both the sand bed reactors and commercial catalyst forms. Field testing is being supported by laboratory tests to screen catalysts for activity at specific flue gas compositions, to investigate catalyst deactivation mechanisms and to investigate methods for regenerating spent catalysts. Laboratory results related to the Site 2 field effort are also included and discussed in this technical note. Preliminary economics, based

  1. Biocatalytic Conversion of Avermectin to 4″-Oxo-Avermectin: Improvement of Cytochrome P450 Monooxygenase Specificity by Directed Evolution▿ †

    PubMed Central

    Trefzer, Axel; Jungmann, Volker; Molnár, István; Botejue, Ajit; Buckel, Dagmar; Frey, Gerhard; Hill, D. Steven; Jörg, Mario; Ligon, James M.; Mason, Dylan; Moore, David; Pachlatko, J. Paul; Richardson, Toby H.; Spangenberg, Petra; Wall, Mark A.; Zirkle, Ross; Stege, Justin T.

    2007-01-01

    Discovery of the CYP107Z subfamily of cytochrome P450 oxidases (CYPs) led to an alternative biocatalytic synthesis of 4″-oxo-avermectin, a key intermediate for the commercial production of the semisynthetic insecticide emamectin. However, under industrial process conditions, these wild-type CYPs showed lower yields due to side product formation. Molecular evolution employing GeneReassembly was used to improve the regiospecificity of these enzymes by a combination of random mutagenesis, protein structure-guided site-directed mutagenesis, and recombination of multiple natural and synthetic CYP107Z gene fragments. To assess the specificity of CYP mutants, a miniaturized, whole-cell biocatalytic reaction system that allowed high-throughput screening of large numbers of variants was developed. In an iterative process consisting of four successive rounds of GeneReassembly evolution, enzyme variants with significantly improved specificity for the production of 4″-oxo-avermectin were identified; these variants could be employed for a more economical industrial biocatalytic process to manufacture emamectin. PMID:17483257

  2. Flue gas desulfurization: the state of the art.

    PubMed

    Srivastava, R K; Jozewicz, W

    2001-12-01

    Coal-fired electricity-generating plants may use SO2 scrubbers to meet the requirements of Phase II of the Acid Rain SO2 Reduction Program. Additionally, the use of scrubbers can result in reduction of Hg and other emissions from combustion sources. It is timely, therefore, to examine the current status of SO2 scrubbing technologies. This paper presents a comprehensive review of the state of the art in flue gas desulfurization (FGD) technologies for coal-fired boilers. Data on worldwide FGD applications reveal that wet FGD technologies, and specifically wet limestone FGD, have been predominantly selected over other FGD technologies. However, lime spray drying (LSD) is being used at the majority of the plants employing dry FGD technologies. Additional review of the U.S. FGD technology applications that began operation in 1991 through 1995 reveals that FGD processes of choice recently in the United States have been wet limestone FGD, magnesium-enhanced lime (MEL), and LSD. Further, of the wet limestone processes, limestone forced oxidation (LSFO) has been used most often in recent applications. The SO2 removal performance of scrubbers has been reviewed. Data reflect that most wet limestone and LSD installations appear to be capable of approximately 90% SO2 removal. Advanced, state-of-the-art wet scrubbers can provide SO2 removal in excess of 95%. Costs associated with state-of-the-art applications of LSFO, MEL, and LSD technologies have been analyzed with appropriate cost models. Analyses indicate that the capital cost of an LSD system is lower than those of same capacity LSFO and MEL systems, reflective of the relatively less complex hardware used in LSD. Analyses also reflect that, based on total annualized cost and SO2 removal requirements: (1) plants up to approximately 250 MWe in size and firing low- to medium-sulfur coals (i.e., coals with a sulfur content of 2% or lower) may use LSD; and (2) plants larger than 250 MWe and firing medium- to high-sulfur coals (i

  3. Flue Gas Desulfurization: The State of the Art.

    PubMed

    Srivastava, R K; Jozewicz, W

    2001-12-01

    Coal-fired electricity-generating plants may use SO2 scrubbers to meet the requirements of Phase II of the Acid Rain SO2 Reduction Program. Additionally, the use of scrubbers can result in reduction of Hg and other emissions from combustion sources. It is timely, therefore, to examine the current status of SO2 scrubbing technologies. This paper presents a comprehensive review of the state of the art in flue gas desulfurization (FGD) technologies for coal-fired boilers. Data on worldwide FGD applications reveal that wet FGD technologies, and specifically wet limestone FGD, have been predominantly selected over other FGD technologies. However, lime spray drying (LSD) is being used at the majority of the plants employing dry FGD technologies. Additional review of the U.S. FGD technology applications that began operation in 1991 through 1995 reveals that FGD processes of choice recently in the United States have been wet limestone FGD, magnesium-enhanced lime (MEL), and LSD. Further, of the wet limestone processes, limestone forced oxidation (LSFO) has been used most often in recent applications. The SO2 removal performance of scrubbers has been reviewed. Data reflect that most wet limestone and LSD installations appear to be capable of ~90% SO2 removal. Advanced, state-of-the-art wet scrubbers can provide SO2 removal in excess of 95%. Costs associated with state-of-the-art applications of LSFO, MEL, and LSD technologies have been analyzed with appropriate cost models. Analyses indicate that the capital cost of an LSD system is lower than those of same capacity LSFO and MEL systems, reflective of the relatively less complex hardware used in LSD. Analyses also reflect that, based on total annualized cost and SO2 removal requirements: (1) plants up to ~250 MWe in size and firing low- to medium-sulfur coals (i.e., coals with a sulfur content of 2% or lower) may use LSD; and (2) plants larger than 250 MWe and firing medium- to high-sulfur coals (i.e., coals with a sulfur

  4. Development of advanced hot-gas desulfurization processes

    SciTech Connect

    Jothimurugesan, K.

    2000-04-17

    Advanced integrated gasification combined cycle (IGCC) power plants nearing completion, such as Sierra-Pacific, employ a circulating fluidized-bed (transport) reactor hot-gas desulfurization (HGD) process that uses 70-180 {micro}m average particle size (aps) zinc-based mixed-metal oxide sorbent for removing H{sub 2}S from coal gas down to less than 20 ppmv. The sorbent undergoes cycles of absorption (sulfidation) and air regeneration. The key barrier issues associated with a fluidized-bed HGD process are chemical degradation, physical attrition, high regeneration light-off (initiation) temperature, and high cost of the sorbent. Another inherent complication in all air-regeneration-based HGD processes is the disposal of the problematic dilute SO{sub 2} containing regeneration tail-gas. Direct Sulfur Recovery Process (DSRP), a leading first generation technology, efficiently reduces this SO{sub 2} to desirable elemental sulfur, but requires the use of 1-3 % of the coal gas, thus resulting in an energy penalty to the plant. Advanced second-generation processes are under development that can reduce this energy penalty by modifying the sorbent so that it could be directly regenerated to elemental sulfur. The objective of this research is to support the near and long term DOE efforts to commercialize the IGCC-HGD process technology. Specifically we aim to develop: optimized low-cost sorbent materials with 70-80 {micro}m average aps meeting all Sierra specs; attrition resistant sorbents with 170 {micro}m aps that allow greater flexibility in the choice of the type of fluidized-bed reactor e.g. they allow increased throughput in a bubbling-bed reactor; and modified fluidizable sorbent materials that can be regenerated to produce elemental sulfur directly with minimal or no use of coal gas. The effort during the reporting period has been devoted to testing the FHR-32 sorbent. FHR-32 sorbent was tested for 50 cycles of sulfidation in a laboratory scale reactor.

  5. Development of advanced hot-gas desulfurization processes

    SciTech Connect

    Jothimurugesan, K.

    1999-10-14

    Advanced integrated gasification combined cycle (IGCC) power plants nearing completion, such as Sierra-Pacific, employ a circulating fluidized-bed (transport) reactor hot-gas desulfurization (HGD) process that uses 70-180 {micro}m average particle size (aps) zinc-based mixed-metal oxide sorbent for removing H{sub 2}S from coal gas down to less than 20 ppmv. The sorbent undergoes cycles of absorption (sulfidation) and air regeneration. The key barrier issues associated with a fluidized-bed HGD process are chemical degradation, physical attrition, high regeneration light-off (initiation) temperature, and high cost of the sorbent. Another inherent complication in all air-regeneration-based HGD processes is the disposal of the problematic dilute SO{sub 2} containing regeneration tail-gas. Direct Sulfur Recovery Process (DSRP), a leading first generation technology, efficiently reduces this SO{sub 2} to desirable elemental sulfur, but requires the use of 1-3 % of the coal gas, thus resulting in an energy penalty to the plant. Advanced second-generation processes are under development that can reduce this energy penalty by modifying the sorbent so that it could be directly regenerated to elemental sulfur. The objective of this research is to support the near and long term DOE efforts to commercialize the IGCC-HGD process technology. Specifically we aim to develop: optimized low-cost sorbent materials with 70-80 {micro}m average aps meeting all Sierra specs; attrition resistant sorbents with 170 {micro}m aps that allow greater flexibility in the choice of the type of fluidized-bed reactor e.g. they allow increased throughput in a bubbling-bed reactor; and modified fluidizable sorbent materials that can be regenerated to produce elemental sulfur directly with minimal or no use of coal gas The effort during the reporting period has been devoted to development of an advanced hot-gas process that can eliminate the problematic SO{sub 2} tail gas and yield elemental sulfur

  6. Development of advanced hot-gas desulfurization processes

    SciTech Connect

    Jothimurugesan, K.

    1999-04-26

    Advanced integrated gasification combined cycle (IGCC) power plants nearing completion, such as Sierra-Pacific, employ a circulating fluidized-bed (transport) reactor hot-gas desulfurization (HGD) process that uses 70-180 {micro}m average particle size (aps) zinc-based mixed-metal oxide sorbent for removing H{sub 2}S from coal gas down to less than 20 ppmv. The sorbent undergoes cycles of absorption (sulfidation) and air regeneration. The key barrier issues associated with a fluidized-bed HGD process are chemical degradation, physical attrition, high regeneration light-off (initiation) temperature, and high cost of the sorbent. Another inherent complication in all air-regeneration-based HGD processes is the disposal of the problematic dilute SO{sub 2} containing regeneration tail-gas. Direct Sulfur Recovery Process (DSRP), a leading first generation technology, efficiently reduces this SO{sub 2} to desirable elemental sulfur, but requires the use of 1-3% of the coal gas, thus resulting in an energy penalty to the plant. Advanced second-generation processes are under development that can reduce this energy penalty by modifying the sorbent so that it could be directly regenerated to elemental sulfur. The objective of this research is to support the near and long term DOE efforts to commercialize the IGCC-HGD process technology. Specifically we aim to develop: optimized low-cost sorbent materials with 70-80 {micro}m average aps meeting all Sierra specs; attrition resistant sorbents with 170 {micro}m aps that allow greater flexibility in the choice of the type of fluidized-bed reactor e.g. they allow increased throughput in a bubbling-bed reactor; and modified fluidizable sorbent materials that can be regenerated to produce elemental sulfur directly with minimal or no use of coal gas. The effort during the reporting period has been devoted to development of optimized low-cost zinc-oxide-based sorbents for Sierra-Pacific. The sorbent surface were modified to prevent

  7. Results of testing various natural gas desulfurization adsorbents

    NASA Astrophysics Data System (ADS)

    Israelson, Gordon

    2004-06-01

    This article presents the results of testing many commercially available and some experimental sulfur adsorbents. The desired result of our testing was to find an effective method to reduce the quantity of sulfur in natural gas to less than 100 ppb volume (0.1 ppm volume). An amount of 100 ppb sulfur is the maximum limit permitted for Siemens Westinghouse solid oxide fuel cells (SOFCs). The tested adsorbents include some that rely only on physical adsorption such as activated carbon, some that rely on chemisorption such as heated zinc oxide, and some that may use both processes. The testing was performed on an engineering scale with beds larger than those used for typical laboratory tests. All tests were done at about 3.45 barg (50 psig). The natural gas used for testing was from the local pipeline in Pittsburgh and averaged 6 ppm volume total sulfur. The primary sulfur species were dimethyl sulfide (DMS), isopropyl mercaptan, tertiary butyl mercaptan, and tetrahydrothiophene. Some tests required several months to achieve a sulfur breakthrough of the bed. It was found that DMS always came through a desulfurizer bed first, independent of adsorption process. Since the breakthrough of DMS always exceeds the 100 ppb SOFC sulfur limit before other sulfurs were detected, an index was created to rate the adsorbents in units of ppm DMS × absorbent bed volume. This index is useful for calculating the expected adsorbent bed lifetime before sulfur breakthrough when the inlet natural gas DMS content is known. The adsorbents that are included in these reports were obtained from suppliers in the United States, the Netherlands, Japan, and England. Three activated carbons from different suppliers were found to have identical performance in removing DMS. One of these activated carbons was operated at four different space velocities and again showed the same performance. When using activated carbon as the basis of comparison for other adsorbents, three high-performance adsorbents

  8. Superoxide radical and UV irradiation in ultrasound assisted oxidative desulfurization (UAOD): A potential alternative for greener fuels

    NASA Astrophysics Data System (ADS)

    Chan, Ngo Yeung

    This study is aimed at improving the current ultrasound assisted oxidative desulfurization (UAOD) process by utilizing superoxide radical as oxidant. Research was also conducted to investigate the feasibility of ultraviolet (UV) irradiation-assisted desulfurization. These modifications can enhance the process with the following achievements: (1) Meet the upcoming sulfur standards on various fuels including diesel fuel oils and residual oils; (2) More efficient oxidant with significantly lower consumption in accordance with stoichiometry; (3) Energy saving by 90%; (4) Greater selectivity in petroleum composition. Currently, the UAOD process and subsequent modifications developed in University of Southern California by Professor Yen's research group have demonstrated high desulfurization efficiencies towards various fuels with the application of 30% wt. hydrogen peroxide as oxidant. The UAOD process has demonstrated more than 50% desulfurization of refractory organic sulfur compounds with the use of Venturella type catalysts. Application of quaternary ammonium fluoride as phase transfer catalyst has significantly improved the desulfurization efficiency to 95%. Recent modifications incorporating ionic liquids have shown that the modified UAOD process can produce ultra-low sulfur, or near-zero sulfur diesels under mild conditions with 70°C and atmospheric pressure. Nevertheless, the UAOD process is considered not to be particularly efficient with respect to oxidant and energy consumption. Batch studies have demonstrated that the UAOD process requires 100 fold more oxidant than the stoichiometic requirement to achieve high desulfurization yield. The expected high costs of purchasing, shipping and storage of the oxidant would reduce the practicability of the process. The excess use of oxidant is not economically desirable, and it also causes environmental and safety issues. Post treatments would be necessary to stabilize the unspent oxidant residual to prevent the waste

  9. Pressurized fluidized-bed hydroretorting of Eastern oil shales -- Sulfur control. Topical report for Subtask 3.1, In-bed sulfur capture tests; Subtask 3.2, Electrostatic desulfurization; Subtask 3.3, Microbial desulfurization and denitrification

    SciTech Connect

    Roberts, M.J.; Abbasian, J.; Akin, C.; Lau, F.S.; Maka, A.; Mensinger, M.C.; Punwani, D.V.; Rue, D.M.; Gidaspow, D.; Gupta, R.; Wasan, D.T.; Pfister, R.M.: Krieger, E.J.

    1992-05-01

    This topical report on ``Sulfur Control`` presents the results of work conducted by the Institute of Gas Technology (IGT), the Illinois Institute of Technology (IIT), and the Ohio State University (OSU) to develop three novel approaches for desulfurization that have shown good potential with coal and could be cost-effective for oil shales. These are (1) In-Bed Sulfur Capture using different sorbents (IGT), (2) Electrostatic Desulfurization (IIT), and (3) Microbial Desulfurization and Denitrification (OSU and IGT). The objective of the task on In-Bed Sulfur Capture was to determine the effectiveness of different sorbents (that is, limestone, calcined limestone, dolomite, and siderite) for capturing sulfur (as H{sub 2}S) in the reactor during hydroretorting. The objective of the task on Electrostatic Desulfurization was to determine the operating conditions necessary to achieve a high degree of sulfur removal and kerogen recovery in IIT`s electrostatic separator. The objectives of the task on Microbial Desulfurization and Denitrification were to (1) isolate microbial cultures and evaluate their ability to desulfurize and denitrify shale, (2) conduct laboratory-scale batch and continuous tests to improve and enhance microbial removal of these components, and (3) determine the effects of processing parameters, such as shale slurry concentration, solids settling characteristics, agitation rate, and pH on the process.

  10. An integrated biodesulfurization process, including inoculum preparation, desulfurization and sulfate removal in a single step, for removing sulfur from oils.

    SciTech Connect

    Tangaromsuk, Jantana; Borole, Abhijeet P; Kruatrachue, Maleeya; Pokethitiyook, Prayad

    2008-01-01

    BACKGROUND: A single-stage reactor, in which the growth of bacterial culture, induction of desulfurizing enzymes, and desulfurization reaction are carried out in a single step, was adopted to investigate desulfurization of DBT at high cell densities. IGTS8 was used as the biocatalyst. Optimal condition for the bacterial growth and DBT desulfurization were also investigated. RESULTS: Optimization of fermentation conditions was necessary to obtain high cell densities including controlling accumulation of acetate. Under optimal operating conditions, the maximum OD600 was measured to be 26.6 at 118 h of cultivation. When biodesulfurization of DBT in model oil with a high cell density culture of IGTS8 was investigated, accumulation of sulfate was found to limit the extent of desulfurization. A sulfate removal step was added to obtain a single-stage integrated biodesulfurization process. Sulfate removal was achieved via an aqueous bleed stream and use of a separation unit to recycle the organic phase. CONCLUSION : A proof of principle of a complete system capable of biocatalyst growth, induction, desulfurization and by-product separation was demonstrated. This system enables simplification of the biodesulfurization process and has potential to lower the operating cost of the bioprocess.

  11. Sequence and molecular characterization of a DNA region encoding the dibenzothiophene desulfurization operon of Rhodococcus sp. strain IGTS8.

    PubMed

    Piddington, C S; Kovacevich, B R; Rambosek, J

    1995-02-01

    Dibenzothiophene (DBT), a model compound for sulfur-containing organic molecules found in fossil fuels, can be desulfurized to 2-hydroxybiphenyl (2-HBP) by Rhodococcus sp. strain IGTS8. Complementation of a desulfurization (dsz) mutant provided the genes from Rhodococcus sp. strain IGTS8 responsible for desulfurization. A 6.7-kb TaqI fragment cloned in Escherichia coli-Rhodococcus shuttle vector pRR-6 was found to both complement this mutation and confer desulfurization to Rhodococcus fascians, which normally is not able to desulfurize DBT. Expression of this fragment in E. coli also conferred the ability to desulfurize DBT. A molecular analysis of the cloned fragment revealed a single operon containing three open reading frames involved in the conversion of DBT to 2-HBP. The three genes were designated dszA, dszB, and dszC. Neither the nucleotide sequences nor the deduced amino acid sequences of the enzymes exhibited significant similarity to sequences obtained from the GenBank, EMBL, and Swiss-Prot databases, indicating that these enzymes are novel enzymes. Subclone analyses revealed that the gene product of dszC converts DBT directly to DBT-sulfone and that the gene products of dszA and dszB act in concert to convert DBT-sulfone to 2-HBP.

  12. Biocatalytic anti-Prelog reduction of prochiral ketones with whole cells of Acetobacter pasteurianus GIM1.158

    PubMed Central

    2014-01-01

    Background Enantiomerically pure alcohols are important building blocks for production of chiral pharmaceuticals, flavors, agrochemicals and functional materials and appropriate whole-cell biocatalysts offer a highly enantioselective, minimally polluting route to these valuable compounds. At present, most of these biocatalysts follow Prelog’s rule, and thus the (S)-alcohols are usually obtained when the smaller substituent of the ketone has the lower CIP priority. Only a few anti-Prelog (R)-specific whole cell biocatalysts have been reported. In this paper, the biocatalytic anti-Prelog reduction of 2-octanone to (R)-2-octanol was successfully conducted with high enantioselectivity using whole cells of Acetobacter pasteurianus GIM1.158. Results Compared with other microorganisms investigated, Acetobacter pasteurianus GIM1.158 was shown to be more effective for the reduction reaction, affording much higher yield, product enantiomeric excess (e.e.) and initial reaction rate. The optimal temperature, buffer pH, co-substrate and its concentration, substrate concentration, cell concentration and shaking rate were 35°C, 5.0, 500 mmol/L isopropanol, 40 mmol/L, 25 mg/mL and 120 r/min, respectively. Under the optimized conditions, the maximum yield and the product e.e. were 89.5% and >99.9%, respectively, in 70 minutes. Compared with the best available data in aqueous system (yield of 55%), the yield of (R)-2-octanol was greatly increased. Additionally, the efficient whole-cell biocatalytic process was feasible on a 200-mL preparative scale and the chemical yield increased to 95.0% with the product e.e. being >99.9%. Moreover, Acetobacter pasteurianus GIM1.158 cells were proved to be capable of catalyzing the anti-Prelog bioreduction of other prochiral carbonyl compounds with high efficiency. Conclusions Via an effective increase in the maximum yield and the product e.e. with Acetobacter pasteurianus GIM1.158 cells, these results open the way to use of whole cells of

  13. Desulfurization of coal. Final report. [Flotation followed by olefin and vinyl monomer treatment

    SciTech Connect

    Dichter, M.; Sanduja, M.

    1980-10-01

    Ohio coal, like many other types of coal, has a high sulfur as well as ash content. We at PRCA, through a series of steps involving the treatment of coal with an olefin-catalyst and/or catalyzed oxidizing system, have established the following: (1) Crushing and pulverizing of coal to a size of 150 to 200 mesh is an important factor in the process of desulfurization, as this allows improvement of the efficiency of flotation and chemical desulfurization. (2) Flotation results in a significant reduction of sulfur and ash content of the coal and reduces the amount of water absorbed on the pulverized coal when petroleum fractions are introduced into the flotation process. Coal containing 4.3% and 2.7% sulfur have been desulfurized to 2.8% to 3.0% and 1.5% to 1.9%, respectively. The ash content has been reduced after flotation from 10.7% to 6.5% of the Pittsburgh No. 8 coal and from 16.5% to 10.5% of a coal provided by Consolidation Coal Co. (3) Chemical treatment with olefins and monomers allows complete removal of the rest of the pyritic sulfur and part of the organic sulfur. The higher molecular weight olefins give better results and an introduction of some maleic anhydride monomer helps to get a higher reduction of the sulfur in the coal. The presence of an alkaline medium (NaOH or Na/sub 2/CO/sub 3/) enhances the sulfur removal efficiency. (4) Elevated temperatures and pressures allows reduction of the time of reaction to obtain lower sulfur content coal. However, the pressure in the range of 100 to 200 psi allows achievement of an optimum desulfurization of treated coal. Even 25 to 30 psi has shown satisfactory results in the same time. (5) The results of desulfurization by a monomer (olefin) treatment are given. Further work on the desulfurization of the Ohio coals is recommended in a small scale pilot plant on a continuous basis. This pilot plant will represent an approximation of a real plant which will allow the necessary insight needed for scale up.

  14. Economic assessment of advanced flue gas desulfurization processes. Final report. Volume 2. Appendices G, H, and I

    SciTech Connect

    Bierman, G. R.; May, E. H.; Mirabelli, R. E.; Pow, C. N.; Scardino, C.; Wan, E. I.

    1981-09-01

    This report presents the results of a project sponsored by the Morgantown Energy Technology Center (METC). The purpose of the study was to perform an economic and market assessment of advanced flue gas desulfurization (FGD) processes for application to coal-fired electric utility plants. The time period considered in the study is 1981 through 1990, and costs are reported in 1980 dollars. The task was divided into the following four subtasks: (1) determine the factors affecting FGD cost evaluations; (2) select FGD processes to be cost-analyzed; (3) define the future electric utility FGD system market; and (4) perform cost analyses for the selected FGD processes. The study was initiated in September 1979, and separate reports were prepared for the first two subtasks. The results of the latter two subtasks appear only in this final report, since the end-date of those subtasks coincided with the end-date of the overall task. The Subtask 1 report, Criteria and Methods for Performing FGD Cost Evaluation, was completed in October 1980. A slightly modified and condensed version of that report appears as Appendix B to this report. The Subtask 2 report, FGD Candidate Process Selection, was completed in January 1981, and the principal outputs of that subtask appear in Appendices C and D to this report.

  15. BIOCATALYTIC SOLVENT-FREE POLYMERIZATION TO PRODUCE HIGH MOLECULAR WEIGHT POLYESTERS. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. ONE STEP BIOCATALYTIC SYNTHESIS OF LINEAR POLYESTERS WITH PENDANT HYDROXYL GROUPS. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  17. RAPID BIOCATALYTIC POLYTRANSESTERIFICATION: REACTION KINETICS IN AN EXOTHERMIC REACTION. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  18. USE OF A BATCH-STIRRED REACTOR TO RATIONALLY TAILOR BIOCATALYTIC POLYTRANSESTERIFICATION. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  19. Integrated process design for biocatalytic synthesis by a Leloir Glycosyltransferase: UDP-glucose production with sucrose synthase.

    PubMed

    Schmölzer, Katharina; Lemmerer, Martin; Gutmann, Alexander; Nidetzky, Bernd

    2017-04-01

    Nucleotide sugar-dependent ("Leloir") glycosyltransferases (GTs), represent a new paradigm for the application of biocatalytic glycosylations to the production of fine chemicals. However, it remains to be shown that GT processes meet the high efficiency targets of industrial biotransformations. We demonstrate in this study of uridine-5'-diphosphate glucose (UDP-glc) production by sucrose synthase (from Acidithiobacillus caldus) that a holistic process design, involving coordinated development of biocatalyst production, biotransformation, and downstream processing (DSP) was vital for target achievement at ∼100 g scale synthesis. Constitutive expression in Escherichia coli shifted the recombinant protein production mainly to the stationary phase and enhanced the specific enzyme activity to a level (∼480 U/gcell dry weight ) suitable for whole-cell biotransformation. The UDP-glc production had excellent performance metrics of ∼100 gproduct /L, 86% yield (based on UDP), and a total turnover number of 103 gUDP-glc /gcell dry weight at a space-time yield of 10 g/L/h. Using efficient chromatography-free DSP, the UDP-glc was isolated in a single batch with ≥90% purity and in 73% isolated yield. Overall, the process would allow production of ∼0.7 kg of isolated product/L E. coli bioreactor culture, thus demonstrating how integrated process design promotes the practical use of a GT conversion. Biotechnol. Bioeng. 2017;114: 924-928. © 2016 Wiley Periodicals, Inc.

  20. Cloning, Expression, Characterization, and Biocatalytic Investigation of the 4-Hydroxyacetophenone Monooxygenase from Pseudomonas putida JD1▿ †

    PubMed Central

    Rehdorf, Jessica; Zimmer, Christian L.; Bornscheuer, Uwe T.

    2009-01-01

    While the number of available recombinant Baeyer-Villiger monooxygenases (BVMOs) has grown significantly over the last few years, there is still the demand for other BVMOs to expand the biocatalytic diversity. Most BVMOs that have been described are dedicated to convert efficiently cyclohexanone and related cyclic aliphatic ketones. To cover a broader range of substrate types and enantio- and/or regioselectivities, new BVMOs have to be discovered. The gene encoding a BVMO identified in Pseudomonas putida JD1 converting aromatic ketones (HAPMO; 4-hydroxyacetophenone monooxygenase) was amplified from genomic DNA using SiteFinding-PCR, cloned, and functionally expressed in Escherichia coli. Furthermore, four other open reading frames could be identified clustered around this HAPMO. It has been suggested that these proteins, including the HAPMO, might be involved in the degradation of 4-hydroxyacetophenone. Substrate specificity studies revealed that a large variety of other arylaliphatic ketones are also converted via Baeyer-Villiger oxidation into the corresponding esters, with preferences for para-substitutions at the aromatic ring. In addition, oxidation of aldehydes and some heteroaromatic compounds was observed. Cycloketones and open-chain ketones were not or poorly accepted, respectively. It was also found that this enzyme oxidizes aromatic ketones such as 3-phenyl-2-butanone with excellent enantioselectivity (E ≫100). PMID:19251889

  1. Whole-cell biocatalytic and de novo production of alkanes from free fatty acids in Saccharomyces cerevisiae.

    PubMed

    Foo, Jee Loon; Susanto, Adelia Vicanatalita; Keasling, Jay D; Leong, Susanna Su Jan; Chang, Matthew Wook

    2017-01-01

    Rapid global industrialization in the past decades has led to extensive utilization of fossil fuels, which resulted in pressing environmental problems due to excessive carbon emission. This prompted increasing interest in developing advanced biofuels with higher energy density to substitute fossil fuels and bio-alkane has gained attention as an ideal drop-in fuel candidate. Production of alkanes in bacteria has been widely studied but studies on the utilization of the robust yeast host, Saccharomyces cerevisiae, for alkane biosynthesis have been lacking. In this proof-of-principle study, we present the unprecedented engineering of S. cerevisiae for conversion of free fatty acids to alkanes. A fatty acid α-dioxygenase from Oryza sativa (rice) was expressed in S. cerevisiae to transform C12-18 free fatty acids to C11-17 aldehydes. Co-expression of a cyanobacterial aldehyde deformylating oxygenase converted the aldehydes to the desired alkanes. We demonstrated the versatility of the pathway by performing whole-cell biocatalytic conversion of exogenous free fatty acid feedstocks into alkanes as well as introducing the pathway into a free fatty acid overproducer for de novo production of alkanes from simple sugar. The results from this work are anticipated to advance the development of yeast hosts for alkane production. Biotechnol. Bioeng. 2017;114: 232-237. © 2016 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

  2. Three-step biocatalytic reaction using whole cells for efficient production of tyramine from keratin acid hydrolysis wastewater.

    PubMed

    Zhang, Hongjuan; Wei, Yu; Lu, Yang; Wu, Siping; Liu, Qian; Liu, Junzhong; Jiao, Qingcai

    2016-02-01

    Tyramine has been paid more attention in recent years as a significant metabolite of tyrosine and catecholamine drug and an intermediate of medicinal material and some drugs. In this study, an effective, green, and three-step biocatalytic synthesis method for production of tyramine starting from serine in keratin acid hydrolysis wastewater was developed and investigated. Serine deaminase from Escherichia coli was first combined with tyrosine phenol-lyase from Citrobacter koseri, to convert L-serine to L-tyrosine. L-Tyrosine can then be decarboxylated to tyramine by tyrosinede carboxylase from Lactobacillus brevis. All these enzymes originated from recombinant whole cells. Serine deaminaseand tyrosine phenol-lyase could efficiently convert L-serine in wastewater to L-tyrosine at pH 8.0, 37 °C, and Triton X-100 of 0.04% when tyrosine phenol-lyase and its corresponding substrates were sequentially added. Tyrosine conversion rate reached 98 % by L-tyrosine decarboxylase. In scale-up study, the conversion yield of L-serine in wastewater to tyrosine was up to 89 %. L-Tyrosine was decarboxylated to tyramine with a high yield 94 %. Tyramine hydrochloride was obtained with a total yield 84 %. This study has provided an efficient way of recycling keratin acid hydrolysis wastewater to produce tyramine.

  3. Whole‐cell biocatalytic and de novo production of alkanes from free fatty acids in Saccharomyces cerevisiae

    PubMed Central

    Foo, Jee Loon; Susanto, Adelia Vicanatalita; Keasling, Jay D.; Leong, Susanna Su Jan

    2016-01-01

    ABSTRACT Rapid global industrialization in the past decades has led to extensive utilization of fossil fuels, which resulted in pressing environmental problems due to excessive carbon emission. This prompted increasing interest in developing advanced biofuels with higher energy density to substitute fossil fuels and bio‐alkane has gained attention as an ideal drop‐in fuel candidate. Production of alkanes in bacteria has been widely studied but studies on the utilization of the robust yeast host, Saccharomyces cerevisiae, for alkane biosynthesis have been lacking. In this proof‐of‐principle study, we present the unprecedented engineering of S. cerevisiae for conversion of free fatty acids to alkanes. A fatty acid α‐dioxygenase from Oryza sativa (rice) was expressed in S. cerevisiae to transform C12–18 free fatty acids to C11–17 aldehydes. Co‐expression of a cyanobacterial aldehyde deformylating oxygenase converted the aldehydes to the desired alkanes. We demonstrated the versatility of the pathway by performing whole‐cell biocatalytic conversion of exogenous free fatty acid feedstocks into alkanes as well as introducing the pathway into a free fatty acid overproducer for de novo production of alkanes from simple sugar. The results from this work are anticipated to advance the development of yeast hosts for alkane production. Biotechnol. Bioeng. 2017;114: 232–237. © 2016 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. PMID:26717118

  4. Biotechnological production of fucosylated human milk oligosaccharides: Prokaryotic fucosyltransferases and their use in biocatalytic cascades or whole cell conversion systems.

    PubMed

    Petschacher, Barbara; Nidetzky, Bernd

    2016-10-10

    Human milk oligosaccharides (HMOs) constitute a class of complex carbohydrates unique to mother's milk and are strongly correlated to the health benefits of breastfeeding in infants. HMOs are important as functional ingredients of advanced infant formula and have attracted broad interest for use in health-related human nutrition. About 50% of the HMOs structures contain l-fucosyl residues, which are introduced into nascent oligosaccharides by enzymatic transfer from GDP-l-fucose. To overcome limitation in the current availability of fucosylated HMOs, biotechnological approaches for their production have been developed. Functional expression of the fucosyltransferase(s) and effective supply of GDP-l-fucose, respectively, are both bottlenecks of the biocatalytic routes of synthesis. Strategies of in vitro and in vivo production of fucosylated HMOs are reviewed here. Besides metabolic engineering for enhanced HMO production in whole cells, the focus is on the characteristics and the heterologous overexpression of prokaryotic α1,2- and α1,3/4-fucosyltransferases. Up to 20g/L of fucosylated HMOs were obtained in optimized production systems. Optimized expression enabled recovery of purified fucosyltransferases in a yield of up to 45mg/L culture for α1,2-fucosyltransferases and of up to 200mg protein/L culture for α1,3/4-fucosyltransferases.

  5. Construction of engineered Saccharomyces cerevisiae strain to improve that whole-cell biocatalytic production of melibiose from raffinose.

    PubMed

    Zhou, Yingbiao; Zhu, Yueming; Men, Yan; Dong, Caixia; Sun, Yuanxia; Zhang, Juankun

    2017-01-18

    There are excessive by-products in the biocatalysis process of this whole-cell biocatalytic production of melibiose from raffinose with current Saccharomyces cerevisiae strains. To solve this problem, we constructed engineered strains based on a liquor yeast (S. cerevisiae) via gene deletion (mel1 gene), heterologous integration (fsy1 or/and ffzi1 gene from Candida magnoliae), and gene overexpression (gcr1 gene). Functional verification showed that deletion of the mel1 gene led to elimination of the reactions catalyzed by α-galactosidase, as well as elimination of the degradation of melibiose and the formation of galactose by-product. Insertion of the fsy1 or/and ffzi1 gene and overexpression of the gcr1 gene could contribute to fructose transport for enhancing the biopurification rate of the fructose by-product. Compared with the wild-type strain, the optimal engineered strain of MP8 (Δmel1::fsy1 cm ::ffzi1 cm ::gcr1 sc ) had improved about 30% on yield, 31% on productivity, and 36% on purity of the melibiose product.

  6. Remaining activity determination of the resid desulfurization catalyst in a commerical plant

    SciTech Connect

    Yung-Ji Tarng; Sheng-Yang Ju

    1996-12-31

    The objective of this paper is to present a method to determine the remaining catalyst activity of the resid desulfurization plant. Using the daily available operating data, we can establish a performance curve which is a temperature versus days on stream curve. By the use of the performance curve, we can in situ predict how much the catalyst life remains. With the knowledge of the catalyst life remaining, plant engineers are able to control the operating conditions to meet the specified run length of the catalyst suggested by the catalyst venders and refinery planning department. There are five heavy oil desulfurization (RDS) plants in Chinese Petroleum Corporation (CPC) to produce the low sulfur fuel oil and low metal content feed stocks for the downstream processes. In general four or five reactors are connected in series for the reacting system and catalysts of various types are loaded in each reactor. 3 refs., 1 fig., 4 tabs.

  7. Enzymatic desulfurization of coal. Second quarterly report, October 1--December 15, 1988

    SciTech Connect

    Marquis, J.K.; Kitchell, J.P.

    1988-12-15

    Our current efforts to develop clean coal technology emphasize the advantages of enzymatic desulfurization techniques and have specifically addressed the potential of using partially-purified extracellular microbial enzymes or commercially available enzymes. Our work is focused on the treatment of ``model`` organic sulfur compounds such as dibenzothiophene (DBT) and ethylphenylsulfide (EPS). Furthermore, we are designing experiments to facilitate the enzymatic process by means of a hydrated organic solvent matrix.

  8. Preparation of sodium humate/{alpha}-aluminum oxide adsorbents for flue gas desulfurization

    SciTech Connect

    Sun, Z.G.; Gao, H.Y.; Hu, G.X.; Li, Y.H.

    2009-06-15

    A new composite adsorbent of sodium humate (HNa)=alpha-aluminium oxide ({alpha}-Al{sub 2}O{sub 3}) for flue gas desulfurization (FGD) was prepared using the impregnation method. Both the adsorbent of {alpha}-Al{sub 2}O{sub 3} and HNa={alpha}-Al{sub 2}O{sub 3} were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy dispersive X-ray spectrometer (EDS), and scanning electron microscope (SEM). Desulfurization activity of the adsorbent impregnated with ammonia (NH{sub 4}OH) was investigated in a fixed-bed quartz reactor. Experimental results indicate that HNa, which coats the {alpha}-Al{sub 2}O{sub 3} fibers impregnated with HNa solution, improved the property of {alpha}-Al{sub 2}O{sub 3} support for FGD. On the other hand, the HNa-coating on the adsorbent of HNa/{alpha}-Al{sub 2}O{sub 3} impregnated with NH{sub 4}OH played an important role in enhancing the desulfurization property of the {alpha}-Al{sub 2}O{sub 3}. Due to the strong adsorption capability of HNa, more NH{sub 4}OH was adsorbed in the adsorbent of HNa/{alpha}-Al{sub 2}O{sub 3} the longer a high sulfur dioxide (SO{sub 2}) conversation rate was maintained. In addition, because the desulfurization product was a compound fertilizer consisting of ammonium sulfate ((NH{sub 4}){sub 2}SO{sub 4}), ammonium humate (HNH{sub 4}), and HNa, the recycling use of {alpha}-Al{sub 2}O{sub 3} was also easily achieved. Thus, this study can provide a new cost-effective way to remove SO{sub 2} from flue gas.

  9. Sulfidation of a Novel Iron Sorbent Supported on Lignite Chars during Hot Coal Gas Desulfurization

    NASA Astrophysics Data System (ADS)

    Yin, Fengkui; Yu, Jianglong; Gupta, Sushil; Wang, Shaoyan; Wang, Dongmei; Yang, Li; Tahmasebi, Arash

    The sulfidation behavior of novel iron oxide sorbents supported using activated-chars during desulfurization of hot coal gases has been studied. The sulfidation of the char-supported sorbents was investigated using a fixed-bed quartz reactor in the temperature range of 673K to 873K. The product gases were analyzed using a GC equipped with a TCD and a FPD detector. The sorbent samples before and after sulfidation were examined using SEM and XRD.

  10. Physicochemical characterizations and desulfurization properties in coal combustion of three calcium and sodium industrial wastes

    SciTech Connect

    Jun Cheng; Junhu Zhou; Jianzhong Liu; Xinyu Cao; Kefa Cen

    2009-05-15

    To recycle industrial wastes and reduce SO{sub 2} pollutant emission in coal combustion, the mineralogical compositions, porosity structures, surface morphologies, and desulfurization properties of three calcium and sodium industrial wastes were investigated via X-ray diffraction (XRD), porosimeter, scanning electron microscopy (SEM), and a fixed-bed reactor. (1) White lime mud (WLM) mainly composed of CaCO{sub 3} with Na{sub 2}O and K{sub 2}O impurities has smaller CaCO{sub 3} particles and a higher surface area than limestone. But calcined WLM has larger CaO particles and a lower surface area than limestone calcined at 1200{sup o}C for 300 s. (2) Calcium carbide residue (CCR) mainly composed of Ca(OH)2, has the highest surface area and smaller Ca(OH){sub 2} particles than the CaCO{sub 3} particles in WLM. Its surface area monotonously and dramatically decreases at 1200{sup o}C for 300 s, but the sintered CaO particles are still smaller than those in the limestone. (3) When brine sludge (BS), mainly composed of NaCl and CaCO{sub 3}, is heated at 1200{sup o}C for 300 s, the NaCl/CaO eutectic solvent facilitates the aggregation of some complex composites to form many larger particles. (4) WLM gives the highest desulfurization efficiency of 80.4% at 1000{sup o}C and 65.0% at 1100{sup o}C in coal combustion. Combined CCR and limestone give a synergistic desulfurization efficiency of 45.8% at 1200{sup o}C. BS with a molar ratio of Na/Ca at 1:15 effectively promotes the synergistic desulfurization efficiency of combined CCR and limestone to a peak of 54.9% at 1200{sup o}C. 23 refs., 10 figs., 3 tabs.

  11. Thermal preparation effects on the x-ray diffractograms of compounds produced during flue gas desulfurization

    SciTech Connect

    Wertz, D.L.; Burns, K.H.; Keeton, R.W.

    1995-12-31

    The diffractograms of syn-gypsum and of flue gas desulfurization products indicate that CaSO{sub 4} {center_dot} 2H{sub 2}O is converted to other phase(s) when heated to 100{degrees}C. Syn-hannebachite CaSO{sub 3}{center_dot}0.5H{sub 2}O is unaffected by similar thermal treatment. 6 refs., 3 figs.

  12. Test and Characterization of Some Zeolite Supported Gas Phase Desulfurization Sorbents

    DTIC Science & Technology

    2009-06-01

    of-the-art SOFC electrode material is improving, the gas phase desulfurization step at high temperature is still essential to SOFCs . Our report ...NOTICES Disclaimers The findings in this report are not to be construed as an official Department of the Army position unless so...the use thereof. Destroy this report when it is no longer needed. Do not return it to the originator. Army Research Laboratory Adelphi, MD

  13. Enzymatic desulfurization of coal. Fourth quarterly report, March 16--June 15, 1989

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.; Marquis, J.K.

    1989-06-16

    Our current efforts to develop clean coal technology emphasize the advantages of enzymatic desulfurization techniques and have specifically addressed the potential of using partially-purified extracellular microbial enzymes as well as commercially available enzymes. Our work is focused on the treatment of ``model`` organic sulfur compounds such as dibenzothiophene (DBT) and ethylphenylsulfide (EPS). Furthermore, we are designing experiments to facilitate the enzymatic process by means of a hydrated organic solvent matrix.

  14. Sulfur oxides control technology series: Flue-gas desulfurization. Dual alkali process. Summary report

    SciTech Connect

    Not Available

    1980-10-01

    The report describes a dual alkali (or double alkali) flue gas desulfurization (FGD), which is a throwaway process in which sulfur dioxide (SO2) is removed from the flue gas by a soluble sodium-based scrubbing liquor. The collected SO2 is precipitated as calcium sulfite (CaSO3), calcium sulfate (CaSO4), or a mixed crystal of both salts, and is purged from the system.

  15. Effects of magnetic fields on improving mass transfer in flue gas desulfurization using a fluidized bed

    NASA Astrophysics Data System (ADS)

    Zhang, Qi; Gui, Keting; Wang, Xiaobo

    2016-02-01

    The effects of magnetic fields on improving the mass transfer in flue gas desulfurization using a fluidized bed are investigated in the paper. In this research, the magnetically fluidized bed (MFB) is used as the reactor in which ferromagnetic particles are fluidized with simulated flue gas under the influence of an external magnetic field. Lime slurry is continuously sprayed into the reactor. As a consequence, the desulfurization reaction and the slurry drying process take place simultaneously in the MFB. In this paper, the effects of ferromagnetic particles and external magnetic fields on the desulphurization efficiency are studied and compared with that of quartz particles as the fluidized particles. Experimental results show that the ferromagnetic particles not only act as a platform for lime slurry to precipitate on like quartz particles, but also take part in the desulfurization reaction. The results also show that the specific surface area of ferromagnetic particles after reaction is enlarged as the magnetic intensity increases, and the external magnetic field promotes the oxidation of S(IV), improving the mass transfer between sulphur and its sorbent. Hence, the efficiency of desulphurization under the effects of external magnetic fields is higher than that in general fluidized beds.

  16. [Domestication study about desulfuration microorganism from oxidation ditch by low concentration SO2].

    PubMed

    Huang, Bing; Shi, Zhe; Wang, Yan-Yan; Zhang, Shi-Ling

    2010-06-01

    An excellent desulfuration microorganism with a quick growth and propagation, high activation, high efficiency of removing SO2 is obtained from oxidation ditch of a city sewage treatment plant by inductive acclimatization over 6 d with low concentration SO2 gas (100-2 000 mg/m3). The desulfurition microorganism get their energy sources for growth from transforming SO2 (SO3(2-)) to SO4(2-). The predominant bacterium of the desulfuration microorganism has the same characteristic with Thiobacillus ferrooxidans (T. ferrooxidans), which showed that it was Gram negative, short rod bacteria with a single polar flagellum under a microscopic examination, and obtained its nourishment through the oxidation of inorganic compounds. The technology process condition of domestication and desulfuration of microorganism are particular studied, and the results showed that aerating time, SO2 flux and time to provide nutriment contained N, P, K to microorganism were very important. They have an ability with degradation rate of 160g/ (m3 x h) and degradation efficiency over 50% to transform sulfite to sulfate in liquid phase. The bacteria have a 98% of removing efficiency and over 80% of biodegradation efficiency for the 5 500 mg/m3 SO2 gas and the outlet concentration of SO2 is lower than 100 mg/m3, and also have a 95% of removing efficiency for 15 000 mg/m3 SO2 gas in the packed tower reactor with Raschig ring at 3s contact time.

  17. Enhanced pervaporative desulfurization by polydimethylsiloxane membranes embedded with silver/silica core-shell microspheres.

    PubMed

    Cao, Ruijian; Zhang, Xiongfei; Wu, Hong; Wang, Jingtao; Liu, Xiaofei; Jiang, Zhongyi

    2011-03-15

    Pervaporative desulfurization based on membrane technology provides a promising alternative for removal of sulfur substances (as represented by thiophene) in fluid catalytic cracking (FCC) gasoline. The present study focused on the performance enhancement of polydimethylsiloxane (PDMS) membrane by incorporation of core-shell structured silver/silica microspheres. A silane coupling agent, N-[3-(trimethoxysily)propyl]-ethylenediamine (TSD), was used to chelate the Ag(+) via its amino groups and attach the silver seeds onto the silica surface via condensation of its methoxyl groups. The resultant microspheres were characterized by Zeta-positron annihilation lifetime spectroscopy (ZetaPALS), inductively coupled plasmaoptical emission spectrophotometer (ICP), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Ag(+)/SiO(2)-PDMS composite membranes were prepared by blending PDMS with the as-synthesized silver/silica microspheres. PALS analysis was used to correlate the apparent fractional free volume with permeation flux. The sorption selectivity towards thiophene was enhanced after incorporation of silver/silica microspheres due to the π-complexation between the silver on the microsphere surface and the thiophene molecules. The pervaporative desulfurization performance of the composite membrane was investigated using thiophene/n-octane mixture as a model gasoline. The composite membrane exhibited an optimum desulfurization performance with a permeation flux of 7.76 kg/(m(2)h) and an enrichment factor of 4.3 at the doping content of 5%.

  18. Competitive adsorption desulfurization performance over K - Doped NiY zeolite.

    PubMed

    Li, Haizheng; Han, Xiaona; Huang, Haokai; Wang, Yuxian; Zhao, Liang; Cao, Liyuan; Shen, Baojian; Gao, Jinsen; Xu, Chunming

    2016-12-01

    NiY and KNiY were successfully prepared by impregnation method and characterized by X-ray diffraction (XRD), N2 sorption (BET), scanning electron microscope (SEM), infrared spectrum (IR) and X-ray Photoelectron Spectroscopy (XPS). The competitive adsorption mechanisms of adsorbents were studied by in situ FTIR to explain different desulfurization performance which was evaluated in a miniature fixed-bed flow by gasoline model compounds with 1-hexene or toluene. NiY and KNiY adsorbents showed better desulfurization performance than HY zeolite due to the high selectivity of loaded active metals. Especially, KNiY adsorbent showed its advantages in desulfurization performance with 5vol% olefins or 5vol% aromatics involvement. It could be assigned that introduced K cation enhanced dispersion and content of active Ni species on the surface which made Ni species reduce easily. On the other hand, adsorption mechanisms showed that the protonation reactions of thiophene and 1-hexene occurred on the Brönsted acid sites of NiY, which resulted in pore blockage and the coverage of adsorption active centers. By doping K cation on NiY, the amount of the Brönsted acid sites of NiY was decreased and protonation reactions were weaken. Therefore, the negative effects of Brönsted acid sites were reduced.

  19. Catalytic Emulsion Based on Janus Nanosheets for Ultra-Deep Desulfurization.

    PubMed

    Xia, Lixin; Zhang, Hairan; Wei, Zhichao; Jiang, Yi; Zhang, Ling; Zhao, Jie; Zhang, Junhui; Dong, Li; Li, Erni; Ruhlmann, Laurent; Zhang, Qian

    2017-02-03

    Catalytic Janus nanosheets were synthesized by using an anion-exchange reaction between heteropolyacids (HPAs) and the modified ionic-liquid (IL) moieties of Janus nanosheets. Their morphology and surface properties were characterized by using SEM, energy-dispersive spectroscopy (EDS), FTIR spectroscopy, and X-ray photoelectron spectroscopy (XPS) studies. Because of their inherent Janus structure, the nanosheets exhibited good amphipathic character with ILs and oil to form a stable ILs-in-oil emulsion. Therefore, these Janus nanosheets can be used as both emulsifiers and catalysts to perform emulsive desulfurization. During this process, sulfur-containing compounds at the interface could be easily oxidized and efficiently removed from a model oil. Application of this Janus emulsion brings an efficient, useful, and green procedure to the desulfurization process. Compared with the desulfurization catalyzed by using HPAs in a conventional two-phase system, the sulfur removal of dibenzothiophene (DBT) achieved in a Janus emulsion system was improved from 68 to 97 % within 1.5 h. Moreover, this emulsion system could be demulsified easily by simple centrifugation to recover both the nanosheets and the ILs. Owing to the good structural stability of the Janus nanosheets, the sulfur removal efficiency of DBT could still reach 99.9 % after the catalytic nanosheets had been recycled at least six times.

  20. Preparation of Ag/TiO2-zeolite adsorbents, their desulfurization performance, and benzothiophene adsorption isotherms

    NASA Astrophysics Data System (ADS)

    Song, Hua; Yang, Gang; Song, Hua-Lin; Wang, Deng; Wang, Xue-Qin

    2017-02-01

    A series of Ag/TiO2-NaY (TY) composite adsorbents were successfully prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, BET, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The effects of TiO2 and Ag contents on the structure and desulfurization performance of NaY zeolite were studied. The results show that anatase phase is the main form of TiO2 in AgTY adsorbent, and the Y-zeolite framework remained unchanged. AgTY with 6 wt % of Ag and 50 wt % of TiO2 exhibited the best desulfurization performance with the effluent volume of 63.2 mL/g at 10 mg/L sulfur breakthrough level (desulfurization rate of 95%). The benzothiophene (BT) removal performance of the various adsorbents follows the order: NaY < TiO2 < TY-50 < AgTY-50-6. The equilibrium data were modeled by Langmuir and Freundlich equations. The Langmuir model can describe well the adsorption isotherms of BT over AgTY.

  1. Desulfurization of dibenzothiophene by a newly isolated Corynebacterium sp. ZD-1 in aqueous phase.

    PubMed

    Wang, Miao-Dong; Li, Wei; Wang, Da-Hui; Shi, Yao

    2004-01-01

    Sulfur emission through fuel combustion is a global problem because it is a major cause of acid rain. Crud oil contains many heterocyclic organic sulfur compounds, among which dibenzothiophene (DBT) and DBTs bearing alkyl substitutions usually are representative compounds. A strain was isolated from refinery sludge and identified as Corynebacterium ZD-1. The behavior of DBT degradation by ZD-1 in aqueous phase was investigated. Corynebacterium ZD-1 could metabolize DBT to 2-hydroxybiphenyl(2-HBP) as the dead-end metabolite through a sulfur-specific pathway. In shake flask culture, ZD-1 had its maximal desulfurization activity in the late exponential growth phase and the specific production rate of 2-HBP was about 0.14 (mmol x kg dry cell(-1) x min(-1), mmol x KDC(-1) x min(-1)). Active resting cells for desulfurization should be prepared only in this period. 2-HBP inhibited the growth of strain ZD-1, the production of DBT degradation enzymes, and the activity of enzymes. Sulfate inhibited the production of dibenzothiophene (DBT) degradation enzymes but had no effect on the enzymes' activity. The production rates of 2-HBP at lower cell densities were higher and the maximum amount conversion of DBT to 2-HBP (0.067 mmol/L) after 8 h was gained at 9.2 g dry cell/L rather higher cell density. The results indicated that this newly isolated strain could be a promising biocatalyst for DBT desulfurization.

  2. [Research on desulfurization using coke-oven wastewater with pulsed corona discharge].

    PubMed

    Shao, Gui-wei; Li, Jin; Wang, Wan-lin; Li, Sheng-li

    2004-03-01

    A recent investigation into the application of pulsed corona discharge process, in which simultaneous SO2 removal from simulated flue gas and coke-oven wastewater degradation, was conducted at Wuhan Integrated Steel Plant. The outcome indicates that coke-oven wastewater had good desulfurization ability, and SO2 removal efficiency increased gradually as the simulated flue gas temperature increasing in the temperature range used during the experiment. When the flow of simulated flue gas was 428 m3/h, the temperature of simulated flue gas was 65 degrees C and coke-oven wastewater flow was 107 L/h, the desulfurization rate was 85%. Introducing pulsed corona discharge to the reactor enhanced the removal efficiencies of SO2, the desulfurization rate increased to 90% when high voltage was 52kV. When SO2 was removed from simulated flue gas by pulsed corona discharge, oil and phenols content in coke-oven wastewater decreased 39.26% and 68.75% respectively, and 99.98% content of cyanide was degraded, which is of important value in solving the inactivation problem of aerobic bacteria in biological treatment of coke-oven wastewater.

  3. Highly stable and regenerable Mn-based/SBA-15 sorbents for desulfurization of hot coal gas.

    PubMed

    Zhang, F M; Liu, B S; Zhang, Y; Guo, Y H; Wan, Z Y; Subhan, Fazle

    2012-09-30

    A series of mesoporous xCuyMn/SBA-15 sorbents with different Cu/Mn atomic ratios were prepared by wet impregnation method and their desulfurization performance in hot coal gas was investigated in a fixed-bed quartz reactor in the range of 700-850°C. The successive nine desulfurization-regeneration cycles at 800°C revealed that 1Cu9Mn/SBA-15 presented high performance with durable regeneration ability due to the high dispersion of Mn(2)O(3) particles incorporated with a certain amount of copper oxides. The breakthrough sulfur capacity of 1Cu9Mn/SBA-15 observed 800°C is 13.8 g S/100g sorbents, which is remarkably higher than these of 40 wt%LaFeO(3)/SBA-15 (4.8 g S/100g sorbents) and 50 wt%LaFe(2)O(x)/MCM-41 (5.58 g S/100g sorbents) used only at 500-550°C. This suggested that the loading of Mn(2)O(3) active species with high thermal stability to SBA-15 support significantly increased sulfur capacity at relatively higher sulfidation temperature. The fresh and used xCuyMn/SBA-15 sorbents were characterized by means of BET, XRD, XPS, XAES, TG/DSC and HRTEM techniques, confirmed that the structure of the sorbents remained intact before and after hot coal gas desulfurization.

  4. Removal of polychlorinated naphthalenes by desulfurization and emissions of polychlorinated naphthalenes from sintering plant

    PubMed Central

    Wang, Mengjing; Liu, Wenbin; Hou, Meifang; Li, Qianqian; Han, Ying; Liu, Guorui; Li, Haifeng; Liao, Xiao; Chen, Xuebin; Zheng, Minghui

    2016-01-01

    The sintering flue gas samples were collected at the inlets and outlets of the desulfurization systems to evaluate the influence of the systems on PCNs emission concentrations, profiles, and emission factors. The PCNs concentrations at the inlets and outlets were 27888–153672 pg m−3 and 11988–42245 pg m−3,respectively. Desulfurization systems showed excellent removal for PCNs, and the removal efficiencies of PCNs increase with increasing chlorination level. Lower chlorinated homologs are more sensitive to the desulfurization process than higher ones. High levels of PCNs were also detected in the gypsum (11600–29720 pg g−1) and fly ash samples (4946–64172 pg g−1). The annual total emissions of PCNs released to flue gas and gypsum from the sintering plants were about 394 kg, 48.5% of which was in gypsum. The surface area of the fly ash samples increased significantly from the first to the fourth stage of the series-connected electrostatic precipitator, accompanying obvious rising of concentration of PCNs in the fly ash samples. PMID:27197591

  5. Numerical simulation and field test study of desulfurization wastewater evaporation treatment through flue gas.

    PubMed

    Deng, Jia-Jia; Pan, Liang-Ming; Chen, De-Qi; Dong, Yu-Quan; Wang, Cheng-Mu; Liu, Hang; Kang, Mei-Qiang

    2014-01-01

    Aimed at cost saving and pollution reduction, a novel desulfurization wastewater evaporation treatment system (DWETS) for handling wet flue gas desulfurization (WFGD) wastewater of a coal-fired power plant was studied. The system's advantages include simple process, and less investment and space. The feasibility of this system has been proven and the appropriate position and number of nozzles, the spray droplet size and flue gas temperature limitation have been obtained by computational fluid dynamics (CFD) simulation. The simulation results show that a longer duct, smaller diameter and higher flue gas temperature could help to increase the evaporation rate. The optimal DWETS design of Shangdu plant is 100 μm droplet sprayed by two nozzles located at the long duct when the flue gas temperature is 130 °C. Field tests were carried out based on the simulation results. The effects of running DWETS on the downstream devices have been studied. The results show that DWETS has a positive impact on ash removal efficiency and does not have any negative impact on the electrostatic precipitator (ESP), flue gas heat exchanger and WFGD. The pH values of the slurry of WFGD slightly increase when the DWETS is running. The simulation and field test of the DWETS show that it is a feasible future technology for desulfurization wastewater treatment.

  6. Semi-wet flue gas desulfurization with a multi-solid fluidized bed

    SciTech Connect

    Lei, Z.; Wu, C.; Xu, B.; Chen, Y.; Liu, B.

    1997-12-31

    In this study, the authors put forward a new flue gas desulfurization process with a Multi-Solid Fluidized Bed. The principle of the method is as follows. The flue gas is supplied to the bottom of the fluidized bed and lime/limestone slurry is dropped from the top to a bed of the coarse particles. The slurry is uniformly dispersed in the bed by the fluidizing coarse particles, so that the slurry can make contact with the flue gas sufficiently. Dried fine particles of desulfurization product are entrained to the gas-solid separator. In this system, the drying process of the slurry is a key point. During the primary work, they investigated the drying mechanism of the limestone slurry containing fine particles in the coarse particle bed. The desulfurization performance of a simulated flue gas has been carried out. It is concluded that: (1) the drying process of the slurry is mainly one of the water involved; (2) the slurry drying process can be separated into two steps with constant and decreasing velocity, respectively; and (3) using this apparatus, more than 95% SO{sub 2} removal can be obtained when Ca/S equals 2.

  7. A multicomponent assembly approach for the design of deep desulfurization heterogeneous catalysts.

    PubMed

    Xu, Yanqi; Xuan, Weimin; Zhang, Mengmeng; Miras, Haralampos N; Song, Yu-Fei

    2016-12-06

    Deep desulfurization is a challenging task and global efforts are focused on the development of new approaches for the reduction of sulfur-containing compounds in fuel oils. In this work, we have proposed a new design strategy for the development of deep desulfurization heterogeneous catalysts. Based on the adopted design strategy, a novel composite material of polyoxometalate (POM)-based ionic liquid-grafted layered double hydroxides (LDHs) was synthesized by an exfoliation/grafting/assembly process. The structural properties of the as-prepared catalyst were characterized using FT-IR, XRD, TG, NMR, XPS, BET, SEM and HRTEM. The heterogeneous catalyst exhibited high activity in deep desulfurization of DBT (dibenzothiophene), 4,6-DMDBT (4,6-dimethyldibenzothiophene) and BT (benzothiophene) at 70 °C in 25, 30 and 40 minutes, respectively. The catalyst can be easily recovered and reused at least ten times without obvious decrease of its catalytic activity. Such excellent sulfur removal ability as well as the cost efficiency of the novel heterogeneous catalyst can be attributed to the rational design, where the spatial proximity of the substrate and the active sites, the immobilization of ionic liquid onto the LDHs via covalent bonding and the recyclability of the catalyst are carefully considered.

  8. Preliminary evaluation of a process using plasma reactions to desulfurize heavy oils. Final report

    SciTech Connect

    Grimes, P.W.; Miknis, F.P.

    1997-09-01

    Western Research Institute (WRI) has conducted exploratory experiments on the use of microwave-induced plasmas to desulfurize heavy oils. Batch mode experiments were conducted in a quartz reactor system using various reactive and nonreactive plasmas. In these experiments a high-sulfur asphalt was exposed to various plasmas, and the degree of conversion to distillate, gas, and solids was recorded. Products from selected experiments were analyzed to determine if the plasma exposure had resulted in a significant reduction in sulfur content. Exploratory experiments were conducted using reactive plasmas generated from hydrogen and methane and nonreactive plasmas generated from nitrogen. The effects of varying exposure duration, sample temperature, and location of the sample with respect to the plasma discharge were investigated. For comparative purposes two experiments were conducted in which the sample was heated under nitrogen with no plasma exposure. Distillates containing approximately 28% less sulfur than the feedstock represented the maximum desulfurization attained in the plasma experiments. It does not appear that plasma reactions using the simple configurations employed in this study represent a viable method for the desulfurization of heavy oils.

  9. Integrating desulfurization with CO{sub 2}-capture in chemical-looping combustion

    SciTech Connect

    Solunke, Rahul; Veser, Goetz

    2011-02-01

    Chemical looping combustion (CLC) is an emerging technology for clean combustion. We have previously demonstrated that the embedding of metal nanoparticles into a nanostructured ceramic matrix can result in unusually active and sinter-resistant nanocomposite oxygen carrier materials for CLC which maintain high reactivity and high-temperature stability even when sulfur contaminated fuels are used in CLC. Here, we propose a novel process scheme for in situ desulfurization of syngas with simultaneous CO{sub 2}-capture in chemical looping combustion by using these robust nanocomposite oxygen carriers simultaneously as sulfur-capture materials. We found that a nanocomposite Cu-BHA carrier can indeed strongly reduce the H{sub 2}S concentration in the fuel reactor effluent. However, during the process the support matrix is also sulfidized and takes part in the redox process of CLC. This results in SO{sub 2} production during the reduction of the oxygen carrier and thus limits the degree of desulfurization attainable with this kind of carrier. Nevertheless, the results suggest that simultaneous desulfurization and CO{sub 2} capture in CLC is feasible with Cu as oxygen carrier as long as appropriate carrier support materials are chosen, and could result in a novel, strongly intensified process for low-emission, high efficiency combustion of sulfur contaminated fuel streams.

  10. Desulfurization of aromatic sulfonates by rhizosphere bacteria: high diversity of the asfA gene.

    PubMed

    Schmalenberger, Achim; Kertesz, Michael A

    2007-02-01

    The plant growth-promoting effect of Pseudomonas putida S-313 is associated with its ability to desulfurize arylsulfonates. To understand this further, other plant-associated bacteria able to desulfurize a range of arylsulfonates were isolated from the rhizospheres of winter and spring barley. The isolates belonged to the beta-proteobacteria, including bacteria from the Variovorax paradoxus group and from the Acidovorax genus. They desulfurized toluenesulfonate to p-cresol, and were found to contain orthologues of the P. putida S-313 asfA gene (> 70% sequence identity to AsfA), which is required for aryldesulfonation in this species. Further putative asfA orthologues were identified in several bacteria and cyanobacteria whose genomes have been sequenced, but of these only Cupriavidus (Ralstonia) metallidurans was able to utilize arylsulfonates as sulfur source. Cultivation of V. paradoxus, C. metallidurans or P. putida S-313 with toluenesulfonate as sulfur source led to a 100-fold increase in expression of the asfA homologues, which was largely repressed when sulfate was added. Polymerase chain reaction with degenerate primers was used to generate asfAB clone libraries from spring- and winter-barley rhizosphere DNA. Cluster analysis of 76 sequenced AsfA fragments revealed a broad diversity, with the majority of the sequences clustered together with AsfA from bacteria that are able to utilize toluenesulfonate as sulfur source. The diversity of asfA in barley rhizosphere underlines the importance of the desulfonation process for bacteria that inhabit the plant rhizosphere.

  11. Proteomics and Metabolomics Analyses to Elucidate the Desulfurization Pathway of Chelatococcus sp.

    PubMed Central

    Chaudhuri, Mihir K.

    2016-01-01

    Desulfurization of dibenzothiophene (DBT) and alkylated DBT derivatives present in transport fuel through specific cleavage of carbon-sulfur (C-S) bonds by a newly isolated bacterium Chelatococcus sp. is reported for the first time. Gas chromatography-mass spectrometry (GC-MS) analysis of the products of DBT degradation by Chelatococcus sp. showed the transient formation of 2-hydroxybiphenyl (2-HBP) which was subsequently converted to 2-methoxybiphenyl (2-MBP) by methylation at the hydroxyl group of 2-HBP. The relative ratio of 2-HBP and 2-MBP formed after 96 h of bacterial growth was determined at 4:1 suggesting partial conversion of 2-HBP or rapid degradation of 2-MBP. Nevertheless, the enzyme involved in this conversion process remains to be identified. This production of 2-MBP rather than 2-HBP from DBT desulfurization has a significant metabolic advantage for enhancing the growth and sulfur utilization from DBT by Chelatococcus sp. and it also reduces the environmental pollution by 2-HBP. Furthermore, desulfurization of DBT derivatives such as 4-M-DBT and 4, 6-DM-DBT by Chelatococcus sp. resulted in formation of 2-hydroxy-3-methyl-biphenyl and 2-hydroxy –3, 3/- dimethyl-biphenyl, respectively as end product. The GC and X-ray fluorescence studies revealed that Chelatococcus sp. after 24 h of treatment at 37°C reduced the total sulfur content of diesel fuel by 12% by per gram resting cells, without compromising the quality of fuel. The LC-MS/MS analysis of tryptic digested intracellular proteins of Chelatococcus sp. when grown in DBT demonstrated the biosynthesis of 4S pathway desulfurizing enzymes viz. monoxygenases (DszC, DszA), desulfinase (DszB), and an NADH-dependent flavin reductase (DszD). Besides, several other intracellular proteins of Chelatococcus sp. having diverse biological functions were also identified by LC-MS/MS analysis. Many of these enzymes are directly involved with desulfurization process whereas the other enzymes/proteins support

  12. Molecular biological enhancement of coal desulfurization. [Thiobacillus cuprinus

    SciTech Connect

    Litchfield, J.H.; Zupancic, T.J.; Kittle, J.D. Jr.; Baker, B.; Palmer, D.T.; Traunero, C.G.; Wyza, R.E.; Schweitzer, A.; Conkle, H.N. ); Chakravarty, L.; Tuovinen, O.H. )

    1991-03-13

    The objective of this project is to produce one or more microorganisms capable of removing the organic and inorganic sulfur in coal. The original specific technical objectives of the project were to: clone and characterize the genes encoding the enzymes of the 4S'' pathway (sulfoxide/sulfone/sulfonate/sulfate) for release of organic sulfur from coal; return multiple copies of genes to the original host to enhance the biodesulfurization activity of the organism; transfer this pathway into a fast-growing chemolithotrophic bacterium; conduct a batch-mode optimization/analysis of scale-up variables.

  13. Tyramine-based enzymatic conjugate repeats for ultrasensitive immunoassay accompanying tyramine signal amplification with enzymatic biocatalytic precipitation.

    PubMed

    Hou, Li; Tang, Yun; Xu, Mingdi; Gao, Zhuangqiang; Tang, Dianping

    2014-08-19

    A new impedimetric immunoassay protocol based on enzyme-triggered formation of tyramine-enzyme repeats on gold nanoparticle (AuNP) was designed for highly sensitive detection of carcinoembryonic antigen (CEA, as a model) by virtue of utilizing enzymatic biocatalytic precipitation toward 4-chloro-1-naphthol (4-CN) on anti-CEA antibody (Ab1)-modified immunosensor. Initially, AuNP was functionalized with horseradish peroxidase and detection antibody (HRP-AuNP-Ab2), and then HRP-tyramine conjugate was utilized for the formation of tyramine-HRP repeats through the triggering of the immobilized HRP on the AuNP with the aid of H2O2. In the presence of target CEA, the carried HRP-tyramine repeats accompanying the sandwiched immunocomplex catalyzed the 4-CN oxidation to produce an insoluble precipitation on the immunosensor, thus causing a local alteration of the conductivity. Three signal-transduction tags including HRP-Ab2, HRP-AuNP-Ab2, and HRP-AuNP-Ab2 with HRP-tyramine repeats were employed for target CEA evaluation, and improved analytical properties were achieved by HRP-AuNP-Ab2 with HRP-tyramine repeats. Using the unique signal-transduction tag, the analytical performance of the impedimetric immunoassay was studied in detail. Under the optimal conditions, the impedimetric immunosensor displayed a wide dynamic working range of between 0.5 pg mL(-1) and 40 ng mL(-1) with a detection limit (LOD) of 0.38 pg mL(-1) relative to target CEA. The coefficients of variation (CVs) were ≤9.3% and 13.3% for the intra-assay and interassay, respectively. The levels of CEA in eight clinical serum specimens were measured by using the developed impedimetric immunosensor. The obtained results correlated well with those from the electrochemiluminescent (ECL)-based immunoassay with a correlation coefficient of 0.998.

  14. Adipic acid enhanced flue gas desulfurization process for industrial boilers. Volume 2. Technical assessment. Project summary

    SciTech Connect

    Behrens, G.P.; Hargrove, O.W.

    1983-03-01

    The SO/sub 2/ removal efficiency with the adipic acid averaged 94.3% over a 30-day period, representing a significant improvement in the performance of the system using only limestone. Economic calculations for an industrial boiler adipic-acid-enhanced limestone FGD system indicate a slight reduction in both capital and operating expenses relative to a limestone-only system designed for 90% SO/sub 2/ control of 3.5% sulfur coal. The costs are competitive with the dual alkali system. The successful demonstration of the adipic-acid-enhanced limestone system increases the number of demonstrated technologies available to a potential user.

  15. Desulfurization and denitrogenation of heavy gas oil by Rhodococcus erythropolis ATCC 4277.

    PubMed

    Maass, D; Todescato, D; Moritz, D E; Oliveira, J Vladimir; Oliveira, D; Ulson de Souza, A A; Guelli Souza, S M A

    2015-08-01

    Some of the noxious atmospheric pollutants such as nitrogen and sulfur dioxides come from the fossil fuel combustion. Biodesulfurization and biodenitrogenation are processes which remove those pollutants through the action of microorganisms. The ability of sulfur and nitrogen removal by the strain Rhodococcus erythropolis ATCC 4277 was tested in a biphasic system containing different heavy gas oil concentrations in a batch reactor. Heavy gas oil is an important fraction of petroleum, because after passing through, the vacuum distillation is incorporated into diesel oil. This strain was able to remove about 40% of the nitrogen and sulfur present in the gas heavy oil. Additionally, no growth inhibition occurred even when in the presence of pure heavy gas oil. Results present in this work are considered relevant for the development of biocatalytic processes for nitrogen and sulfur removal toward building feasible industrial applications.

  16. Interaction between Ni and HZSM-5 in aromatization-enhanced reactive adsorption desulfurization catalysts for FCC gasoline upgrading.

    PubMed

    Zhao, Jinchong; Zhang, Lulu; She, Nannan; Liu, Yunqi; Chai, Yongming; Liu, Chenguang

    A compound catalyst (RA) consisted of Ni, ZnO and HZSM-5 with functions of reactive adsorption desulfurization (RADS) and olefin aromatization for fluid catalytic cracking (FCC) gasoline upgrading was prepared. X-ray powder diffraction (XRD), temperature-programmed reduction and low-temperature N2 adsorption were used to characterize the properties of the catalysts. Performance evaluation by FCC gasoline was carried out, and the result showed that the catalyst RA performed well in desulfurization and aromatization. For comparison, RADS catalyst (represented by DS) consisted of Ni and ZnO and aromatization catalyst (represented by Ar) consisted of HZSM-5 were prepared, respectively. They were combined in different ways to help investigating interaction between Ni and HZSM-5. Performance evaluated by FCC gasoline showed that catalyst RA performed best in desulfurization with a slight octane number loss. Interaction between Ni and HZSM-5 is a significant factor which influences the performance of the catalyst.

  17. Evaluation of sulfur-reducing microorganisms for organic desulfurization. Final technical report, September 1, 1990--August 31, 1991

    SciTech Connect

    Miller, K.W.

    1991-12-31

    Because of substantial portion of the sulfur in Illinois coal is organic, microbial desulfurization of sulfidic and thiophenic functionalities could hold great potential for completing pyritic sulfur removal. We are testing the hypothesis that organic sulfur can be reductively removed as H{sub 2}S through the activities of anaerobic microorganisms. Our objectives for this year include the following: (1) To obtain cultures that will reductively desulfurize thiophenic model compounds. In addition to crude oil enrichments begun last year, we sampled municipal sewage sludge. (2) To continue to work toward optimizing the activity of the DBDS-reducing cultures obtained during the previous year. (3) To expand coal desulfurization work to include other coals including Illinois Basin Coal 101 and a North Dakota lignite, which might be more susceptible to the dibenzyldisulfide reducing cultures due to its lower rank. (4) To address the problem of sulfide sorption, by investigating the sorption capacity of coals in addition to Illinois Basin Coal 108.

  18. Identification and Cloning of Genes Involved in Specific Desulfurization of Dibenzothiophene by Rhodococcus sp. Strain IGTS8.

    PubMed

    Denome, S A; Olson, E S; Young, K D

    1993-09-01

    The gram-positive bacterium Rhodococcus sp. strain IGTS8 is able to remove sulfur from certain aromatic compounds without breaking carbon-carbon bonds. In particular, sulfur is removed from dibenzothiophene (DBT) to give the final product, 2-hydroxybiphenyl. A genomic library of IGTS8 was constructed in the cosmid vector pLAFR5, but no desulfurization phenotype was imparted to Escherichia coli. Therefore, IGTS8 was mutagenized, and a new strain (UV1) was selected that had lost the ability to desulfurize DBT. The genomic library was transferred into UV1, and several colonies that had regained the desulfurization phenotype were isolated, though free plasmid could not be isolated. Instead, vector DNA had integrated into either the chromosome or a large resident plasmid. DNA on either side of the inserted vector sequences was cloned and used to probe the original genomic library in E. coli. This procedure identified individual cosmid clones that, when electroporated into strain UV1, restored desulfurization. When the origin of replication from a Rhodococcus plasmid was inserted, the efficiency with which these clones transformed UV1 increased 20- to 50-fold and they could be retrieved as free plasmids. Restriction mapping and subcloning indicated that the desulfurization genes reside on a 4.0-kb DNA fragment. Finally, the phenotype was transferred to Rhodococcus fascians D188-5, a species normally incapable of desulfurizing DBT. The mutant strain, UV1, and R. fascians produced 2-hydroxybiphenyl from DBT when they contained appropriate clones, indicating that the genes for the entire pathway have been isolated.

  19. Purification of CYP2B-like protein from feral leaping mullet (Liza saliens) liver microsomes and its biocatalytic, molecular, and immunological characterization.

    PubMed

    Bozcaarmutlu, Azra; Arinç, Emel

    2008-01-01

    In this study, CYP2B-immunoreactive protein was purified to electrophoretic homogeneity from the liver microsomes of leaping mullet. The purified cytochrome P450 (CYP) gave a single band on sodium dodecyl sulfate-polyacrylamide gel electrophoresis having a M(r) of 49,300 Da. Absolute absorption spectrum of the purified CYP showed a maximum at 417 nm and CO-difference spectrum of dithionite-reduced cytochrome P450 gave a peak at 450 nm. The purified CYP was found to be active in N-demethylation of benzphetamine, erythromycin, and ethylmorphine, and O-dealkylation of pentoxyresorufin in the reconstituted system. However, it was unable to catalyze O-dealkylation of ethoxyresorufin, methoxyresorufin, benzyloxyresorufin, and hydroxylation of lauric acid and aniline. The purified CYP showed strong cross-reactivity with anti-sheep lung CYP2B, a homologue of CYP2B4. N-terminal amino acid sequence of the mullet P450 had the highest degree of homology with CYP2Bs among the known CYPs. Spectral, electrophoretic, immunochemical, N-terminal amino acid sequence, and biocatalytic properties of the purified CYP are most similar to those of mammalian cytochrome P4502B. All these data indicate that the purified CYP is certainly 2B-like. In this study, we not only purified biocatalytically active CYP2B-like protein from fish, but also demonstrated detailed functional properties of CYP2B-like protein for the first time.

  20. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Quarterly technical progress report No. 1, October--December 1986

    SciTech Connect

    Jha, M.C.; Baltich, L.K.

    1987-02-23

    AMAX Research & Development Center (AMAX R&D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such As size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  1. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Volume 1, Bench-scale testing and analysis

    SciTech Connect

    Jha, M.C.; Berggren, M.H.

    1989-05-02

    AMAX Research & Development Center (AMAX R&D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such As size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  2. An efficient approach for conversion of 5-substituted 2-thiouridines built in RNA oligomers into corresponding desulfured 4-pyrimidinone products.

    PubMed

    Chwialkowska, Anna; Wielgus, Ewelina; Leszczynska, Grazyna; Sobczak, Milena; Mikolajczyk, Barbara; Sochacka, Elzbieta; Nawrot, Barbara

    2015-08-15

    An efficient approach for the desulfuration of C5-substituted 2-thiouridines (R5S2U) bound in the RNA chain exclusively to 4-pyrimidinone nucleoside (R5H2U)-containing RNA products is proposed. This post-synthetic transformation avoids the preparation of a suitably protected H2U phosphoramidite, which otherwise would be necessary for solid-phase synthesis of the modified RNA. Optimization of the desulfuration, which included reaction stoichiometry, time and temperature, allowed to transform a set of ten R5S2U-RNAs into their R5H2U-RNA congeners in ca. 90% yield.

  3. Determination of dispersion parameters for oxidizing air and the oxidation rate of calcium sulfites in a pilot desulfurization plant

    SciTech Connect

    Burenkov, D.K.; Derevich, I.V.; Rzaev, A.I.

    1995-10-01

    In the effort to remove sulfur oxides from waste gases, the widest use is gained by desulfurization plants based on wet collection of sulfur dioxide in empty absorbers in which a limestone-gypsum suspension is sprayed, with gypsum being produced as a commodity product. Dispersion of oxidizing air in a model liquid and the oxidation rate of calcium sulfites in a suspension contained in the sump of a pilot desulfurization plant absorber are studied experimentally. Flow velocities, bubble trajectories, and oxidation rates were determined and are presented.

  4. Advanced sulfur control concepts in hot-gas desulfurization technology: Phase 1, Feasibility of the direct production of elemental sulfur during the regeneration of high temperature desulfurization sorbents

    SciTech Connect

    Lopez, A.; White, J.; Groves, F.R.; Harrison, D.P.

    1994-10-01

    This topical report de-scribes the results of Phase 1 research performed during the first six months of a three-year contract to study the feasibility of the direct production of elemental sulfur during the regeneration of high temperature desulfurization sorbents. Much effort has gone into the development of a high-temperature meal oxide sorbent process for removal of H{sub 2}S from the coal gas. A number of sorbents based upon metals such as zinc, iron, manganese and others have been studied. In order for high temperature desulfurization to be economical it is necessary that the sorbents be regenerated to permit multicycle operation. Current methods of sorbent regeneration involve oxidation of the metal sulfide to reform the metal oxide and free the sulfur as SO{sub 2}. An alternate regeneration process in which the sulfur is liberated in elemental form is preferable. The overall objective of the current research is to study simpler and economically superior processing of known sorbents capable of producing elemental sulfur during regeneration. This topical report summarizes the first steps of this effort. A literature search has been completed to identify possible regeneration concepts and to collect relevant thermodynamic, kinetic, and process data. Three concepts involving reaction with SO{sub 2}, partial oxidation using an O{sub 2} {minus} H{sub 2}O mixture, and steam regeneration have been identified. The first two concepts result in the direct production of elemental sulfur while H{sub 2}S is the product of steam regeneration. This concept is of potential interest, however, since existing Claus technology can be used to convert H{sub 2}S to elemental sulfur. Following the literature search, a thermodynamic analysis, based upon free-energy minimization was carried out to evaluate candidate sorbents for possible use with the three regeneration concepts.

  5. Influence of Fe loadings on desulfurization performance of activated carbon treated by nitric acid.

    PubMed

    Guo, Jia-Xiu; Shu, Song; Liu, Xiao-Li; Wang, Xue-Jiao; Yin, Hua-Qiang; Chu, Ying-Hao

    2017-02-01

    A series of Fe supported on activated carbon treated by nitric acid are prepared by incipient wetness impregnation with ultrasonic assistance and characterized by N2 adsorption-desorption, X-ray diffraction, Fourier transform infrared spectrum and X-ray photoelectron spectroscopy. It has shown that Fe loadings significantly influence the desulfurization activity. Fe/NAC5 exhibits an excellent removal ability of SO2, corresponding to breakthrough sulfur capacity of 323 mg/g. With the increasing Fe loadings, the generated Fe3O4 and Fe2SiO4 increase, but Fe2(SO4)3 is observed after desulfurization. Fe/NAC1 has a Brunauer-Emmett-Teller (BET) surface area of 925 m(2)/g with micropore surface area of 843 m(2)/g and total pore volume of 0.562 cm(3)/g including a micropore volume of 0.300 cm(3)/g. With the increasing Fe loadings, BET surface area and micropore volume decrease, and those of Fe/NAC10 decrease to 706 m(2)/g and 0.249 cm(3)/g. The Fe loadings influence the pore-size distribution, and SO2 adsorption mainly reacts in micropores at about 0.70 nm. C=O and C-O are observed for all samples before SO2 removal. After desulfurization, the C-O stretching is still detected, but the C=O stretching vibration of carbonyl groups disappears. The stretching of S-O or S=O in sulfate is observed at 592 cm(-1) for the used sample, proving that the existence of [Formula: see text].

  6. Pilot-plant technical assessment of wet flue gas desulfurization using limestone

    SciTech Connect

    Ortiz, F.J.G.; Vidal, F.; Ollero, P.; Salvador, L.; Cortes, V.; Gimenez, A.

    2006-02-15

    An experimental study was performed on a countercurrent pilot-scale packed scrubber for wet flue gas desulfurization (FGD). The flow rate of the treated flue gas was around 300 Nm{sup 3}/h, so the pilot-plant capacity is one of the largest with respect to other published studies on a pilot-plant wet FGD. The tests were carried out at an SO{sub 2} inlet concentration of 2000 ppm by changing the recycle slurry pH to around 4.8 and the L/G ratio to between 7.5 and 15. Three types of limestone were tested, obtaining desulfurization efficiencies from 59 to 99%. We show the importance of choosing an appropriate limestone in order to get a better performance from the FGD plant. Thus, it is important to know the reactivity (on a laboratory scale) and the sorbent utilization (on a pilot-plant scale) in order to identify if a limestone is reactive enough and to compare it with another type. In addition, by using the transfer-unit concept, a function has been obtained for the desulfurization efficiency, using the L/G ratio and the recycle slurry pH as independent variables. The Ca/S molar ratio is related to these and to the SO{sub 2} removal efficiency. This function, together with a simplified function of the operation variable cost, allows us to determine the pair (L/G ratio and pH) to achieve the desired SO{sub 2} removal with the minimum operation cost. Finally, the variable operation costs between packed towers and spray scrubbers have been compared, using as a basis the pilot packed tower and the industrial spray column at the Compostilla Power Station's FGD plant (in Leon, Spain).

  7. Mass spectrometric detection of CYP450 adducts following oxidative desulfuration of methyl parathion.

    PubMed

    Kyle, Patrick B; Smith, Stanley V; Baker, Rodney C; Kramer, Robert E

    2013-07-01

    Cytochrome P450 (CYP)-mediated desulfuration of methyl parathion results in mechanism-based inhibition of the enzyme. Although previous data suggest that reactive sulfur is released and binds to the apoprotein, the identities of neither the adduct(s) nor the affected amino acid(s) have been clearly determined. In this study, nanospray tandem mass spectroscopy was used to analyze peptide digests of CYP resolved by SDS-PAGE from liver microsomes of male rats following incubation in the absence or presence of methyl parathion. Oxidative desulfuration was confirmed by measurement of methyl paraoxon, and inhibition of specific CYP isozymes was determined by measurement of testosterone hydroxylation. Total CYP content was quantified spectrophotometrically. Incubation of microsomes with methyl parathion decreased CYP content by 58%. This effect was not associated with a comparable increase in absorbance at 420 nm, suggesting the displacement of heme from the apoprotein. Rates of testosterone 2β- and 6β-hydroxylation, respectively, were reduced to 8 and 2%, implicating CYP3A and CYP2C11 in the oxidative desulfuration of methyl parathion. Mass spectrometric analysis identified 96 amu adducts to cysteines 64 and 378 of CYP3A1. In addition, a peptide containing cysteine 433 that coordinates with heme was possibly modified as it was detected in control, but not methyl parathion samples. A comparison of rat CYP3A1 with human CYP3A4 suggests that cysteines 64 and 378 reside along the substrate channel, remote from the active site. Alteration of these residues might modulate substrate entry to the binding pocket of the enzyme.

  8. Advances on simultaneous desulfurization and denitrification using activated carbon irradiated by microwaves.

    PubMed

    Ma, Shuang-Chen; Gao, Li; Ma, Jing-Xiang; Jin, Xin; Yao, Juan-Juan; Zhao, Yi

    2012-06-01

    This paper describes the research background and chemistry of desulfurization and denitrification technology using microwave irradiation. Microwave-induced catalysis combined with activated carbon adsorption and reduction can reduce nitric oxide to nitrogen and sulfur dioxide to sulfur from flue gas effectively. This paper also highlights the main drawbacks of this technology and discusses future development trends. It is reported that the removal of sulfur dioxide and nitric oxide using microwave irradiation has broad prospects for development in the field of air pollution control.

  9. Adipic acid-enhanced limestone flue gas desulfurization system commercial demonstration. [Missouri

    SciTech Connect

    Hargrove, O.W. Jr.; Colley, J.D.; Mobley, J.D.

    1981-01-01

    A full-scale demonstration carried out at Springfield, Mo City Utilities Southwest Power Plant in 1980-1981 on adipic acid enhanced limestone flue gas desulfurization system is reported. The major process findings during the demonstration are discussed. It is found that adipic acid is a viable means for improving SO/sub 2/ removal in scrubbers which are limited from a dissolved alkalinity standpoint. Dibasic acid (a mixture of glutaric, adipic, and succinic acids) is a technically viable alternative to adipic acid. 6 refs.

  10. Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

    USGS Publications Warehouse

    Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.; Kruse, C.W.

    1987-01-01

    A method using stable isotope ratio analysis to monitor the reactivity of sulfur forms in coal during thermal and chemical desulfurization processes has been developed at the Illinois State Geological Survey. The method is based upon the fact that a significant difference exists in some coals between the 34S/32S ratios of the pyritic and organic sulfur. A screening method for determining the suitability of coal samples for use in isotope ratio analysis is described. Making these special coals available from coal sample programs would assist research groups in sorting out the complex sulfur chemistry which accompanies thermal and chemical processing of high sulfur coals. ?? 1987.

  11. Process for the manufacture of an attrition resistant sorbent used for gas desulfurization

    DOEpatents

    Venkataramani, Venkat S.; Ayala, Raul E.

    2003-09-16

    This process produces a sorbent for use in desulfurization of coal gas. A zinc titanate compound and a metal oxide are mixed by milling the compounds in an aqueous medium, the resulting mixture is dried and then calcined, crushed, sleved and formed into pellets for use in a moving-bed reactor. Metal oxides suitable for use as an additive in this process include: magnesium oxide, magnesium oxide plus molybdenum oxide, calcium oxide, yttrium oxide, hafnium oxide, zirconium oxide, cupric oxide, and tin oxide. The resulting sorbent has a percentage of the original zinc or titanium ions substituted for the oxide metal of the chosen additive.

  12. Sodium-limestone double alkali flue gas desulfurization process with improved limestone utilization

    SciTech Connect

    Biolchini, R.J.; Boward, W.L. Jr.; Wang, K.H.

    1987-08-18

    This patent describes a sodium-limestone double alkali process for the continuous desulfurization of flue gas, having the steps of absorbing sulfur dioxide from an SO/sub 2/-containing gas stream in an absorber with an aqueous solution of sodium sulfite and sodium bisulfite, diverting at least a portion of the absorber effluent solution for regeneration with limestone, introducing limestone into the diverted absorber effluent solution to convert bisulfite to sulfite, separating by-product solids from the limestone-treated solution, and returning regenerated solution to the absorber, the improvement for increasing the utilization of the limestone used during the regeneration operation.

  13. Molten-Caustic-Leaching (Gravimelt) System Integration Project, Phase 2

    SciTech Connect

    Not Available

    1993-03-01

    This is a report of the maintenance, refurbishment, modifications, and off-line circuit component testing of the integrated test circuit of the Molten-Caustic-Leaching (MCL or Gravimelt) process for the desulfurization and demineralization of coal. The project is sponsored by the Pittsburgh Energy Technology Center of the US Department of Energy under Contract No. DE-AC22-86-PC91257.

  14. Microbial reduction of SO{sub 2} and NO{sub x} as a means of by-product recovery/disposal from regenerable processes for the desulfurization of flue gas. Final report

    SciTech Connect

    Sublette, K.L.

    1994-03-01

    The main objective of this research was to investigate microorganisms capable of fossil fuel flue gas desulfurization and denitrification. The study used municipal sewage sludge as a carbon and energy source for SO{sub 2}-reducing cultures. The individual tasks developed a consortium of sulfate-reducing bacteria, investigated the design parameters for a continuous process, preformed a cost analysis, and screened sulfate-reducing bacteria. In the investigation of microbial reduction of NO{sub x} to nitrogen, tasks included screening denitrifying bacteria for NO and NO{sub 2} activity, developing optimum NO-reducing cultures, and investigating design parameters for a continuous system. This final report reviews the work previous to the current project, describes project objectives and the specific work plan, and reports results from the work completed during the previous reporting periods.

  15. Alcohol Selectivity in a Synthetic Thermophilic n-Butanol Pathway Is Driven by Biocatalytic and Thermostability Characteristics of Constituent Enzymes

    PubMed Central

    Loder, Andrew J.; Zeldes, Benjamin M.; Garrison, G. Dale; Lipscomb, Gina L.; Adams, Michael W. W.

    2015-01-01

    n-Butanol is generated as a natural product of metabolism by several microorganisms, but almost all grow at mesophilic temperatures. A synthetic pathway for n-butanol production from acetyl coenzyme A (acetyl-CoA) that functioned at 70°C was assembled in vitro from enzymes recruited from thermophilic bacteria to inform efforts for engineering butanol production into thermophilic hosts. Recombinant versions of eight thermophilic enzymes (β-ketothiolase [Thl], 3-hydroxybutyryl-CoA dehydrogenase [Hbd], and 3-hydroxybutyryl-CoA dehydratase [Crt] from Caldanaerobacter subterraneus subsp. tengcongensis; trans-2-enoyl-CoA reductase [Ter] from Spirochaeta thermophila; bifunctional acetaldehyde dehydrogenase/alcohol dehydrogenase [AdhE] from Clostridium thermocellum; and AdhE, aldehyde dehydrogenase [Bad], and butanol dehydrogenase [Bdh] from Thermoanaerobacter sp. strain X514) were utilized to examine three possible pathways for n-butanol. These pathways differed in the two steps required to convert butyryl-CoA to n-butanol: Thl-Hbd-Crt-Ter-AdhE (C. thermocellum), Thl-Hbd-Crt-Ter-AdhE (Thermoanaerobacter X514), and Thl-Hbd-Crt-Ter-Bad-Bdh. n-Butanol was produced at 70°C, but with different amounts of ethanol as a coproduct, because of the broad substrate specificities of AdhE, Bad, and Bdh. A reaction kinetics model, validated via comparison to in vitro experiments, was used to determine relative enzyme ratios needed to maximize n-butanol production. By using large relative amounts of Thl and Hbd and small amounts of Bad and Bdh, >70% conversion to n-butanol was observed in vitro, but with a 60% decrease in the predicted pathway flux. With more-selective hypothetical versions of Bad and Bdh, >70% conversion to n-butanol is predicted, with a 19% increase in pathway flux. Thus, more-selective thermophilic versions of Bad, Bdh, and AdhE are needed to fully exploit biocatalytic n-butanol production at elevated temperatures. PMID:26253677

  16. Desulfurization of 4-methyl dibenzothiophene using titanium supported Keggin type polyoxometalate

    NASA Astrophysics Data System (ADS)

    Lesbani, Aldes; Anggraini, Ana; Mohadi, Risfidian; Rohendi, Dedi; Said, Muhammad

    2017-03-01

    Titanium supported Keggin type polyoxometalate H5PV2Mo10O40.nH2O has been prepared using tetra isopropyl orthotitanate by sol-gel method and microemulsion to form H5PV2Mo10O40/TiO2. Compound H5PV2Mo10O40.nH2O/TiO2 was characterized using FTTR spectroscopy, X-Ray analysis, and acidity measurement. FTTR spectrum showed that all vibration of titanium and polyoxometalate were appeared in H5PV2Mo10O40.nH2O/TiO2 with decreasing crystallinity. The acidity of H5PV2Mo10O40.nH2O/TiO2 was higher than H5PV2Mo10O40.nH2O. Desulfurization of 4-methyl dibenzothiophene (4-MDBT) using H5PV2Mo10O40.nH2O/TiO2 as catalyst resulted conversion of 4-MDBT was 99% and higher than desulfurization using H5PV2Mo10O40.nH2O under mild conditions.

  17. Status of METC investigations of coal gas desulfurization at high temperature. [Zinc ferrite

    SciTech Connect

    Steinfeld, G.

    1984-03-01

    This report documents the continuing effort at the US Department of Energy/Morgantown Energy Technology Center (METC) to develop a hot-gas desulfurization process for coal-derived gas, primarily for application to molten carbonate fuel cells. Metal oxide sorbents were tested on lab-scale test equipment, and it was determined that scale-up of the process was warranted. A larger, skid-mounted test unit was therefore designed, constructed, and installed on a sidestream of the DOE/METC fixed-bed gasifier. A first series of tests was conducted during Gasifier Run 101. These tests served to shake down the test unit, and provide data on the performance of the test unit operating on coal-derived gas. Overall, the process operated well on fixed-bed, air-blown gasifier gas. Sulfur levels in exit dry gas were reduced to less than 10 ppM. Regeneration appears to restore the sulfur-removing capacity of the sorbent. Sorbent integrity was maintained during the test period, which incorporated three sulfidations. It is recommended that treatment of the regeneration offgas be investigated, and that testing and development of a system to reduce the sulfur in this gas to elemental sulfur be initiated. In addition, it is suggested that a multiple reactor system be planned for continuous operation, to allow for long-term tests of downstream users of desulfurized gas. 7 references, 18 figures, 9 tables.

  18. Effect of the water-vapor content on the oxidative desulfurization of sulfur-rich coal

    SciTech Connect

    S. Pysh'yev; K. Shevchuk; L. Chmielarz; P. Kutrowski; A. Pattek-Janczyk

    2007-01-15

    Ukrainian sulfur-rich coal containing about 3.6 mass % of sulfur was studied. The desulfurization process was performed in the fluidized-bed reactor in dry (4 vol % of H{sub 2}O vapor) and wet (30-70 vol % of H{sub 2}O vapor) atmospheres in the temperature range of 350-450{sup o}C. A significant influence of the water-vapor content in the reaction mixture on the sulfur removal during the oxidative desulfurization of the coal was observed especially at low temperatures. The extent of FeS{sub 2} oxidation, the main sulfur-containing compound, was studied by Moessbauer spectroscopy. The Moessbauer data revealed different iron-containing products (FeSO{sub 4}nH{sub 2}O, Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4}, and Fe{sub 1-x}S) formed in the course of the process carried out in dry and wet atmospheres. The promoting effect of water vapor on the pyrite transformation was observed especially at low temperatures. The mechanism of this promotion on the molecular scale was proposed. 19 refs., 6 figs., 4 tabs.

  19. Hg2+ reduction and re-emission from simulated wet flue gas desulfurization liquors.

    PubMed

    Wo, Jingjing; Zhang, Meng; Cheng, Xiaoya; Zhong, Xiaohang; Xu, Jiang; Xu, Xinhua

    2009-12-30

    In this study, considering that Hg(2+) in wet flue gas desulfurization (FGD) systems can easily be reduced and then released into atmosphere, causing secondary pollution, the researches about Hg(2+) reduction and Hg(0) re-emission mechanism were carried out. The effects of several experimental parameters on the reduction were studied, including initial pH, temperature, and concentrations of Cl(-) and S(IV). Our experimental results indicated that Cl(-) had a restraining effect on the Hg(2+) reduction and Hg(0) re-emission, after 24h reaction, only 20.5% of Hg(2+) was reduced with 100mM Cl(-) in simulated desulfurization solution. Cl(-) can slow Hg(2+) reduction and Hg(0) re-emissions dramatically through changing reaction mechanism, with formation of new intermediate: ClHgSO(3)(-), which can decompose to Hg(0), but much more slowly than Hg(SO(3))(2)(2-) or HgSO(3). Simulating the conditions of the practical application (initial pH 5, T=50 degrees C, S(IV)=5 mM, Cl(-)=100 mM), we also found that Ca(2+), NO(3)(-), F(-), etc. all had obvious effects on reduction rates. Based on the material balance and characteristic of the reactants, the reduction emission mechanism of Hg(2+) has been established, providing theoretical basis for industrial application of mercury control in wet FGD systems.

  20. Distribution and quality of carbonate rock for desulfurization in coal combustion processes

    SciTech Connect

    Eggleston, J.R.; Kress, T.H.

    1995-12-31

    To meet the requirements of the Federal Clean Air Act of 1970 and the Amendments of 1977 and 1990, coal-burning power plants will use large tonnages of carbonate rock (limestone and dolomite) and lime for flue gas desulfurization, fluidized bed combustion, and other processes designed to minimize air pollution. By January 1, 2000, the end of Phase 2 of Title IV of the Clean Air Act, all plants having a capacity of 25 MW or more must restrict their sulfur emissions to 1.2 lb per million Btu or less. As power companies endeavor to comply with this regulation, they will need to identify resources of limestone and dolomite having specific quality and grindability characteristics, in sufficient quantity for their needs and within proximity to their plants. A study is underway at the US Geological Survey (USGS) to identify limestone resources in the Eastern US that are best suited for desulfurization in the various combustion systems. Carbonate resources are being identified, quantified, and characterized on the basis of their sorbent properties and proximity to potential markets. In addition, the USGS has developed a carbonate data base that includes approximately 1,500 chemically analyzed samples from the US. The current study focuses on limestones that are suited for wet scrubber operations and have at least 90% CaCO{sub 3}.

  1. Use Of limestone resources in flue-gas desulfurization power plants in the Ohio River Valley

    USGS Publications Warehouse

    Foose, M.P.; Barsotti, A.F.

    1999-01-01

    In 1994, more than 41 of the approximately 160 coal-fired, electrical- power plants within the six-state Ohio River Valley region used flue-gas desulfurization (FGD) units to desulfurize their emissions, an approximately 100% increase over the number of plants using FGD units in 1989. This increase represents a trend that may continue with greater efforts to meet Federal Clean Air Act standards. Abundant limestone resources exist in the Ohio River Valley and are accessed by approximately 975 quarries. However, only 35 of these are believed to have supplied limestone for FGD electrical generating facilities. The locations of these limestone suppliers do not show a simple spatial correlation with FGD facilities, and the closest quarries are not being used in most cases. Thus, reduction in transportation costs may be possible in some cases. Most waste generated by FGD electrical-generating plants is not recycled. However, many FGD sites are relatively close to gypsum wallboard producers that may be able to process some of their waste.

  2. Development of a hot-gas desulfurization system for IGCC applications

    SciTech Connect

    Gupta, R.; McMichael, W.J.; Gangwal, S.K.; Jain, S.C.; Dorchak, T.P.

    1992-12-31

    Integrated gasification combined cycle (IGCC) power plants are being advanced worldwide to produce electricity from coal because of their superior environmental performance, economics, and efficiency in comparison to conventional coal-based power plants. One key component of an advanced IGCC power plant is a hot-gas desulfurization system employing regenerable sorbents. To carry out hot-gas desulfurization in a fluidized-bed reactor, it is necessary that the sorbents have high attrition resistance, while still maintaining high chemical reactivity and sulfur absorption capacity. Also, efficient processes are needed for the treatment of SO{sub 2}-containing regeneration off-gas to produce environmentally benign waste or useful byproducts. A series of durable zinc titanate sorbents were formulated and tested in a bench-scale fluidized-bed reactor system. Reactive sorbents were developed with addition resistance comparable to fluid-bed cracking (FCC) catalysts used in petroleum refineries. In addition, progress continues on the development of the Direct Sulfur Recovery Process (DSRP) for converting SO{sub 2} in the regeneration off-gas to elemental sulfur. Plans are under way to test these bench-scale systems at gasifier sites with coal gas. This paper describes the status and future plans for the demonstration of these technologies.

  3. Potential Agricultural Uses of Flue Gas Desulfurization Gypsum in the Northern Great Plains

    SciTech Connect

    DeSutter, T.M.; Cihacek, L.J.

    2009-07-15

    Flue gas desulfurization gypsum (FGDG) is a byproduct from the combustion of coal for electrical energy production. Currently, FGDG is being produced by 15 electrical generating stations in Alabama, Florida, Indiana, Iowa, Kentucky, Ohio, North Carolina, South Carolina, Tennessee, Texas, and Wisconsin. Much of this byproduct is used in the manufacturing of wallboard. The National Network for Use of FGDG in Agriculture was initiated to explore alternative uses of this byproduct. In the northern Great Plains (North Dakota, South Dakota, and Montana), FGDG has the potential to be used as a Ca or S fertilizer, as an acid soil ameliorant, and for reclaiming or mitigating sodium-affected soils. Greater than 1.4 million Mg of FGDG could initially be used in these states for these purposes. Flue gas desulfurization gypsum can be an agriculturally important resource for helping to increase the usefulness of problem soils and to increase crop and rangeland production. Conducting beneficial use audits would increase the public awareness of this product and help identify to coal combustion electrical generating stations the agriculturally beneficial outlets for this byproduct.

  4. Efficient desulfurization by polymer-inorganic nanocomposite membranes fabricated in reverse microemulsion.

    PubMed

    Li, Ben; Yu, Shengnan; Jiang, Zhongyi; Liu, Wanpeng; Cao, Ruijian; Wu, Hong

    2012-04-15

    The sulfur in gasoline will convert to SO(2) after combustion under high temperature, which adversely affects human health and the environment. Membrane technique in particular pervaporation offers a number of potential advantages over conventional FCC gasoline desulfurization processes. The present study focuses on the performance enhancement of PDMS membrane by incorporating silica nanoparticles. Specifically, silica nanoparticles formed by the catalysis and templating of protamine in w/o reverse microemulsion are in situ embedded into PDMS bulk matrix, endowing the resultant oleophilic nanocomposite membranes with appropriate free volume properties and superior separation performance. Through the rational manipulation of biomimetic mineralization at water-oil interface, silica particles with uniform size are acquired. Following this protocol, by introducing organic PDMS oligomers into the oil phase, PDMS-SiO(2) nanocomposite membranes are prepared in a facile way. The resultant nanocomposite membranes display superior permeability and permselectivity in the pervaporative desulfurization using thiophene/n-octane binary mixture as model gasoline, for example, under the condition of 500 ppm sulfur in feed (40 L/h) at 30°C, an enrichment factor of 4.83-5.82 with a normalized permeation rate of 6.61-10.76 × 10(-5)kgm/m(2)h is acquired.

  5. Catalytic seawater flue gas desulfurization process: an experimental pilot plant study

    SciTech Connect

    F. Vidal B.; P. Ollero; F.J. Gutierrez Ortiz; A. Villanueva

    2007-10-15

    In previous articles by the authors on seawater S(IV) oxidation kinetics, a significant catalytic effect was demonstrated by means of a commercially available activated carbon. The aims of this study carried out at pilot plant scale were to assess the use of high-efficiency structured packing and to validate the positive results obtained previously in laboratory studies. A comparison between a packed tower and a spray column was made by maintaining the same desulfurization efficiency. A 47% reduction in seawater flow can be obtained with a packed tower. This option seems to be more economical, with a reduction in operation costs of least of 33%. With the appropriate activated carbon, it is possible to reach a greater oxidation rate at a low pH level than by operating conventionally at a high pH level without a catalyst. A preliminary technical and financial comparison between the advanced seawater desulfurization process (equipped with a packed tower and a catalytic oxidation plant) and the conventional process (spray tower and noncatalytic oxidation) was carried out. 18 refs., 4 figs., 4 tabs.

  6. Land application uses for dry flue gas desulfurization by-products: Phase 3

    SciTech Connect

    Dick, W.; Bigham, J.; Forster, R.; Hitzhusen, F.; Lal, R.; Stehouwer, R.; Traina, S.; Wolfe, W.; Haefner, R.; Rowe, G.

    1999-01-31

    New flue gas desulfurization (FGD) scrubbing technologies create a dry, solid by-product material consisting of excess sorbent, reaction product that contains sulfate and sulfite, and coal fly ash. Generally, dry FGD by-products are treated as solid wastes and disposed in landfills. However, landfill sites are becoming scarce and tipping fees are constantly increasing. Provided the environmental impacts are socially and scientifically acceptable, beneficial uses via recycling can provide economic benefits to both the producer and the end user of the FGD. A study titled ''Land Application Uses for Dry Flue Gas Desulfurization By-Products'' was initiated in December, 1990 to develop and demonstrate large volume, beneficial uses of FGD by-products. Phase 1 and Phase 2 reports have been published by the Electric Power Research Institute (EPRI), Palo Alto, CA. Phase 3 objectives were to demonstrate, using field studies, the beneficial uses of FGD by-products (1) as an amendment material on agricultural lands and on abandoned surface coal mine land, (2) as an engineering material for soil stabilization and raid repair, and (3) to assess the environmental and economic impacts of such beneficial uses. Application of dry FGD by-product to three soils in place of agricultural limestone increased alfalfa (Medicago sativa L.) and corn (Zea may L.) yields. No detrimental effects on soil and plant quality were observed.

  7. Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance

    SciTech Connect

    Zhang, Shuna; Zhang, Shujuan; Song, Limin; Wu, Xiaoqing; Fang, Sheng

    2014-05-01

    Graphical abstract: Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance. - Highlights: • Three-dimensional Ni{sub 2}P has been prepared using foam nickel as a template. • The microstructures interconnected and formed sponge-like porous networks. • Three-dimensional Ni{sub 2}P shows superior hydrodesulfurization activity. - Abstract: Three-dimensional microstructured nickel phosphide (Ni{sub 2}P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni{sub 2}P samples, as interconnected networks, maintained the original mesh structure of foamed nickel. The crystal structure and morphology of the as-synthesized Ni{sub 2}P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the three-dimensionally structured Ni{sub 2}P was postulated and discussed in detail. To investigate its catalytic properties, SiO{sub 2} supported three-dimensional Ni{sub 2}P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni{sub 2}P/SiO{sub 2}.

  8. [Influence and mechanism of calcium-based desulfurizer on NO conversion in fluidized bed of coal].

    PubMed

    Zhang, Dongping; Chi, Yong; Yan, Jianhua; Li, Xiangpai; Cao, Yuchun; Cen, Kefa

    2003-01-01

    On the experimental table of fluidized bed which scale was phi 150 mm x 1000 mm and temperature interval was from 840 degrees C to 960 degrees C, the influence of desulfurizer variety, particle size and molar ratios Ca/S on nitrogen conversion to NO were studied. This paper elaborated on the mechanism of calcium-based desulfurizer lead to the increase of NO conversion rate. Experiment presented that given identical quantities, burnt calcium had maximum NO conversion rate, then limestone, calcite last. Nitrogen conversion to NO increased with increasing molar ratios Ca/S. When the particle size was between 1-2 mm, the NO conversion rate was the maximum, second was 2-3 mm, the last 0.2-1 mm. HCl, HF, SO2 decreased with calcium addition. At the same time H, OH, HO2 radicals increased. The CO oxidation was favored, the reaction of monoxide and NO catalyzed by char, sand, ash will weaken, therefore NO content will increase.

  9. Hot coal gas desulfurization with manganese-based sorbents. Final report, September 1992--December 1994

    SciTech Connect

    Hepworth, M.T.; Slimane, R.B.

    1994-11-01

    The focus of much current work being performed by the Morgantown Energy Technology Center (METC) of the Department of Energy on hot coal-derived fuel gas desulfurization is in the use of zinc-based sorbents. METC has shown interest in formulating and testing manganese-based pellets as alternative effective sulfur sorbents in the 700 to 1200{degree}C temperature range. To substantiate the potential superiority of Mn-based pellets, a systematic approach toward the evaluation of the desulfurizing power of single-metal sorbents is developed based on thermodynamic considerations. This novel procedure considered several metal-based sorbents and singled out manganese oxide as a prime candidate sorbent capable of being utilized under a wide temperature range, irrespective of the reducing power (determined by CO{sub 2}/CO ratio) of the fuel gas. Then, the thermodynamic feasibility of using Mn-based pellets for the removal of H{sub 2}S from hot-coal derived fuel gases, and the subsequent oxidative regeneration of loaded (sulfided) pellets was established. It was concluded that MnO is the stable form of manganese for virtually all commercially available coal-derived fuel gases. In addition, the objective of reducing the H{sub 2}S concentration below 150 ppMv to satisfy the integrated gasification combined cycle system requirement was shown to be thermodynamically feasible. A novel process is developed for the manufacture of Mn-based spherical pellets which have the desired physical and chemical characteristics required.

  10. A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels

    NASA Astrophysics Data System (ADS)

    Toutov, Anton A.; Salata, Mike; Fedorov, Alexey; Yang, Yun-Fang; Liang, Yong; Cariou, Renan; Betz, Kerry N.; Couzijn, Erik P. A.; Shabaker, John W.; Houk, Kendall N.; Grubbs, Robert H.

    2017-02-01

    Hydrodesulfurization (HDS) is the process by which sulfur-containing impurities are removed from petroleum streams, typically using a heterogeneous, sulfided transition metal catalyst under high H2 pressures and temperatures. Although generally effective, a major obstacle that remains is the desulfurization of highly refractory sulfur-containing heterocycles, such as 4,6-dimethyldibenzothiophene (4,6-Me2DBT), which are naturally occurring in fossil fuels. Homogeneous HDS strategies using well-defined molecular catalysts have been designed to target these recalcitrant S-heterocycles; however, the formation of stable transition metal sulfide complexes following C-S bond activation has largely prevented catalytic turnover. Here we show that a robust potassium (K) alkoxide (O)/hydrosilane (Si)-based ('KOSi') system efficiently desulfurizes refractory sulfur heterocycles. Subjecting sulfur-rich diesel (that is, [S] ∼ 10,000 ppm) to KOSi conditions results in a fuel with [S] ∼ 2 ppm, surpassing ambitious future governmental regulatory goals set for fuel sulfur content in all countries.

  11. Desulfurization in reducing atmosphere and ammonia injection denitrification in a coal-fired fluidized bed combustor with fly-ash recycle

    NASA Astrophysics Data System (ADS)

    Zhong, Zhaoping; Lan, Jixiang; Han, Yongsheng; Wu, Xin; Zheng, Haiyun

    1997-03-01

    With the rising of IGCC and the second generation PFBC-CC, and with the development of technology of staged combustion to lower emission of NOx, the desulfurization efficiency under reducing atmosphere is raised. In this paper, with the application of the fly-ash recycle and two-stage combustion technologies in a fluidized bed combustor, the desulfurization test under reducing atmosphere is described. Meanwhile, ammonia injection test was also conducted. Results show that desulfurization under reducing atmosphere has higher efficiency, and ammonia injection denitrification effect is very perfect.

  12. A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization.

    PubMed

    Du, Shuting; Li, Fen; Sun, Qiming; Wang, Ning; Jia, Mingjun; Yu, Jihong

    2016-02-25

    Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.

  13. Impact of Leaching Conditions on Constituents Release from Flue Gas Desulfurization Gypsum (FGDG) and FGDG-Soil Mixture

    EPA Science Inventory

    The interest in using Flue Gas Desulfurization Gypsum(FGDG) has increased recently. This study evaluates the leaching characteristics of trace elements in "modern" FGDG (produced after fly ash removal) and FGDG-mixed soil (SF) under different environmental conditions using rece...

  14. Synthesis, characterization and application of 1-butyl-3 methylimidazolium chloride as green material for extractive desulfurization of liquid fuel.

    PubMed

    Dharaskar, Swapnil A; Varma, Mahesh N; Shende, Diwakar Z; Yoo, Chang Kyoo; Wasewar, Kailas L

    2013-01-01

    The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, (1)H-NMR, and (13)C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30°C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency.

  15. Synthesis, Characterization and Application of 1-Butyl-3 Methylimidazolium Chloride as Green Material for Extractive Desulfurization of Liquid Fuel

    PubMed Central

    Dharaskar, Swapnil A.; Varma, Mahesh N.; Shende, Diwakar Z.; Yoo, Chang Kyoo; Wasewar, Kailas L.

    2013-01-01

    The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, 1H-NMR, and 13C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30°C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency. PMID:24307868

  16. A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

    PubMed

    Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

    2016-01-04

    Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

  17. High H2O-resistance CaO-MnOx/MSU-H sorbents for hot coal gas desulfurization.

    PubMed

    Xia, Hong; Liu, Bingsi

    2017-02-15

    A series of xMnyCa/MSU-H sorbents with various Mn/Ca molar ratio were first designed and synthesized with a sol-gel method. The desulfurization performance of the new sorbent was investigated at 600-800°C in hot coal gas. 90Mn10Ca/MSU-H exhibited better desulfurization performance at 750°C with a breakthrough sulfur capacity (BSC) of 18.69g S/100g sorbent compared to other supported Mn-based sorbents (13.2g S/100g sorbent) in similar desulfurization condition, and strong durability in multiple sulfidation-regeneration cycles using oxidation/reduction regeneration method which resolved the scientific issue of that CaSO4 is hardly decomposed to CaO. The introduction of Ca species effectively promoted the dispersion of active constituents, which improved the desulfurization activity. More importantly, 90Mn10Ca/MSU-H showed excellent H2O-resistance ability due to the fact that CaO enhanced the sorption of H2O. Moreover, the utilization of MSU-H with large pore size and excellent thermal stability effectively assured fast mass-transfer and confined the migration of active particles, which led to long lifetime stability of sorbents.

  18. Use of animal waste and flue gas desulfurized gypsum to improve forage production on reclaimed mine soil in Mississippi

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reclaimed mine soils amended with flue gas desulfurized (FGD) gypsum may tolerate higher levels of animal manure, and would therefore be more productive in the long-term. Studies were conducted in respread soil during the first year of land reclamation at Red Hills Mine, a surface lignite mine in no...

  19. Three annual flue gas desulfurization gypsum applications on macronutrient and micronutrient losses in runoff from bermudagrass fertilized with poultry litter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Considerable amounts of flue gas desulfurization (FGD) gypsum are being produced as a by-product of generating electricity. As a result, beneficial reuse of this by-product is being sought to reduce landfilling and its associated cost. The use of this byproduct as a low-cost soil amendment for suppl...

  20. Recovery of lead from lead paste in spent lead acid battery by hydrometallurgical desulfurization and vacuum thermal reduction.

    PubMed

    Ma, Yunjian; Qiu, Keqiang

    2015-06-01

    Lead sulfate, lead oxides and lead metal are the main component of lead paste in spent lead acid battery. When lead sulfate was desulfurized and transformed into lead carbonate by sodium carbonate, lead metal and lead oxides remained unchanged. Lead carbonate is easily decomposed to lead oxide and carbon dioxide under high temperature. Namely, vacuum thermal process is the reduction reaction of lead oxides. A compatible environmental process consisted of hydrometallurgical desulfurization and vacuum thermal reduction to recycle lead was investigated in this research. Lead paste was firstly desulfurized with sodium carbonate, by which, the content of sulfur declined from 7.87% to 0.26%. Then, the desulfurized lead paste was reduced by charcoal under vacuum. Under the optimized reaction conditions, i.e., vacuum thermal reduction at temperature 850°C under 20 Pa for 45 min, a 22.11×10(-2) g cm(-2) min(-1) reduction rate, and a 98.13% direct recovery ratio of fine lead (99.77%) had been achieved, respectively.

  1. Mercury emission and plant uptake of trace elements during early stage of soil amendment using flue gas desulfurization materials.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A pilot-scale field study was carried out to investigate the distribution of Hg and other selected elements in the three potential mitigation pathways, i.e., emission to ambient air, uptake by surface vegetation (i.e., grass), and rainfall infiltration, after flue gas desulfurization (FGD) material ...

  2. Desulfurization characteristics of rapidly hydrated sorbents with various adhesive carrier particles for a semidry CFB-FGD system.

    PubMed

    You, Changfu; Li, Yuan

    2013-03-19

    Semidry flue gas desulfurization (FGD) experiments were conducted using rapidly hydrated sorbents with four different adhesive carrier particles: circulation ash from a circulating fluidized bed boiler (CFBB circulation ash), fly ash from the first electrical field of the electrostatic precipitator of a circulating fluidized bed boiler (CFBB ESP ash), fly ash from a chain boiler (chain boiler ash), and river sand smaller than 1 mm. The influences of various adhesive carrier particles and operating conditions on the desulfurization characteristics of the sorbents were investigated, including sprayed water, reaction temperature, and the ratio of calcium to sulfur (Ca/S). The experimental results indicated that the rapidly hydrated sorbents had better desulfurization characteristics by using adhesive carrier particles which possessed better pore, adhesion, and fluidization characteristics. The desulfurization efficiency of the system increased as the reaction temperature decreased, it improved from 35% to 90% as the mass flow rate of the sprayed water increased from 0 to 10 kg/h, and it increased from 65.6% to 82.7% as Ca/S increased from 1.0 to 2.0. Based on these findings, a new semidry circulating fluidized bed (CFB)-FGD system using rapidly hydrated sorbent was developed. Using the rapidly hydrated sorbent, this system uses a cyclone separator instead of an ESP or a bag filter to recycle the sorbent particles, thereby decreasing the system flow resistance, saving investment and operating costs of the solids collection equipment.

  3. Integrated lipase production and in situ biodiesel synthesis in a recombinant Pichia pastoris yeast: an efficient dual biocatalytic system composed of cell free enzymes and whole cell catalysts

    PubMed Central

    2014-01-01

    Background Lipase-catalyzed biotransformation of acylglycerides or fatty acids into biodiesel via immobilized enzymes or whole cell catalysts has been considered as one of the most promising methods to produce renewable and environmentally friendly alternative liquid fuels, thus being extensively studied so far. In all previously pursued approaches, however, lipase enzymes are prepared in an independent process separated from enzymatic biodiesel production, which would unavoidably increase the cost and energy consumption during industrial manufacture of this cost-sensitive energy product. Therefore, there is an urgent need to develop novel cost-effective biocatalysts and biocatalytic processes with genuine industrial feasibility. Result Inspired by the consolidated bioprocessing of lignocellulose to generate bioethanol, an integrated process with coupled lipase production and in situ biodiesel synthesis in a recombinant P. pastoris yeast was developed in this study. The novel and efficient dual biocatalytic system based on Thermomyces lanuginosus lipase took advantage of both cell free enzymes and whole cell catalysts. The extracellular and intracellular lipases of growing yeast cells were simultaneously utilized to produce biodiesel from waste cooking oils in situ and in one pot. This integrated system effectively achieved 58% and 72% biodiesel yield via concurrent esterified-transesterified methanolysis and stepwise hydrolysis-esterification at 3:1 molar ratio between methanol and waste cooking oils, respectively. Further increasing the molar ratio of methanol to waste cooking oils to 6:1 led to an 87% biodiesel yield using the stepwise strategy. Both water tolerance and methanol tolerance of this novel system were found to be significantly improved compared to previous non-integrated biodiesel production processes using separately prepared immobilized enzymes or whole cell catalysts. Conclusion We have proposed a new concept of integrated biodiesel production

  4. Synthesis of bi-metallic Au-Ag nanoparticles loaded on functionalized MCM-41 for immobilization of alkaline protease and study of its biocatalytic activity

    NASA Astrophysics Data System (ADS)

    Sadjadi, M. S.; Farhadyar, N.; Zare, K.

    2009-10-01

    In this work, Au-Ag nanoparticles (Au-Ag-bi-MNPs) have been prepared on amine functionalized Si-MCM-41 (NH 2-Si-MCM-41) particles through a reduction of AgNO 3 and HAuCl 4 by NaBH 4 at ambient conditions. Au-Ag-bi-MNPs loaded on the NH2-Si-MCM-41, provide a good biocompatible surface for immobilization of the enzyme alkaline protease. This immobilization, presumably due to bonding between core shell nanoparticles and OH in serine 183 in alkaline protease seems to be of an ionic exchange nature. We found that the alkaline protease immobilized on the Au-Ag-bi-MNPs/Si-MCM-41 is an active biocatalyst, stable at different pH and temperature. The bio catalytic activity of free alkaline protease in solution was 64 U/mg (Units per milligram), whereas that of the alkaline protease immobilized on Au-Ag-bi-MNPs/Si-MCM-41 was 75 U/mg. This improvement of the biocatalytic activity may be due to a really increased activity per molecule of immobilized enzyme or to a purification of the enzyme. The alkaline protease molecules immobilized on the (Au-Ag)/ NH 2-MCM-41 surface retained as much as 80% of the catalytic activity recorded at pH=8, and showed significant catalytic activity of alkaline protease in the bioconjugate material. The biocatalytic materials were easily separated from the reaction medium by mild centrifugation and exhibits excellent reuse and stability characteristics over four successive cycles. The optimum temperature ranged from 35 ∘C-55 ∘C and pH=8 for bioactivity of the alkaline protease in the assembly system was observed to be higher than that of the free enzyme in solution. The enzyme biocatalytic activity was monitored by UV-visible spectroscopy. Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and dispersive analysis of X-RAY (EDAX) were used to characterize the size and morphology of the prepared materials.

  5. Coal desulfurization by bacterial treatment and column flotation. Final report

    SciTech Connect

    Kawatra, S.K.

    1994-06-01

    A review of the literature showed that bacterial leaching, using the microorganism Thiobacillus ferrooxidans, was a very effective technique for removing pyrite from coal, as it could dissolve even the finest pyrite particles without the need for expensive reagents or extreme processing conditions. Unfortunately, bacterial leaching is also rather slow, and so the initial goal of this research was to decrease the leaching time as much as possible. However, this still left the bacteria needing approximately a week to remove half of the pyritic sulfur, and so a faster technique was sought. Since it had been reported in the literature that T. ferrooxidans could be used to depress the flotation of pyrite during froth flotation of coal, this was investigated further. By studying the recovery mechanisms of coal-pyrite in froth flotation, it was found that pyrite was being recovered by entrainment and by locking to coal particles, not by true flotation of hydrophobic pyrite. Therefore, no pyrite depressant could be of any significant benefit for keeping pyrite out of the coal froth product, and it was much more important to prevent entrainment from occurring. Countercurrent flotation columns were invented to essentially eliminate entrainment effects, by washing the froth and reducing mixing of the froth and tailings products. Existing flotation columns tend to be quite simple, and in order to give reasonable product quality they must be very tall (typically 30--45 feet). As a result, they have difficulty in handling the high froth volumes which occur in coal flotation, and are awkward to install in existing plants. The bulk of this project therefore concentrated on developing an improved coal flotation column, and testing it under actual plant conditions.

  6. Enhanced durability of desulfurization sorbents for fluidized-bed applications

    SciTech Connect

    Gupta, R.P.; Gangwal, S.K.

    1992-11-01

    To extend the operating temperature range and further improve the durability of fluidizable sorbents, zinc titanate, another leading regenerable sorbent, was selected for development in the later part of this project. A number of zinc titanate formulations were prepared in the 50 to 300 {mu}m range using granulation and spray drying methods. Important sorbent preparation variables investigated included zinc to titanium ratio, binder type, binder amount, and various chemical additives such as cobalt and molybdenum. A number of sorbents selected on the basis of screening tests were subjected to bench-scale testing for 10 cycles at high temperature, high pressure (HTHP) conditions using the reactor system designed and constructed during the base program. This reactor system is capable of operation either as a 2.0 in. or 3.0 in. I.D. bubbling bed and is rated up to 20 atm operation at 871{degrees}C. Bench-scale testing variables included sorbent type, temperature (550 to 750{degrees}C), gas type (KRW or Texaco gasifier gas), steam content of coal gas, and fluidizing gas velocity (6 to 15 cm/s). The sorbents prepared by spray drying showed poor performance in terms of attrition resistance and chemical reactivity. On the other hand, the granulation method proved to be very successful. For example, a highly attrition-resistant zinc titanate formulation, ZT-4, prepared by granulation exhibited virtually no zinc loss and demonstrated a constant high reactivity and sulfur capacity over 10 cycles, i.e., approximately a 60 percent capacity utilization, with Texaco gas at 750{degrees}C, 15 cm/s fluidizing velocity and 15 atm pressure. The commercial potential of the granulation method for zinc titanate manufacture was demonstrated by preparing two 80 lb batches of sorbent with zinc to titanium mol ratios of 0.8 and 1.5.

  7. Enhanced durability of desulfurization sorbents for fluidized-bed applications

    SciTech Connect

    Gupta, R.P.; Gangwal, S.K.

    1992-11-01

    To extend the operating temperature range and further improve the durability of fluidizable sorbents, zinc titanate, another leading regenerable sorbent, was selected for development in the later part of this project. A number of zinc titanate formulations were prepared in the 50 to 300 [mu]m range using granulation and spray drying methods. Important sorbent preparation variables investigated included zinc to titanium ratio, binder type, binder amount, and various chemical additives such as cobalt and molybdenum. A number of sorbents selected on the basis of screening tests were subjected to bench-scale testing for 10 cycles at high temperature, high pressure (HTHP) conditions using the reactor system designed and constructed during the base program. This reactor system is capable of operation either as a 2.0 in. or 3.0 in. I.D. bubbling bed and is rated up to 20 atm operation at 871[degrees]C. Bench-scale testing variables included sorbent type, temperature (550 to 750[degrees]C), gas type (KRW or Texaco gasifier gas), steam content of coal gas, and fluidizing gas velocity (6 to 15 cm/s). The sorbents prepared by spray drying showed poor performance in terms of attrition resistance and chemical reactivity. On the other hand, the granulation method proved to be very successful. For example, a highly attrition-resistant zinc titanate formulation, ZT-4, prepared by granulation exhibited virtually no zinc loss and demonstrated a constant high reactivity and sulfur capacity over 10 cycles, i.e., approximately a 60 percent capacity utilization, with Texaco gas at 750[degrees]C, 15 cm/s fluidizing velocity and 15 atm pressure. The commercial potential of the granulation method for zinc titanate manufacture was demonstrated by preparing two 80 lb batches of sorbent with zinc to titanium mol ratios of 0.8 and 1.5.

  8. BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

    SciTech Connect

    1998-05-01

    The Direct Sulfur Recovery Process (DSRP) is a one- or two-stage catalytic reduction process for efficiently converting to elemental sulfur up to 98 percent or more of the sulfur dioxide (SO{sub 2}) contained in the regeneration offgas streams produced in advanced integrated gasification combined cycle (IGCC) power systems. The DSRP reacts the regeneration offgas with a small slipstream of coal gas to effect the desired reduction. In this project the DSRP was demonstrated with actual coal gas (as opposed to the simulated laboratory mixtures used in previous studies) in a 75-mm, 1-L size fixed-bed reactor. Integrated with this testing, a US Department of Energy/Research Triangle Institute (DOE/RTI) patented zinc titanate-based fluidizable sorbent formulation was tested in a 75-mm (3-in.) diameter fluidized-bed reactor, and the regeneration offgas from that test was treated with the bench-unit DSRP. The testing was conducted at the DOE Federal Energy Technology Center (FETC)-Morgantown in conjunction with test campaigns of the pilot-scale gasifier there. The test apparatus was housed in a mobile laboratory built in a specially equipped office trailer that facilitated moving the equipment from RTI in North Carolina to the West Virginia test site. A long duration test of the DSRP using actual coal gas and simulated regeneration offgas showed no degradation in efficiency of conversion to elemental sulfur after 160 h of catalyst exposure. An additional exposure (200 h) of that same catalyst charge at the General Electric pilot gasifier showed only a small decline in performance. That problem is believed to have been caused by tar and soot deposits on the catalyst, which were caused by the high tar content of the atypical fixed-bed gasifier gas. A six-fold larger, single-stage skid-mounted DSRP apparatus was fabricated for additional, larger-scale slipstream testing.

  9. 1,3-Diferuloyl-sn-glycerol from the biocatalytic transesterification of ethyl 4-hydroxy-3-methoxy cinnamic acid (ethyl ferulate) and soybean oil.

    PubMed

    Compton, David L; Laszlo, Joseph A

    2009-06-01

    1,3-Diferuloyl-sn-glycerol is found ubiquitously throughout the plant kingdom, possessing ultraviolet adsorbing and antioxidant properties. Diferuloyl glycerol was synthesized and isolated as a byproduct in up to 5% yield from a pilot plant scale packed-bed, biocatalytic transesterification of ethyl ferulate with soybean oil or mono- and diacylglycerols from soybean oil. The yield of the diferuloyl glycerol byproduct was directly proportional to the overall water concentration of the bioreactor. The isolated diferuloyl glycerol exhibited good ultraviolet adsorbing properties, 280-360 nm with a lambda(max) 322 nm, and compared well to the efficacy of commercial sunscreen active ingredients. The antioxidant capacity of diferuloyl glycerol (0.25-2.5 mM) was determined by its ability to scavenge 2,2-diphenyl-1-picrylhydrazyl radicals and was comparable to that of ferulic acid. At current pilot plant scale production capacity, 120 kg diferuloyl glycerol byproduct could be isolated per year.

  10. Solvent Stability Study with Thermodynamic Analysis and Superior Biocatalytic Activity of Burkholderia cepacia Lipase Immobilized on Biocompatible Hybrid Matrix of Poly(vinyl alcohol) and Hypromellose.

    PubMed

    Badgujar, Kirtikumar C; Bhanage, Bhalchandra M

    2014-12-26

    In the present study, we have synthesized a biocompatible hybrid carrier of hypromellose (HY) and poly(vinyl alcohol) (PVA) for immobilization of Burkholderia cepacia lipase (BCL). The immobilized biocatalyst HY:PVA:BCL was subjected to determination of half-life time (τ) and deactivation rate constant (K(D)) in various organic solvents. Biocatalyst showed higher τ-value in a nonpolar solvent like cyclohexane (822 h) as compared to that of a polar solvent such as acetone (347 h), which signifies better compatibility of biocatalyst in the nonpolar solvents. Furthermore, the K(D)-value was found to be less in cyclohexane (0.843 × 10(-3)) as compared to acetone (1.997 × 10(-3)), indicating better stability in the nonpolar solvents. Immobilized-BCL (35 mg) was sufficient to achieve 99% conversion of phenethyl butyrate (natural constituent of essential oils and has wide industrial applications) using phenethyl alcohol (2 mmol) and vinyl butyrate (6 mmol) at 44 °C in 3 h. The activation energy (E(a)) was found to be lower for immobilized-BCL than crude-BCL, indicating better catalytic efficiency of immobilized lipase BCL. The immobilized-BCL reported 6-fold superior biocatalytic activity and 8 times recyclability as compared to crude-BCL. Improved catalytic activity of immobilized enzyme in nonpolar media was also supported by thermodynamic activation parameters such as enthalpy (ΔH(⧧)), entropy (ΔS(⧧)) and Gibb's free energy (ΔG(⧧)) study, which showed that phenethyl butyrate synthesis catalyzed by immobilized-BCL was feasible as compared to crude-BCL. The present work explains a thermodynamic investigation and superior biocatalytic activity for phenethyl butyrate synthesis using biocompatible immobilized HY:PVA:BCL in nonaqueous media for the first time.

  11. Bioorganometallic chemistry: biocatalytic oxidation reactions with biomimetic nad+/nadh co-factors and [cp*rh(bpy)h]+ for selective organic synthesis

    SciTech Connect

    Lutz, Jochen; Hollman, Frank; Ho, The Vinh; Schnyder, Adrian; Fish, Richard H.; Schmid, Andreas

    2004-03-09

    The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural nicotinamide adenine dinucleotide (NAD{sup +}) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzylnicotinamide bromide, 1a. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfers, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH{sub 2} possibly reacting with the precatalyst, [Cp*Rh(bpy)(H{sub 2}O)](Cl){sub 2}, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH{sub 2} groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H2O)](Cl){sub 2}, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product.

  12. Chemical formulation and combined process for inhibiting deposition and corrosion in cooling water and gypsum scaling in flue gas desulfurization scrubber systems

    SciTech Connect

    Mouche, R.J.; Lin, M.L.; Ekis, E.W. Jr.

    1989-05-30

    A combined cooling water/flue gas desulfurization process is described comprising: (a) contacting a gas with water in a cooling tower the gas having a lower temperature than the water such that upon contact the water is cooled by the transfer of thermal energy from the water to the gas. The water comprising between about 0.2 and about 100 ppm active by weight of an inhibitor formulation comprising polyacrylate, polymaleic anhydride, and phosphonate; (b) contacting a sulfur-containing gas with reagent slurry in a flue gas desulfurizer thereby desulfurizing the sulfur containing gas; and (c) supplying at least a portion of the water from the cooling tower to make up at least a portion of wash water in the desulfurizer, the water being supplied in an amount sufficient to maintain between about 0.01 and about 20 ppm active by weight of the inhibitor formulation in the reagent wash water.

  13. High volume-high value usage of flue gas desulfurization (FGD) by- products in underground mines. Quarterly report, April 1--June 30, 1996

    SciTech Connect

    1996-12-31

    The target for the project has been shifted from filling, highwall mine adits to filling auger holes with FGD material to provide a stable highwall for automated highwall mining. As reported previously, this shift in emphasis is economically desirable and practical, as the filling operation is safer and permits access to ``locked in`` high quality coal behind existing auger holes. As also reported previously, the fill material was shifted from dry FGD materials to a Fluidized Bed Combustion fly ash from the Archer Daniel Midland No. 6 facility in Illinois. Previous reports have summarized the characterization of this material for the project. However, due mostly to economic concerns with prehydration and transport of the Archer Daniel Midland (ADM6) material, several new desulfurization by-products stored at the Costain facility in Allen, Kentucky were considered during, this quarter. At this stage of the project, the change in fill material required rapid assessment in much the same way an applied working project would demand quick evaluation. This change thus provided an opportunity to demonstrate a rapid assessment of material suitability. The results described below were obtained in a short time frame, and with the exception of characterizing the long term swell and durability of the products, the rapid assessment was a success. No rapid assessment methodology for long term behavior has been developed at this time. The mineralogical characteristics of the two Costain materials will not be summarized in detail here. Unlike the ADM6 ash, the spray dryer and FBC materials currently under review do not include the large percentages of free lime (CaO) that was shown to cause high mixing temperatures in the nonprehydrated ADM6 product. This absence of free lime in the raw by-products is immediately evident when mixing with water, as no significant heating of the mixture is observed.

  14. Project: "Project!"

    ERIC Educational Resources Information Center

    Grayson, Katherine

    2007-01-01

    In November 2006, the editors of "Campus Technology" launched their first-ever High-Resolution Projection Study, to find out if the latest in projector technology could really make a significant difference in teaching, learning, and educational innovation on US campuses. The author and her colleagues asked campus educators,…

  15. Biocatalytic Synthesis of Vanillin

    PubMed Central

    Li, Tao; Rosazza, John P. N.

    2000-01-01

    The conversions of vanillic acid and O-benzylvanillic acid to vanillin were examined by using whole cells and enzyme preparations of Nocardia sp. strain NRRL 5646. With growing cultures, vanillic acid was decarboxylated (69% yield) to guaiacol and reduced (11% yield) to vanillyl alcohol. In resting Nocardia cells in buffer, 4-O-benzylvanillic acid was converted to the corresponding alcohol product without decarboxylation. Purified Nocardia carboxylic acid reductase, an ATP and NADPH-dependent enzyme, quantitatively reduced vanillic acid to vanillin. Structures of metabolites were established by 1H nuclear magnetic resonance and mass spectral analyses. PMID:10653736

  16. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Zhao, Liang; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-01

    To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  17. Desulfurization Characteristics of Fly Ash Recirculation and Combustion in the Circulating Fluidized Bed Boiler

    NASA Astrophysics Data System (ADS)

    Li, S. F.; Fang, M. X.; Yu, B.; Wang, Q. H.; Luo, Z. Y.

    The experiments of the fly ash recycle combustion using Guizhou anthracite were carried out in a bench scale circulating fluidized bed (CFB) combustor. Effects of some key operating parameters such as recycle ash to coal mass ratio (Ca to S molar ratio), temperature, reactivation modeof fly ash, circulation rateand fluidization velocity on the desulfurization efficiency were intensively investigated. It is shown that thelimestone utilization efficiency could be improved about 30% with the following operating conditions: the mass ratio of fly ash (reactivated by water and dried at 90°C) to coal was 0.45, the furnace temperature was 880°C, the water to ash mass ratio was 4.5% (the water-to-calcium molar ratio was 0.55) and circulation rate was 18.

  18. Study of gypsum crystal nucleation and growth rates in simulated flue gas desulfurization liquors. Final report

    SciTech Connect

    Randolph, A.D.; Etherton, D.

    1981-06-01

    The kinetics of gypsum crystal nucleation and growth rates were measured in flue gas desulfurization (FGD) scrubber liquors. Variables studied were parent seed crystal size and mass; the organic additives citric acid, adipic acid, sodium dodecylbenzene sulfonate, and Calgon CL246 polyacrylic acid formulation; and pH. Citric acid produced gypsum crystals with a more favorable columnar structure. Lower pH resulted in increased nucleation rates. Stable secondary nucleation was observed in the presence of retained parent gypsum seed crystals of size >150 ..mu..m. Growth and nucleation rates were correlated using reaction kinetic models. These kinetics were then used in rigorous computer simulations to predict crystal-size distribution (CSD) with different scrubber configurations. Scrubber process configurations employing classified product removal were calculated to produce a gypsum sludge having a mean particle size up to twice as large as the particle size with unclassified operation.

  19. Method for reducing sulfate formation during regeneration of hot-gas desulfurization sorbents

    DOEpatents

    Bissett, Larry A.; Strickland, Larry D.; Rockey, John M.

    1994-01-01

    The regeneration of sulfur sorbents having sulfate forming tendencies and used for desulfurizing hot product gas streams such as provided by coal gasification is provided by employing a two-stage regeneration method. Air containing a sub-stoichiometric quantity of oxygen is used in the first stage for substantially fully regenerating the sorbent without sulfate formation and then regeneration of the resulting partially regenerated sorbent is completed in the second stage with air containing a quantity of oxygen slightly greater than the stoichiometric amount adequate to essentially fully regenerate the sorbent. Sulfate formation occurs in only the second stage with the extent of sulfate formation being limited only to the portion of the sulfur species contained by the sorbent after substantially all of the sulfur species have been removed therefrom in the first stage.

  20. Method for the desulfurization of hot product gases from coal gasifier

    DOEpatents

    Grindley, Thomas

    1988-01-01

    The gasification of sulfur-bearing coal produces a synthesis gas which contains a considerable concentration of sulfur compounds especially hydrogen sulfide that renders the synthesis gas environmentally unacceptable unless the concentration of the sulfur compounds is significantly reduced. To provide for such a reduction in the sulfur compounds a calcium compound is added to the gasifier with the coal to provide some sulfur absorption. The synthesis gas from the gasifier contains sulfur compounds and is passed through an external bed of a regenerable solid absorbent, preferably zinc ferrite, for essentially completed desulfurizing the hot synthesis gas. This absorbent is, in turn, periodically or continuously regenerated by passing a mixture of steam and air or oxygen through the bed for converting absorbed hydrogen sulfide to sulfur dioxide. The resulting tail gas containing sulfur dioxide and steam is injected into the gasifier where the sulfur dioxide is converted by the calcium compound into a stable form of sulfur such as calcium sulfate.

  1. Development of sorbents for high-temperature desulfurization in moving-bed systems

    SciTech Connect

    Ayala, R.E.; Chuck, T.; Gal, E.; Gupta, R.P.

    1994-10-01

    The objective of the option 3 program within this contract is to develop chemically reactive and mechanically durable mixed-metal oxide sorbent formulations that are suitable for moving-bed, high-temperature, desulfurization of coal gas. One optimum formulation will be evaluated in a pressurized 50-cycle bench-scale test. Work on zinc titanate formulations was initiated under the option 2 program and is continued under the present option 3 program along with testing of other mixed-metal oxides. One of the major limitations for large-scale use of mixed-metal oxides is the observed weakening and physical deterioration of the pellet and spalling during repetitive use in cycles of absorption and regeneration. A need exists to determine best operating conditions that minimize sulfate formation and prevent mechanical degradation. Results from materials tests on 5 zinc-based sorbents are given.

  2. Model predictive control of a wet limestone flue gas desulfurization pilot plant

    SciTech Connect

    Perales, A.L.V.; Ollero, P.; Ortiz, F.J.G.; Gomez-Barea, A.

    2009-06-15

    A model predictive control (MPC) strategy based on a dynamic matrix (DMC) is designed and applied to a wet limestone flue gas desulfurization (WLFGD) pilot plant to evaluate what enhancement in control performance can be achieved with respect to a conventional decentralized feedback control strategy. The results reveal that MPC can significantly improve both reference tracking and disturbance rejection. For disturbance rejection, the main control objective in WLFGD plants, selection of tuning parameters and sample time, is of paramount importance due to the fast effect of the main disturbance (inlet SO{sub 2} load to the absorber) on the most important controlled variable (outlet flue gas SO{sub 2} concentration). The proposed MPC strategy can be easily applied to full-scale WLFGD plants.

  3. Experimental investigation and modeling of a wet flue gas desulfurization pilot plant

    SciTech Connect

    Kiil, S.; Michelsen, M.L.; Dam-Johansen, K.

    1998-07-01

    A detailed model for a wet flue gas desulfurization (FGD) pilot plant, based on the packed tower concept, has been developed. All important rate-determining steps, absorption of SO{sub 2}, oxidation of HSO{sub 3}{sup {minus}}, dissolution of limestone, and crystallization of gypsum were included. Population balance equations, governing the description of particle size distributions of limestone in the plant, were derived. Model predictions were compared to experimental data such as gas-phase concentration profiles of SO{sub 2}, slurry pH profiles, solids content of the slurry, liquid-phase concentrations, and residual limestone in the gypsum. Simulations were found to match experimental data for the two limestone types investigated. A parameter study of the model was conducted with the purpose of validating assumptions and extracting information on wet FGD systems. The modeling tools developed may be applicable to other wet FGD plants.

  4. Integrated Mg/TiO2-ionic liquid system for deep desulfurization

    NASA Astrophysics Data System (ADS)

    Yin, Yee Cia; Kait, Chong Fai; Fatimah, Hayyiratul; Wilfred, Cecilia

    2014-10-01

    A series of Mg/TiO2 photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%.

  5. Controllability analysis and decentralized control of a wet limestone flue gas desulfurization plant

    SciTech Connect

    Perales, A.L.V.; Ortiz, F.J.G.; Ollero, P.; Gil, F.M.

    2008-12-15

    Presently, decentralized feedback control is the only control strategy used in wet limestone flue gas desulfurization (WLFGD) plants. Proper tuning of this control strategy is becoming an important issue in WLFGD plants because more stringent SO{sub 2} regulations have come into force recently. Controllability analysis is a highly valuable tool for proper design of control systems, but it has not been applied to WLFGD plants so far. In this paper a decentralized control strategy is designed and applied to a WLFGD pilot plant taking into account the conclusions of a controllability analysis. The results reveal that good SO{sub 2} control in WLFGD plants can be achieved mainly because the main disturbance of the process is well-aligned with the plant and interactions between control loops are beneficial to SO{sub 2} control.

  6. Calcium bisulfite oxidation rate in the wet limestone-gypsum flue gas desulfurization process

    SciTech Connect

    Lancia, A.; Musmarra, D.

    1999-06-01

    In this paper oxidation of calcium bisulfite in aqueous solutions was studied, in connection with the limestone-gypsum flue gas desulfurization process. Experimental measurements of the oxidation rate were carried out in a laboratory scale stirred reactor with continuous feeding of both gas and liquid phase. A calcium bisulfite clear solution was used as liquid phase, and pure oxygen or mixtures of oxygen and nitrogen were used as gas phase. Experiments were carried out at T = 45 C varying the composition of the liquid phase and the oxygen partial pressure. Manganous sulfate was used as catalyst. The analysis of the experimental results showed that the kinetics of bisulfite oxidation in the presence of MnSO{sub 4} follow a parallel reaction mechanism, in which the overall reaction rate can be calculated as the sum between the uncatalyzed rate (3/2 order in bisulfite ion) and the catalyzed reaction rate (first order in manganous ion).

  7. Transport—Reaction process in the reaction of flue gas desulfurization

    NASA Astrophysics Data System (ADS)

    Yan, Yan; Peng, Xiaofeng; Lee, Duu Jong

    2000-12-01

    A theoretical investigation was conducted to study the transport-reaction process in the spray-drying flue gas desulfurization. A transport-reaction model of single particle was proposed, which considered the water evaporation from the surface of droplet and the reaction at the same time. Based on this model, the reaction rate and the absorbent utilization can be calculated. The most appropriate particle radius and the initial absorbent concentration can be deduced through comparing the wet lifetime with the residence time, the result shows in the case that the partial pressure of vapor in the bulk flue gas is 2000Pa, the optimum initial radius and absorbent concentration are 210 310 µ m and 23% respectively. The model can supply the optimum parameters for semi-dry FGD system designed.

  8. Carbonation of gypsum from wet flue gas desulfurization process: experiments and modeling.

    PubMed

    Tan, Wenyi; Zhang, Zixin; Li, Hongyi; Li, Youxu; Shen, Zewen

    2017-02-13

    In this paper, waste gypsum from wet flue gas desulfurization (WFGD) mixed with NH3·H2O was applied for CO2 absorption in the solid-liquid-gas phase system. The effects of operation temperature, CO2 flow rates, and ammonia-to-gypsum ratio on carbonation process were discussed. Meanwhile, a model for CO2 absorption in the suspension of WFGD gypsum and ammonia was established. The results indicate that higher temperature favors the reaction, and WFGD gypsum conversion can be achieved above 90% even at lower ammonia-to-gypsum ratio, while CO2 conversion reaches 90% and ammonia utilization is up to 83.69%. The model fits well with the experimental results at various CO2 flow rates and predicts the concentration distribution of the main species, including CO2 absorbed, NH2COO(-), and HCO3(-).

  9. Enzymatic desulfurization of coal. Fifth quarterly report, June 16--September 15, 1989

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.; Marquis, J.K.

    1989-11-07

    Our experimental approach focuses on the use of enzymes which catalyze the addition of oxygen to organic compounds. In tailoring the application of these enzymes to coal processing, we are particularly interested in ensuring that oxidation occurs at sulfur and not at carbon-carbon bonds. Previous studies with DBT have shown that the reaction most frequently observed in microbial oxidative pathways is one in which DBT is oxidized at ring carbons. These reactions, as we have said, are accompanied by a considerable decrease in the energy content of the compound. In addition, microbial pathways have been identified in which the sulfur atom is sequentially oxidized to sulfoxide, to sulfone, to sulfonate, and finally to sulfuric acid. In this case, the fuel value of the desulfurized compounds is largely retained. We are evaluating the potential of commercially available enzymes to selectively catalyze oxidation at sulfur.

  10. Enzymatic desulfurization of coal. Seventh quarterly report, December 16, 1989--March 15, 1990

    SciTech Connect

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.

    1990-03-23

    Our experimental approach focuses on the use of enzymes which catalyze the addition of oxygen to organic compounds. In tailoring the application of these enzymes to coal processing, we are particularly interested in ensuring that oxidation occurs at sulfur and not at carbon-carbon bonds. Previous studies with DBT have shown that the reaction most frequently observed in microbial oxidative pathways is one in which DBT is oxidized at ring carbons. These reactions, as we have said, are accompanied by a considerable decrease in the energy content of the compound. In addition, microbial pathways have been identified in which the sulfur atom is sequentially oxidized to sulfoxide, to sulfone, to sulfonate, and finally to sulfuric acid. In this case, the fuel value of the desulfurized compounds is largely retained. We are evaluating the potential of commercially available enzymes to perform this function.

  11. Identification and determination of selenosulfate and selenocyanate in flue gas desulfurization waters.

    PubMed

    Petrov, Panayot K; Charters, Jeffrey W; Wallschläger, Dirk

    2012-02-07

    In this work, 13 selenium species in flue gas desulfurization (FGD) waters from coal-fired power plants were separated and quantified using anion-exchange chromatography coupled to inductively coupled plasma mass spectrometry. For the first time, we identified both selenosulfate (SeSO(3)(2-)) and selenocyanate (SeCN(-)) in such waters, using retention time matching and confirmation by electrospray mass spectrometry. Besides selenite and selenate, selenosulfate was the most frequently occurring selenium species. It occurred in most samples and constituted a major fraction (up to 63%) of the total selenium concentration in waters obtained from plants employing inhibited oxidation scrubbers. Selenocyanate occurred in about half of the tested samples, but was only a minor species (up to 6% of the total selenium concentration). Nine additional Se-containing compounds were found in FGD waters, but they remain unidentified at this point.

  12. Hot particulate removal and desulfurization results from the METC integrated gasification and hot gas cleanup facility

    SciTech Connect

    Rockey, J.M.

    1995-06-01

    The Morgantown Energy Technology Center (METC) is conducting experimental testing using a 10-inch diameter fluid-bed gasifier (FBG) and modular hot gas cleanup rig (MGCR) to develop advanced methods for removing contaminants in hot coal gasifier gas streams for commercial development of integrated gasification combined-cycle (IGCC) power systems. The program focus is on hot gas particulate removal and desulfurization technologies that match the temperatures and pressures of the gasifier, cleanup system, and power generator. The purpose of this poster is to present the program objectives and results of the work conducted in cooperation with industrial users and vendors to meet the vision for IGCC of reducing the capital cost per kilowatt to $1050 and increasing the plant efficiency to 52% by the year 2010.

  13. Influence of Basicity and MgO on Fluidity and Desulfurization Ability of High Aluminum Slag

    NASA Astrophysics Data System (ADS)

    Wang, Ping; Meng, Qing-min; Long, Hong-ming; Li, Jia-xin

    2016-08-01

    The viscosity of experimental slag, which was mixed based on the composition of a practical blast furnace slag, was measured in this paper. The influence of Al2O3 and MgO content, basicity R2 = w(CaO)/w(SiO2) on the fluidity of slag was studied. The stepwise regression analysis in SPSS was used to reveal the relationship between sulfur distribution coefficient LS and slag composition as well as furnace temperature. The results show that increasing of MgO up to 12% can decrease the slag viscosity. The w(MgO) should be controlled below 8% when there is 20% Al2O3 in the slag. Temperature of hot metal and content of CaO in slag are the two dominant factors on the desulfurization capacity of slag.

  14. Integrated Mg/TiO{sub 2}-ionic liquid system for deep desulfurization

    SciTech Connect

    Yin, Yee Cia; Kait, Chong Fai E-mail: hayyiratulfatimah@yahoo.com Fatimah, Hayyiratul E-mail: hayyiratulfatimah@yahoo.com Wilfred, Cecilia E-mail: hayyiratulfatimah@yahoo.com

    2014-10-24

    A series of Mg/TiO{sub 2} photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%.

  15. Simultaneous desulfurization and dephosphorization reactions of molten iron by soda ash treatment

    NASA Astrophysics Data System (ADS)

    Mori, Katsumi; Wada, Harue; Pehlke, Robert D.

    1985-06-01

    Desulfurization and dephosphorization reactions of molten iron by soda ash has been studied on laboratory heats of Fe-C, Fe-C-S, Fe-C-P, and Fe-C-S-P alloys at 1573 and 1623 K. The alloys were melted in helium gas flow and preheated soda ash was added; metal samples were taken at certain time intervals and analyzed for sulfur, phosphorus, and carbon. Evolved gas samples were also taken at certain time intervals and analyzed. The phosphorus and sulfur contents in metals decreased rapidly, reaching the lowest values two to four minutes after the soda ash addition. The degree of desulfurization was generally greater than that of dephosphorization, and both degrees were higher at lower reaction temperature. The major component of evolved gas was CO with small amounts of CO2. Phosphorus appeared to form a stable phosphate compound with Na2O, possibly 3Na2O-P2O5, in the slag phase. Soda ash reacts with carbon resulting in decarburization of molten iron and vaporization of sodium; this reaction may cause the fading of soda ash and can be expressed as: Na2CO3(1) + (1 + x) C = (1 - xNa2O(1) + 2 xNa(g_ + (2 + xCO(g). For the phosphorus containing melt, the reaction can be expressed as: Na2CO3(l) + yC + 2 x/3 P = x(Na2O · 1/3P2O5)(1) + (2 - y - 8 x/3)Na2O(l) + 2(-l + y + 5 x/3)Na(g) + (1 + y)CO(g) and for the sulfur containing melt: Na2O(l) + C + S = Na2S(l) + CO(g).

  16. Evidences for CYP3A4 autoactivation in the desulfuration of dimethoate by the human liver.

    PubMed

    Buratti, Franca M; Testai, Emanuela

    2007-11-20

    Dimethoate (DIM) is an organophosphorothionate (OPT) pesticide used worldwide as a systemic insecticide and acaricide. It is characterized by low-to-moderate acute mammalian toxicity; similarly to the other OPT pesticides, its mode of action is mediated by the inhibition of acetylcholinesterase (AChE), exerted by its toxic metabolite dimethoate-oxon or omethoate (OME), which is also used as a direct acting pesticide. Human hepatic DIM bioactivation to the toxic metabolite OME has been characterized by using c-DNA expressed human CYPs and human liver microsomes (HLM) also in the presence of CYP-specific chemical inhibitors, with a method based on AChE inhibition. The obtained kinetic parameters and AChE IC(50) have been compared with those previously obtained with other OPTs, indicating a lower efficiency in DIM desulfuration reaction and a lower potency in inhibiting AChE. Results showed that, similarly to the other OPTs tested so far, at low DIM concentration OME formation is mainly catalysed by CYP1A2, while the role of 3A4 is relevant at high DIM levels. Differently from the other OPTs, DIM desulfuration reaction showed an atypical kinetic profile, likely due to CYP3A4 autoactivation. The sigmoidicity degree of the activity curve increased with the level of CYP3A4 in HLM or disappeared in the presence of a CYP3A4 chemical inhibitor. This atypical kinetic behaviour can be considered one of the possible explanations for the recent findings that among patients hospitalized following OPT intoxication, DIM ingestion gave different symptoms and more severe poisoning (23.1% of fatal cases versus total) than chlorpyrifos (8% of deaths), which has a lower LD(50) value. Since DIM-poisoned patients poorly responded to pralidoxime, the possibility to use CYP3A4 inhibitors could be considered as a complementary treatment.

  17. The desulfurization of flue gas at the Mae Moh Power Plant Units 12 and 13

    SciTech Connect

    Haemapun, C.

    1993-12-31

    As pollution of air, water and ground increasingly raises worldwide concern, the responsible national and international authorities establish and issue stringent regulations in order to maintain an acceptable air quality in the environment. In Thailand, the Electricity Generating Authority of Thailand (EGAT) takes full responsibility in environmental protection matters as well as in generating the electricity needed to supply the country`s very rapid power demand growth. Due to the rapidly increasing electricity demand of the country, EGAT had decided to install two further lignite-fired units of 300 MW each (Units 12 and 13) at the Mae Moh power generation station and they are now under construction. The arrangement and the capacity of all the power plant units are as shown. In 1989, EGAT started the work on the flue gas desulfurization system of Mae Moh power plant units 12 and 13 as planned. A study has been conducted to select the most suitable and most economical process for flue gas desulfurization. The wet scrubbing limestone process was finally selected for the two new units. Local limestone will be utilized in the process, producing a by-product of gypsum. Unfortunately, natural gypsum is found in abundance in Thailand, so the produced gypsum will be treated as landfill by mixing it with ash from the boilers of the power plants and then carrying it to the ash dumping area. The water from the waste ash water lake is utilized in the process as much as possible to minimize the requirement of service water, which is a limited resource. The Mae Moh power generation station is situated in the northern region of Thailand, 600 km north of Bangkok and about 30 km east of the town of Lampang, close to the Mae Moh lignite mine. Three lignite-fired units (Units 1-3) of 75 MW each, four units (Units 4-7) of 150 MW each and four units (Units 8-11) of 300 MW each are in operation.

  18. High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

    NASA Technical Reports Server (NTRS)

    Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

    2007-01-01

    Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

  19. Research on Identification and Screen of Microbial Desulfurization Strains for Petroleum

    NASA Astrophysics Data System (ADS)

    Xiaojuan, Tian; Lingtian, Tang; Li'e, Peng; Xinghong, Li

    The oil-contaminated soil sample was acquired from Shengli Oilfield and Jidong Oilfield and cultured with enrichment technology. Then 21 desulfurization strains were separated from the sample, from which a high efficiency desulfurization strain TV9704 was selected. The strain could neither grow with n-dodecane, n-hexadecane, liquid paraffin, naphthalene or diesel as a carbon source and energy source, nor obviously reduce oil combustion value. It could use thiophene or dibenzothiophene (DBT) as the sole sulfur source. In the experiment, the concentrations of thiophene and DBT were measured by UV spectrophotometer. After being cultured in the culture medium with an initial concentration of 63.2 mmol/L respectively for 48 h and 144 h, the degradation rates of the strain TV9704 on thiophene were 39.0% and 63.8%; the DBT with an initial concentration of 2.7 mmol/L was degraded by 1.46 mmol/L after cultured for 72 h. When sodium acetate and glycerol were chosen as carbon source, the ethanol could enhance the degradation rate of TV9704 on DBT significantly. Strain TV9704 was identified by China Industrial Culture Collection Center (CICC) as a Bacillus sp., Gram-positive, obligate aerobic, which forms a circular orange colony on the nutrition gravy plate. The 16SrDNA gene sequencing test and analysis was carried out on strain TV9704, finding that its homologies with the most similar species Bacillus aquimaris and Bacillus marisflavi were 99.2% and 98.2% respectively, but a larger difference existed between their cell morphological characteristics and physiological and biochemical characteristics, therefore strain TV9704 may be a new species because it was impossible to be categorized to any population.

  20. Coal desulfurization

    NASA Technical Reports Server (NTRS)

    Corcoran, William H. (Inventor); Vasilakos, Nicholas P. (Inventor); Lawson, Daniel D. (Inventor)

    1982-01-01

    A method for enhancing solubilizing mass transport of reactive agents into and out of carbonaceous materials, such as coal. Solubility parameters of mass transfer and solvent media are matched to individual peaks in the solubility parameter spectrum of coals to enhance swelling and/or dissolution. Methanol containing reactive agent carriers are found particularly effective for removing organic sulfur from coals by chlorinolysis.

  1. Preparation of AAO-CeO2 nanotubes and their application in electrochemical oxidation desulfurization of diesel.

    PubMed

    Du, Xiaoqing; Yang, Yumeng; Yi, Chenxi; Chen, Yu; Cai, Chao; Zhang, Zhao

    2017-02-10

    The coaxial arrays of AAO-CeO2 NTs have been successfully galvanostatically deposited on an anode, characterized and adopted as a catalyst for removing organic sulfurs from diesel. The influence of the main electrochemical oxidation factors on the efficiency of desulfurization have also been investigated. The results show that the fabrication process of AAO-CeO2 NTs is accompanied by the formation of a new phase, namely Al3Ce, and the main oxidation products of the diesel are soluble inorganic sulphides, especially Ce2(SO4)3. When compared with dibenzothiophene and 4, 6-dimethyldibenzothiophene, benzothiophene is much more easily removed, with a removal efficiency that reaches 87.2%. Finally, a possible electrochemical oxidation desulfurization pathway for diesel is proposed.

  2. Anaerobic desulfurization of ground rubber with the thermophilic archaeon Pyrococcus furiosus--a new method for rubber recycling.

    PubMed

    Bredberg, K; Persson, J; Christiansson, M; Stenberg, B; Holst, O

    2001-01-01

    The anaerobic sulfur-reducing archaeon Pyrococcus furiosus was investigated regarding its capacity to desulfurize rubber material. The microorganism's sensitivity towards common rubber elastomers and additives was tested and several were shown to be toxic to P. furiosus. The microorganism was shown to utilize sulfur in vulcanized natural rubber and an increase in cell density was obtained when cultivated in the presence of spent tire rubber. Ethanol-leached cryo-ground tire rubber treated with P. furiosus for 10 days was vulcanized together with virgin rubber material (15% w/w) and the mechanical properties of the resulting material were determined. The increase in the stress at break value and the decrease in swell ratio and stress relaxation rate obtained for material containing microbially treated rubber (compared to untreated material) show the positive effects of microbial desulfurization on rubber.

  3. Quantification of gypsum crystal nucleation, growth, and breakage rates in a wet flue gas desulfurization pilot plant

    SciTech Connect

    Hansen, B.B.; Kiil, S.; Johnsson, J.E.

    2009-10-15

    The aim of this work is to study the influence of nucleation, growth and breakage on the particle size distribution (PSD) of gypsum crystals produced by the wet flue gas desulfurization (FGD) process. The steady state PSD, obtained in a falling film wet FGD pilot plant during desulfurization of a 1000 ppm(V) SO{sub 2} gas stream, displayed a strong nonlinear behaviour (in a ln(n(l)) vs. I plot) at the lower end of the particle size range, compared to the well-known linear mixed suspension mixed product removal model. A transient population balance breakage model, fitted to experimental data, was able to model an increase in the fraction of small particles, but not to the extent observed experimentally. A three-parameter, size-dependent growth model, previously used for sodium sulphate decahydrate and potash alum, was able to describe the experimental data, indicating either size-dependent integration kinetics or growth rate dispersion.

  4. Preparation of AAO-CeO2 nanotubes and their application in electrochemical oxidation desulfurization of diesel

    NASA Astrophysics Data System (ADS)

    Du, Xiaoqing; Yang, Yumeng; Yi, Chenxi; Chen, Yu; Cai, Chao; Zhang, Zhao

    2017-02-01

    The coaxial arrays of AAO-CeO2 NTs have been successfully galvanostatically deposited on an anode, characterized and adopted as a catalyst for removing organic sulfurs from diesel. The influence of the main electrochemical oxidation factors on the efficiency of desulfurization have also been investigated. The results show that the fabrication process of AAO-CeO2 NTs is accompanied by the formation of a new phase, namely Al3Ce, and the main oxidation products of the diesel are soluble inorganic sulphides, especially Ce2(SO4)3. When compared with dibenzothiophene and 4, 6-dimethyldibenzothiophene, benzothiophene is much more easily removed, with a removal efficiency that reaches 87.2%. Finally, a possible electrochemical oxidation desulfurization pathway for diesel is proposed.

  5. Selective desulfurization of cysteine in the presence of Cys(Acm) in polypeptides obtained by native chemical ligation.

    PubMed

    Pentelute, Brad L; Kent, Stephen B H

    2007-02-15

    Increased versatility for the synthesis of proteins and peptides by native chemical ligation requires the ability to ligate at positions other than Cys. Here, we report that Raney nickel can be used under standard conditions for the selective desulfurization of Cys in the presence of Cys(Acm). This simple and practical tactic enables the more common Xaa-Ala junctions to be used as ligation sites for the chemical synthesis of Cys-containing peptides and proteins. [reaction: see text].

  6. Kinetics of Mn-based sorbents for hot coal gas desulfurization. Quarterly progress report, July 15, 1995--September 15, 1995

    SciTech Connect

    Hepworth, M.T.

    1995-09-15

    The Morgantown Energy Technology Center (METC) of the U.S. Department of Energy (DOE) is actively pursuing the development of reliable and cost-effective processes to clean coal gasifier gases for application to integrated gasification combined cycle (IGCC) and molten carbonate fuel cell (MCFC) power plants. A large portion of gas cleanup research has been directed towards hot gas desulfurization using Zn-based sorbents. However, zinc titinate sorbents undergo reduction to the metal at temperatures approaching 700{degrees}C. In addition, sulfate formation during regeneration leads to spalling of reactive 293 surfaces. Due to zinc-based sorbent performance, METC has shown interest in formulating and testing manganese-based sorbents. Westmoreland and Harrison evaluated numerous candidate sulfur sorbents and identified Mn as a good candidate. Later, Turkdogan and Olsson tested manganese-based sorbents which demonstrated superior desulfurization capacity under high temperatures, and reducing conditions. Recently, Ben-Slimane and Hepworth conducted several studies on formulating Mn-sorbents and desulfurizing a simulated fuel gas. Although thermodynamics predicts higher over-pressures with Mn verses Zn, under certain operating conditions Mn-based sorbents may obtain < 20 ppmv. In addition, the manganese-sulfur-oxygen (Mn-S-O) system does not reduce to the metal under even highly reducing gases at high temperatures (550-900{degrees}C). Currently, many proposed IGCC processes include a water quench prior to desulfurization. This is for two reasons; limitations in the process hardware (1000{degrees}C), and excessive Zn-based sorbent loss (about 700{degrees}C). With manganese the water quench is obviated due to sorbent loss, as Mn-based sorbents have been shown to retain reactivity under cycling testing at 900{degrees}C. This reduces system hardware, and increases thermal efficiency while decreasing the equilibrium H{sub 2}S over-pressure obtainable with a manganese sorbent.

  7. Bench-scale demonstration of hot-gas desulfurization technology. Quarterly report, October 1 - December 31, 1994

    SciTech Connect

    1994-12-31

    The U.S. Department of Energy (DOE), Morgantown Energy Technology Center (METC), is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal gas) streams of integrated gasification combined-cycle (IGCC) power systems. The programs focus on hot-gas particulate removal and desulfurization technologies that match or nearly match the temperatures and pressures of the gasifier, cleanup system, and power generator. The work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs. Hot-gas desulfurization research has focused on regenerable mixed-metal oxide sorbents which can reduce the sulfur in coal gas to less than 20 ppmv and can be regenerated in a cyclic manner with air for multicycle operation. Zinc titanate (Zn{sub 2}TiO{sub 4} or ZnTiO{sub 3}), formed by a solid-state reaction of zinc (ZnO) and titanium dioxide (TiO{sub 2}), is currently one of the leading sorbents. This report summarizes the highlights and accomplishments of the October slipstream test run of the Zinc Titanate Fluid Bed Desulfurization/Direct Sulfur Recovery Process (ZTFBD/DSRP) Mobile Laboratory at the Department of Energy`s Morgantown Energy Technology Center. Although the run had to be shortened due to mechanical problems with METC`s gasifier, there was sufficient on-stream time to demonstrate highly successful operation of both the zinc titanate fluid bed desulfurization and the DSRP with actual coal gas.

  8. Characterization and comparative study of coal combustion residues from a primary and additional flue gas secondary desulfurization process

    SciTech Connect

    Gomes, S.; Francois, M.; Evrard, O.; Pellissier, C.

    1998-11-01

    An extensive characterization and comparative study was done on two flue gas desulfurization (FGD) residues derived from the same coal. LR residues (originated from Loire/Rhone in the south of Lyon, France) are obtained after a primary desulfurization process (SO{sub 2} is trapped by reaction with CaO at a temperature of about 1100 C), and LM residues (originating from La Maxe, near Metz in the east of France) are obtained after an additional secondary desulfurization process (SO{sub 2} is removed further by reaction with Ca(OH){sub 2} at a temperature of about 120 C). Various and complementary investigation methods were used to determine their chemical, physical, and mineralogical properties: x-ray fluorescence and diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetry analysis, granulometric distribution, pycnometric density, BET specific surface area and pH, conductivity measurements, and chemical analysis of their insoluble fraction. The FGD residues contain basically two main components: a silico-aluminous fly ash part and calcic FGD phases. In the LR residues the two components can be considered as independent, whereas they are linked in the LM residues because chemical reactions have occurred, leading to the formation of silico-calcic gel CSH, hydrated aluminate AFm, and AFt phases.

  9. Investigations in physical mechanism of the oxidative desulfurization process assisted simultaneously by phase transfer agent and ultrasound.

    PubMed

    Bhasarkar, Jaykumar B; Chakma, Sankar; Moholkar, Vijayanand S

    2015-05-01

    This paper attempts to discern the physical mechanism of the oxidative desulfurization process simultaneously assisted by ultrasound and phase transfer agent (PTA). With different experimental protocols, an attempt is made to deduce individual beneficial effects of PTA and ultrasound on the oxidative desulfurization system, and also the synergy between the effects of PTA and ultrasound. Effect of PTA is more marked for mechanically stirred system due to mass transfer limitations, while intense emulsification due to ultrasound helps overcome the mass transfer limitations and reduces the extent of enhancement of oxidation by PTA. Despite application of PTA and ultrasound, the intrinsic factors and properties of the reactants such as polarity (and hence partition coefficient) and diffusivity have a crucial effect on the extent of oxidation. The intrinsic reactivity of the oxidant also plays a vital role, as seen from the extent of oxidation achieved with performic acid and peracetic acid. The interfacial transport of oxidant in the form of oxidant-PTA complex reduces the undesired consumption of oxidant by the reducing species formed during transient cavitation in organic medium, which helps effective utilization of oxidant towards desulfurization.

  10. A fiber optics system for monitoring utilization of ZnO adsorbent beds during desulfurization for logistic fuel cell applications

    NASA Astrophysics Data System (ADS)

    Sujan, Achintya; Yang, Hongyun; Dimick, Paul; Tatarchuk, Bruce J.

    2016-05-01

    An in-situ fiber optic based technique for direct measurement of capacity utilization of ZnO adsorbent beds by monitoring bed color changes during desulfurization for fuel cell systems is presented. Adsorbents composed of bulk metal oxides (ZnO) and supported metal oxides (ZnO/SiO2 and Cusbnd ZnO/SiO2) for H2S removal at 22 °C are examined. Adsorbent bed utilization at breakthrough is determined by the optical sensor as the maximum derivative of area under UV-vis spectrum from 250 to 800 nm observed as a function of service time. Since the response time of the sensor due to bed color change is close to bed breakthrough time, a series of probes along the bed predicts utilization of the portion of bed prior to H2S breakthrough. The efficacy of the optical sensor is evaluated as a function of inlet H2S concentration, H2S flow rate and desulfurization in presence of CO, CO2 and moisture in feed. A 6 mm optical probe is employed to measure utilization of a 3/16 inch ZnO extrudate bed for H2S removal. It is envisioned that with the application of the optical sensor, desulfurization can be carried out at high adsorbent utilization and low operational costs during on-board miniaturized fuel processing for logistic fuel cell power systems.

  11. Multiphase Modeling of Bottom-Stirred Ladle for Prediction of Slag-Steel Interface and Estimation of Desulfurization Behavior

    NASA Astrophysics Data System (ADS)

    Singh, Umesh; Anapagaddi, Ravikiran; Mangal, Saurabh; Padmanabhan, Kuppuswamy Anantha; Singh, Amarendra Kumar

    2016-06-01

    Ladle furnace is a key unit in which various phenomena such as deoxidation, desulfurization, inclusion removal, and homogenization of alloy composition and temperature take place. Therefore, the processes present in the ladle play an important role in determining the quality of steel. Prediction of flow behavior of the phases present in the ladle furnace is needed to understand the phenomena that take place there and accordingly control the process parameters. In this study, first a mathematical model is developed to analyze the transient three-phase flow present. Argon gas bottom-stirred ladle with off-centered plugs has been used in this study. Volume of fluid method is used in a computational fluid dynamics (CFD) model to capture the behavior of slag, steel, and argon interfaces. The results are validated with data from literature. Eye opening and slag-steel interfacial area are calculated for different operating conditions and are compared with experimental and simulated results cited in literature. Desulfurization rate is then predicted using chemical kinetic equations, interfacial area, calculated from CFD model, and thermodynamic data, obtained from the Thermo-Calc software. Using the model, it is demonstrated that the double plug purging is more suitable than the single plug purging for the same level of total flow. The advantage is more distinct at higher flow rates as it leads higher interfacial area, needed for desulfurization and smaller eye openings (lower oxygen/nitrogen pickup).

  12. Deep extractive and oxidative desulfurization of dibenzothiophene with C5H9NO·SnCl2 coordinated ionic liquid.

    PubMed

    Li, Fa-tang; Kou, Cheng-guang; Sun, Zhi-min; Hao, Ying-juan; Liu, Rui-hong; Zhao, Di-shun

    2012-02-29

    A new C5H9NO·SnCl2 coordinated ionic liquid (IL) was prepared by reacting N-methyl-pyrrolidone with anhydrous SnCl2. Desulfurization of dibenzothiophene (DBT) via extraction and oxidation with C5H9NO·SnCl2 IL as extractant, H2O2 and equal mol of CH3COOH as oxidants was investigated. The Nernst partition coefficients k(N) of C5H9NO·SnCl2 IL for the DBT in n-octane was above 5.0, showing its excellent extraction ability. During the oxidative desulfurization process, the optimal molar ratio of H2O2/DBT was six. Sulfur removal of DBT in n-octane was 94.8% in 30 min at 30 °C under the conditions of H2O2/DBT molar ratio of six and V (IL):V (oil)=1:3. Moreover, the sulfur removal increased with increasing temperature because of the high reaction rate constant, low viscosity, and high solubility of dibenzothiophene-sulfone in the IL. The kinetics of oxidative desulfurization of DBT was also investigated, and the apparent activation energy was found to be 32.5 kJ/mol. The IL could be recycled six times without a significant decrease in activity.

  13. Comparative studies of phenotypic and genetic characteristics between two desulfurizing isolates of Rhodococcus erythropolis and the well-characterized R. erythropolis strain IGTS8.

    PubMed

    Santos, Silvia C C; Alviano, Daniela S; Alviano, Celuta S; Goulart, Fátima R V; de Pádula, Marcelo; Leitão, Alvaro C; Martins, Orlando B; Ribeiro, Claudia M S; Sassaki, Mônica Y M; Matta, Carla P S; Bevilaqua, Juliana; Sebastián, Gina V; Seldin, Lucy

    2007-06-01

    Two Rhodococcus erythropolis isolates, named A66 and A69, together with the well-characterized R. erythropolis strain IGTS8 were compared biochemically and genetically. Both isolates, like strain IGTS8, desulfurized DBT to 2-hydroxybiphenyl (2-HBP), following the 4S pathway of desulfurization. Strain IGTS8 showed the highest (81.5%) desulfurization activity in a medium containing DBT at 30 degrees C. Strain A66 showed approximately the same desulfurization activity either when incubated at 30 degrees C or at 37 degrees C, while strain A69 showed an increase of desulfurization efficiency (up to 79%) when incubated at 37 degrees C. Strains A66 and A69 were also able to grow using various organosulfur or organonitrogen-compounds as the sole sulfur or nitrogen sources. The biological responses of A66, A69 and IGTS8 strains to a series of mutagens and environmental agents were evaluated, trying to mimic actual circumstances involved in exposure/handling of microorganisms during petroleum biorefining. The results showed that strains A69 and IGTS8 were much more resistant to UVC treatment than A66. The three desulfurization genes (dszA, dszB and dszC) present in strains A66 and A69 were partially characterized. They seem to be located on a plasmid, not only in the strain IGTS8, but also in A66 and A69. PCR amplification was observed using specific primers for dsz genes in all the strains tested; however, no amplification product was observed using primers for carbazole (car) or quinoline (qor) metabolisms. All this information contributes to broaden our knowledge concerning both the desulfurization of DBT and the degradation of organonitrogen compounds within the R. erythropolis species.

  14. Desulfurization of phosphorothioate oligonucleotides via the sulfur-by-oxygen replacement induced by the hydroxyl radical during negative electrospray ionization mass spectrometry.

    PubMed

    Wu, Lianming; White, David E; Ye, Connie; Vogt, Frederick G; Terfloth, Gerald J; Matsuhashi, Hayao

    2012-07-01

    While the occurrence of desulfurization of phosphorothioate oligonucleotides in solution is well established, this study represents the first attempt to investigate the basis of the unexpected desulfurization via the net sulfur-by-oxygen (S-O) replacement during negative electrospray ionization (ESI). The current work, facilitated by quantitative mass deconvolution, demonstrates that considerable desulfurization can take place even under common negative ESI operating conditions. The extent of desulfurization is dependent on the molar phosphorothioate oligonucleotide-to-hydroxyl radical ratio, which is consistent with the corona discharge-induced origin of the hydroxyl radical leading to the S-O replacement. This hypothesis is supported by the fact that an increase of the high-performance liquid chromatography (HPLC) flow rate and the on-column concentration of a phosphorothioate oligonucleotide, as well as a decrease of the electrospray voltage reduce the degree of desulfurization. Comparative LC-tandem mass spectrometry (MS/MS) sequencing of a phosphorothioate oligonucleotide and its corresponding desulfurization product revealed evidence that the S-O replacement occurs at multiple phosphorothioate internucleotide linkage sites. In practice, the most convenient and effective strategy for minimizing this P = O artifact is to increase the LC flow rate and the on-column concentration of phosphorothioate oligonucleotides. Another approach to mitigate possible detrimental effects of the undesired desulfurization is to operate the ESI source at a very low electrospray voltage to diminish the corona discharge; however this will significantly compromise sensitivity when analyzing the low-level P = O impurities in phosphorothioate oligonucleotides.

  15. Pyrite surface characterization and control for advanced fine coal desulfurization technologies. Ninth quarterly technical progress report, September 1, 1992-- December 31, 1992

    SciTech Connect

    Wang, X.H.; Leonard, J.W.; Parekh, B.K.; Jiang, C.L.

    1992-12-31

    This is the 9th quarterly technical progress report for the project entitled ``Pyrite surface characterization and control for advanced fine coal desulfurization technologies``, DE-FG22-90PC90295. The work presented in this report was performed from September 1, 1992 to November 31, 1992. The objective of the project is to conduct extensive fundamental studies on the surface chemistry of pyrite oxidation and flotation and to understand how the alteration of the coal-pyrite surface affects the efficiency of pyrite rejection in coal flotation. During this reporting period, the surface oxidation of pyrite in various electrolytes was investigated. It has been demonstrated, for the first time, that borate, a pH buffer and electrolyte used by many previous investigators in studying sulfide mineral oxidation, actively participates in the surface oxidation of pyrite. In borate solutions, the surface oxidation of pyrite is tronly enhanced. The anodic oxidation potential of pyrite is lowered by more than 0.4 volts. The initial reaction of the borate enhanced pyrite oxidation can be described by:FeS{sub 2} + B(OH){sub 4}{sup =} ------> [S{sub 2}Fe-B(OH){sub 4}]{sub surf} + e. This reaction is irreversible and is controlled by the mass-transfer of borate species from the solution to the surface. It has been shown that the above reaction inhibits the adsorption of xanthate on pyrite. Comparative studies have been made with other sulfide minerals. The solution chemistry of the iron-borate systems have been studied to understand the electrochemical results.

  16. BIOCATALYTIC POLYESTER SYNTHESIS: ANALYSIS OF THE EVOLUTION OF MOLECULAR WEIGHT AND END-GROUP FUNCTIONALITY. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  17. Immobilization of the α-amylase of Bacillus amyloliquifaciens TSWK1-1 for the improved biocatalytic properties and solvent tolerance.

    PubMed

    Kikani, B A; Pandey, S; Singh, S P

    2013-05-01

    The α-amylase of Bacillus amyloliquifaciens TSWK1-1 (GenBank Number, GQ121033) was immobilized by various methods, including ionic binding with DEAE cellulose, covalent coupling with gelatin and entrapment in polyacrylamide and agar. The immobilization of the purified enzyme was most effective with the DEAE cellulose followed by gelatin, agar and polyacrylamide. The K m increased, while V max decreased upon immobilization on various supports. The temperature and pH profiles broadened, while thermostability and pH stability enhanced after immobilization. The immobilized enzyme exhibited greater activity in various non-ionic surfactants, such as Tween-20, Tween-80 and Triton X-100 and ionic surfactant, SDS. Similarly, the enhanced stability of the immobilized α-amylase in various organic solvents was among the attractive features of the study. The reusability of the immobilized enzyme in terms of operational stability was assessed. The DEAE cellulose immobilized α-amylase retained its initial activity even after 20 consequent cycles. The DEAE cellulose immobilized enzyme hydrolyzed starch with 27 % of efficiency. In summary, the immobilization of B. amyloliquifaciens TSWK1-1 α-amylase with DEAE cellulose appeared most suitable for the improved biocatalytic properties and stability.

  18. Biocatalytic Synthesis of Flavor Ester “Pentyl Valerate” Using Candida rugosa Lipase Immobilized in Microemulsion Based Organogels: Effect of Parameters and Reusability

    PubMed Central

    Raghavendra, Tripti; Panchal, Nilam; Divecha, Jyoti; Shah, Amita; Madamwar, Datta

    2014-01-01

    Pentyl valerate was synthesized biocatalytically using Candida rugosa lipase (CRL) immobilized in microemulsion based organogels (MBGs). The optimum conditions were found to be pH 7.0, temperature of 37°C, ratio of concentration of water to surfactant (Wo) of 60, and the surfactant sodium bis-2-(ethylhexyl)sulfosuccinate (AOT) for MBG preparation. Although kinetic studies revealed that the enzyme in free form had high affinity towards substrates (Km = 23.2 mM for pentanol and 76.92 mM for valeric acid) whereas, after immobilization, the Km values increased considerably (74.07 mM for pentanol and 83.3 mM for valeric acid) resulting in a slower reaction rate, the maximum conversion was much higher in case of immobilized enzyme (~99%) as compared to free enzyme (~19%). Simultaneous effects of important parameters were studied using response surface methodology (RSM) conjugated with Box-Behnken design (BBD) with five variables (process parameters), namely, enzyme concentration, initial water content (Wo), solvent used for MBG preparation, substrate ratio and time, and response as the final product formation, that is, pentyl valerate (%). The MBGs were reused for 10 consecutive cycles for ester synthesis. Efficacy of AOT/isooctane as dehydrating agent for extracting excess water from MBGs was found to exert a positive effect on the esterification reaction. PMID:25093166

  19. Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell

    PubMed Central

    Xu, Pei; Du, Peng-Xuan; Zong, Min-Hua; Li, Ning; Lou, Wen-Yong

    2016-01-01

    The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol. PMID:27185089

  20. Highly sensitive photoelectrochemical immunoassay with enhanced amplification using horseradish peroxidase induced biocatalytic precipitation on a CdS quantum dots multilayer electrode.

    PubMed

    Zhao, Wei-Wei; Ma, Zheng-Yuan; Yu, Pei-Pei; Dong, Xiao-Ya; Xu, Jing-Juan; Chen, Hong-Yuan

    2012-01-17

    Herein we demonstrate the protocol of a biocatalytic precipitation (BCP)-based sandwich photoelectrochemical (PEC) horseradish peroxidase (HRP)-linked immunoassay on the basis of their synergy effect for the ultrasensitive detection of mouse IgG (antigen, Ag) as a model protein. The hybrid film consisting of oppositely charged polyelectrolytes and CdS quantum dots (QDs) is developed by the classic layer by layer (LbL) method and then employed as the photoactive antibody (Ab) immobilization matrix for the subsequent sandwich-type Ab-Ag affinity interactions. Improved sensitivity is achieved through using the bioconjugates of HRP-secondary antibodies (Ab(2)). In addition to the much enhanced steric hindrance compared with the original one, the presence of HRP would further stimulate the BCP onto the electrode surface for signal amplification, concomitant to a competitive nonproductive absorption that lowers the photocurrent intensity. As a result of the multisignal amplification in this HRP catalyzed BCP-based PEC immunoassay, it possesses excellent analytical performance. The antigen could be detected from 0.5 pg/mL to 5.0 ng/mL with a detection limit of 0.5 pg/mL.

  1. Biocatalytic behaviour of immobilized Rhizopus oryzae lipase in the 1,3-selective ethanolysis of sunflower oil to obtain a biofuel similar to biodiesel.

    PubMed

    Luna, Carlos; Verdugo, Cristóbal; Sancho, Enrique D; Luna, Diego; Calero, Juan; Posadillo, Alejandro; Bautista, Felipa M; Romero, Antonio A

    2014-08-04

    A new biofuel similar to biodiesel was obtained in the 1,3-selective transesterification reaction of sunflower oil with ethanol using as biocatalyst a Rhizopus oryzae lipase (ROL) immobilized on Sepiolite, an inorganic support. The studied lipase was a low cost powdered enzyme preparation, Biolipase-R, from Biocon-Spain, a multipurpose additive used in food industry. In this respect, it is developed a study to optimize the immobilization procedure of these lipases on Sepiolite. Covalent immobilization was achieved by the development of an inorganic-organic hybrid linker formed by a functionalized hydrocarbon chain with a pendant benzaldehyde, bonded to the AlPO4 support surface. Thus, the covalent immobilization of lipases on amorphous AlPO4/sepiolite (20/80 wt %) support was evaluated by using two different linkers (p-hydroxybenzaldehyde and benzylamine-terephthalic aldehyde, respectively). Besides, the catalytic behavior of lipases after physical adsorption on the demineralized sepiolite  was also evaluated. Obtained results indicated that covalent immobilization with the p-hydroxybenzaldehyde linker gave the best biocatalytic behavior. Thus, this covalently immobilized lipase showed a remarkable stability as well as an excellent capacity of reutilization (more than five successive reuses) without a significant loss of its initial catalytic activity. This could allow a more efficient fabrication of biodiesel minimizing the glycerol waste production.

  2. Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell

    NASA Astrophysics Data System (ADS)

    Xu, Pei; Du, Peng-Xuan; Zong, Min-Hua; Li, Ning; Lou, Wen-Yong

    2016-05-01

    The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol.

  3. Biocatalytic synthesis of flavor ester "pentyl valerate" using Candida rugosa lipase immobilized in microemulsion based organogels: effect of parameters and reusability.

    PubMed

    Raghavendra, Tripti; Panchal, Nilam; Divecha, Jyoti; Shah, Amita; Madamwar, Datta

    2014-01-01

    Pentyl valerate was synthesized biocatalytically using Candida rugosa lipase (CRL) immobilized in microemulsion based organogels (MBGs). The optimum conditions were found to be pH 7.0, temperature of 37 °C, ratio of concentration of water to surfactant (Wo) of 60, and the surfactant sodium bis-2-(ethylhexyl)sulfosuccinate (AOT) for MBG preparation. Although kinetic studies revealed that the enzyme in free form had high affinity towards substrates (K(m) = 23.2 mM for pentanol and 76.92 mM for valeric acid) whereas, after immobilization, the K(m) values increased considerably (74.07 mM for pentanol and 83.3 mM for valeric acid) resulting in a slower reaction rate, the maximum conversion was much higher in case of immobilized enzyme (~99%) as compared to free enzyme (~19%). Simultaneous effects of important parameters were studied using response surface methodology (RSM) conjugated with Box-Behnken design (BBD) with five variables (process parameters), namely, enzyme concentration, initial water content (Wo), solvent used for MBG preparation, substrate ratio and time, and response as the final product formation, that is, pentyl valerate (%). The MBGs were reused for 10 consecutive cycles for ester synthesis. Efficacy of AOT/isooctane as dehydrating agent for extracting excess water from MBGs was found to exert a positive effect on the esterification reaction.

  4. Understanding the plasticity of the alpha/beta hydrolase fold: lid swapping on the Candida antarctica lipase B results in chimeras with interesting biocatalytic properties.

    PubMed

    Skjøt, Michael; De Maria, Leonardo; Chatterjee, Robin; Svendsen, Allan; Patkar, Shamkant A; Ostergaard, Peter R; Brask, Jesper

    2009-02-13

    The best of both worlds. Long molecular dynamics (MD) simulations of Candida antarctica lipase B (CALB) confirmed the function of helix alpha5 as a lid structure. Replacement of the helix with corresponding lid regions from CALB homologues from Neurospora crassa and Gibberella zeae resulted in new CALB chimeras with novel biocatalytic properties. The figure shows a snapshot from the MD simulation. The Candida antarctica lipase B (CALB) has found very extensive use in biocatalysis reactions. Long molecular dynamics simulations of CALB in explicit aqueous solvent confirmed the high mobility of the regions lining the channel that leads into the active site, in particular, of helices alpha5 and alpha10. The simulation also confirmed the function of helix alpha5 as a lid of the lipase. Replacing it with corresponding lid regions from the CALB homologues from Neurospora crassa and Gibberella zeae resulted in two new CALB mutants. Characterization of these revealed several interesting properties, including increased hydrolytic activity on simple esters, specifically substrates with C(alpha) branching on the carboxylic side, and much increased enantioselectivity in hydrolysis of racemic ethyl 2-phenylpropanoate (E>50), which is a common structure of the profen drug family.

  5. Pb(II) removal from aqueous solution by a low-cost adsorbent dry desulfurization slag

    NASA Astrophysics Data System (ADS)

    Wu, Qiong; You, Ruirong; Clark, Malcolm; Yu, Yan

    2014-09-01

    A collectable and non-sintered material prepared as hollow cylindrical shaped pellet from dry desulfurization slag (FGD ash) and ordinary Portland cement (OPC) for wastewater treatments is tested. The characteristic results of powder X-ray diffraction (XRD) and infrared absorption spectroscopy (IR) show that -OH, CO32-, SO32- and SO42- are the possible functional groups responsible for Pb uptake. Adsorption data indicate that Pb removal is pH dependent and optimal at pH 6, with a very rapid initial removal that reaches equilibrium in about 90 min. A maximum removal of 99.2% is seen for 5 mg/L (pH of 6); higher initial Pb concentrations reduce overall removal efficiencies, but generate higher surface loadings. Adsorption process correlates well with both Langmuir and Freundlich models, although the Langmuir isotherm is more favored, providing a maximum adsorption capacity (Qm) of 130.2 mg/g (13 wt%). Pseudo-second order rate kinetic model best describes the Pb removal, and calculated RL values between 0 and 1, indicate a favored adsorption process that is chemisorption limited. SEM and EDAX analysis of the surface and fracture surface show that Pb occurs as surface precipitates and that Pb is not distributed to the inner core of the pellet. This study demonstrates that dry FGD ash could be successfully used for wastewater Pb removal.

  6. State-of-the-art review of materials-related problems in flue gas desulfurization systems

    SciTech Connect

    Maiya, P. S.

    1980-10-01

    This report characterizes the chemical and mechanical environments to which the structural components used in flue-gas desulfurization (FGD) are exposed. It summarizes the necessary background information pertinent to various FGD processes currently in use, with particular emphasis on lime/limestone scrubbing technology, so that the materials problems and processing variables encountered in FGD systems can be better defined and appreciated. The report also describes the materials currently used and their performance to date in existing wet scrubbers. There is little doubt that with more extensive use of coal and flue-gas scrubbers by utilities and other segments of private industry, a better understanding of the material failure mechanisms, performance limitations, and potential problem areas is required for the design of more reliable and cost-effective FGD systems. To meet the above objectives, a materials evaluation program is proposed. The important experimental variables and the number of tests required to evaluate a given material are discussed. 55 references, 9 figures, 6 tables.

  7. Effects of salts on preparation and use of calcium silicates for flue gas desulfurization

    SciTech Connect

    Kind, K.K.; Wassermann, P.D.; Rochelle, G.T. )

    1994-02-01

    High surface area calcium silicate hydrates that are highly reactive with SO[sub 2] can be made by slurrying fly ash and lime in water at elevated temperatures for several hours. This concept is the basis for the ADVACATE (ADVAnced siliCATE) process for flue gas desulfurization. This paper examines the impact of salts on such a system. Two low calcium fly ashes, from the Shawnee and Clinch River power plants, were examined. The addition of gypsum (CaSO[sub 4][center dot]2H[sub 2]O) or calcium chloride to the slurry system increased the dissolved calcium concentration, allowing the reaction rate to increase and the maximum surface area to more than double in some cases. This increase came despite a lower solution hydroxide level. The salts also enhanced the reaction of the sorbent with sulfur dioxide. This resulted from the higher equilibrium moisture on the sorbent at any humidity due to the deliquescent properties of some of the salts used (calcium chloride and calcium nitrate). Solids made without the deliquescent salts exhibited equilibrium moisture adsorption consistent with a type-II BET isotherm while the deliquescent salts caused hysteresis in the adsorption/desorption isotherm. 22 refs., 10 figs., 2 tabs.

  8. Bio-desulfurization of biogas using acidic biotrickling filter with dissolved oxygen in step feed recirculation.

    PubMed

    Chaiprapat, Sumate; Charnnok, Boonya; Kantachote, Duangporn; Sung, Shihwu

    2015-03-01

    Triple stage and single stage biotrickling filters (T-BTF and S-BTF) were operated with oxygenated liquid recirculation to enhance bio-desulfurization of biogas. Empty bed retention time (EBRT 100-180 s) and liquid recirculation velocity (q 2.4-7.1 m/h) were applied. H2S removal and sulfuric acid recovery increased with higher EBRT and q. But the highest q at 7.1 m/h induced large amount of liquid through the media, causing a reduction in bed porosity in S-BTF and H2S removal. Equivalent performance of S-BTF and T-BTF was obtained under the lowest loading of 165 gH2S/m(3)/h. In the subsequent continuous operation test, it was found that T-BTF could maintain higher H2S elimination capacity and removal efficiency at 175.6±41.6 gH2S/m(3)/h and 89.0±6.8% versus S-BTF at 159.9±42.8 gH2S/m(3)/h and 80.1±10.2%, respectively. Finally, the relationship between outlet concentration and bed height was modeled. Step feeding of oxygenated liquid recirculation in multiple stages clearly demonstrated an advantage for sulfide oxidation.

  9. Ionic liquids screening for desulfurization of natural gasoline by liquid-liquid extraction.

    PubMed

    Likhanova, Natalya V; Guzmán-Lucero, Diego; Flores, Eugenio A; García, Paloma; Domínguez-Aguilar, Marco A; Palomeque, Jorge; Martínez-Palou, Rafael

    2010-11-01

    Seventy five ionic liquids (ILs) were tested as a sequestering agent of sulfured compounds in natural gasoline (NG). Desulphurization of NG was performed by means of liquid-liquid extraction method at room temperature and atmospheric pressure. Experimental ILs containing imidazolium, pyridinium, and ammonium cations along with organic and inorganic anions were synthesized conventionally and under microwave and sonochemical conditions. The effect of the molecular structure of ILs on the desulfurization efficiency of NG with high sulfur content was evaluated. Analysis indicated that the anion type played a more important role than the cation on the desulphurization process. ILs based on halogen-ferrates and halogen-aluminates exhibited the highest efficiency in sulfur removal, and their efficiency is further improved when there is an excess of metallic salt in a ratio of at least 1:1.3 during the synthesis of the corresponding IL. An explanation for the ability of metallic ILs to remove sulfur-containing compounds from natural gasoline based on the ratio of the ionic charge to the atomic radius is proposed. Furthermore, a method to recover and reuse water-sensitive to halogenated precursors is described.

  10. Heterogeneous oxidative desulfurization of diesel fuel catalyzed by mesoporous polyoxometallate-based polymeric hybrid.

    PubMed

    Yang, Huawei; Jiang, Bin; Sun, Yongli; Zhang, Luhong; Huang, Zhaohe; Sun, Zhaoning; Yang, Na

    2017-03-10

    In this work, the simple preparation of novel polymer supported polyoxometallates (POMs) catalysts has been reported. Soluble task-specific cross-linked poly (ionic liquid) (PIL) was prepared with N,​N-​dimethyl-​dodecyl-​(4-​vinylbenzyl) ammonium chloride and divinylbenzene as co-monomers. The as-prepared cationic PILs were assembled with different commercial POMs to form the interlinked mesoporous catalysts, and the formation mechanism was provided. The catalytic oxidation activities of the catalysts were closely related to the formation pathway of their corresponding peroxide active species. The catalyst with H2W12O42(10-) as counterion, which exhibited the best activity in the oxidation of benzothiophene (BT) and dibenzothiophene (DBT) to sulfones in model oil with hydrogen peroxide (H2O2, 30wt%) as oxidant, was characterized by different techniques and systematically studied for its sulfur removal performance. As for the oxidative desulfurization of a real diesel, it was observed that almost all of the original sulfur compounds could be completely converted, and the catalyst could be reused for at least eight cycles without noticeable changes in both catalytic activity and chemical structure. In the end, a catalytic mechanism was put forward with the assistant of Raman analysis.

  11. Dry injection flue gas desulfurization process using absorptive soda ash sorbent

    SciTech Connect

    Cyran, M.J.; Copenhafer, W.C.

    1986-05-13

    A dry injection flue gas desulfurization process is described which comprises injecting a dry soda ash sorbent, which is a particulate solid derived from calcination under non-sintering conditions of a NaHCO/sub 3/-containing compound, into a SO/sub 2/-contaminated flue gas stream that contains moisture in an amount of 0.5-10 wt% H/sub 2/O and is at a temperature of 100/sup 0/-175/sup 0/C; providing an amount of injected sorbent and sufficient gas-sorbent contact time such that a substantial portion, at least 40%, of the sorbent sodium content is utilized at NSR=1, in reducing the concentration of SO/sub 2/ in the gas stream, collecting the sorbent in a solids-collection device which is a fabric filter baghouse or an electrostatic precipitator; discharging collected sorbent from the solids-collection device; the dry soda ash sorbent being a porous calcine obtained from calcination of sodium sesquicarbonate, sodium bicarbonate, Wegscheider's salt or mixtures of these, and further characterized by having a minimum surface area of at least 2 m/sup 2//g and a residual bicarbonate content of less than 10 wt% NaHCO/sub 3/.

  12. The effects of flue gas desulfurization (FGD) system additives on solid by-products. Final report

    SciTech Connect

    Huyck, K.A.; Tatum, G.S.; DeKraker, D.P.

    1995-12-01

    This study was designed to examine characteristics of by-products from flue gas desulfurization (FGD) systems that use performance-enhancing additives. The by-products were evaluated for handling, disposal, properties, and utilization potential. This study was designed to identify potential operation-limiting consequences (fatal flaws) caused by using FGD system additives. It was not intended to be an all-encompassing study of the possible process, environmental, and utilization circumstances at each plant. Seven utilities conducting additive testing agreed to provide samples for this study both before and during their testing. Solid samples were collected from FGD systems using the following additives: di-basic acid (DBA), which is a mixture of succinic, glutaric, and adipic acids; formate; sulfur; ethylene diamine tetraacetic acid (EDTA); and chloride. Changes in handling properties that may alter process operations were observed at sites where DBS was used. Changes in leaching behavior, permeability and unconfined compressive strength (properties that affect by-product disposal properties) showed no clear trend for additive or system type. The intent of this study is to provide an overall assessment of potential system-limiting effects of FGD additive use. There were no overriding problems relating to disposal with the use of additives. However, properties of solids produced with and without additives should be tested at each site prior to use of an FGD system additive. This is necessary because of the variability in state disposal and permitting requirements and the influence of specific operating conditions on by-product properties.

  13. Effect of heavy metals on the stabilization of mercury(II) by DTCR in desulfurization solutions.

    PubMed

    Hou, Jiaai; Lu, Rongjie; Sun, Mingyang; Baig, Shams Ali; Tang, Tingmei; Cheng, Lihua; Xu, Xinhua

    2012-05-30

    Several heavy metals, including Cu(2+), Ni(2+), Pb(2+), and Zn(2+), were investigated in simulated desulfurization solutions to evaluate their interferences with Hg(2+) during the reaction with dithiocarbamate type chelating resin (DTCR). Appropriate DTCR dosage and the effect of pH were also explored with respect to restoration of high Hg(2+) precipitation efficiency and reduction of mercury concentrations. The experimental results suggested that increasing heavy metal concentration inhibited Hg(2+) precipitation efficiency to a considerable extent and the inhibition order of the four heavy metals was Cu(2+)>Ni(2+)>Pb(2+)>Zn(2+). However, the coordination ability was closely related to the configuration and the orbital hybridization of each metal. In the cases of Cu(2+) and Pb(2+), increased DTCR dosage was beneficial to Hg(2+) precipitation, which could lay the foundation of practical applications of DTCR dosage for industrial wastewater treatment. The enhanced Hg(2+) precipitation performance seen for increasing pH might have come from the deprotonation of sulfur atoms on the DTCR functional groups and the formation of metal hydroxides (M(OH)(2), M=Cu, Pb, Hg).

  14. Global evaluation of mass transfer effects: In-duct injection flue gas desulfurization

    SciTech Connect

    Cole, J.A.; Newton, G.H.; Kramlich, J.C.; Payne, R.

    1990-09-30

    Sorbent injection is a low capital cost, low operating cost approach to SO{sub 2} control targeted primarily at older boilers for which conventional fuel gas desulfurization is not economically viable. Duct injection is one variation of this concept in which the sorbent, either a dry powder or a slurry, is injected into the cooler regions of the boiler, generally downstream of the air heaters. The attractiveness of duct injection is tied to the fact that it avoids much of the boiler heat transfer equipment and thus has minimal impact of boiler performance. Both capital and operating cost are low. This program has as its objectives three performance related issues to address: (1) experimentally identify limits on sorbent performance. (2) identify and test sorbent performance enhancement strategies. (3) develop a compute model of the duct injection process. Two major tasks are described: a laboratory-scale global experiment and development of process model. Both are aimed at understanding and quantifying the rate-limiting processes which control SO{sub 2} capture by lime slurry during boiler duct injection. 29 refs., 35 figs., 4 tabs.

  15. Attapulgite-CeO2/MoS2 ternary nanocomposite for photocatalytic oxidative desulfurization

    NASA Astrophysics Data System (ADS)

    Li, Xiazhang; Zhang, Zuosong; Yao, Chao; Lu, Xiaowang; Zhao, Xiaobing; Ni, Chaoying

    2016-02-01

    Novel attapulgite(ATP)-CeO2/MoS2 ternary nanocomposites were synthesized by microwave assisted assembly method. The structures of the nanocomposites were characterized by XRD, FT-IR, UV-vis, XPS and in situ TEM. The photocatalytic activities of ATP-CeO2/MoS2 composites were investigated by degradating dibenzothiophene (DBT) in gasoline under visible light irradiation. The effect of the mass ratio of CeO2 to MoS2 on photocatalytic activity was investigated. The results indicate that the three-dimensional network structure is firmly constructed by ATP skeleton, CeO2 particles and MoS2 nanosheet which effectively increase the surface area of the composites and promote the separation of electrons and holes by resulting electronic transmission channels of multi-channel in space. The degradation rate of DBT can reach 95% under 3 h irradiation when the mass ratio of CeO2/MoS2 is 4/10. A plausible mechanism for the photocatalytic oxidative desulfurization of this nanocomposite is put forward.

  16. Plant species for revegetation of a saline flue gas desulfurization sludge pond

    SciTech Connect

    Salo, L.F.; Artiola, J.F.; Goodrich-Mahoney, J.W.

    1996-07-01

    Codisposing saline wastewater from electrical generating stations with flue gas desulfurization (FGD) scrubber sludge simplifies waste disposal but produces a saline waste that will later require revegetation. This waste is low in macronutrients, contains high levels of salts and B, and has a fine texture. This study identified plants, based on germination test results, that show promise for sowing at an evaporation pound in eastern Arizona where scrubber sludge and wastewater are codisposed. Forty-four grass, forb, and shrub accessions germinated on filter paper in saline water from the disposal pond. Dilutions of disposal pone water with untreated well water from the site ranged in EC from 0.17 to 3.03 S m{sup {minus}1}. Our criteria for evaluating plants to be used in revegetating saline FGD sludge were: (1) ability to germinate in increasing levels of disposal pond water and (2) ease of establishment from seed. The percentage of pond water that would reduce germination to 50% that of well-water controls (P{sub 50}) ranged as high as >100 for the most tolerant plants. 32 refs., 3 tabs.

  17. Biogas desulfurization and biogas upgrading using a hybrid membrane system--modeling study.

    PubMed

    Makaruk, A; Miltner, M; Harasek, M

    2013-01-01

    Membrane gas permeation using glassy membranes proved to be a suitable method for biogas upgrading and natural gas substitute production on account of low energy consumption and high compactness. Glassy membranes are very effective in the separation of bulk carbon dioxide and water from a methane-containing stream. However, the content of hydrogen sulfide can be lowered only partially. This work employs process modeling based upon the finite difference method to evaluate a hybrid membrane system built of a combination of rubbery and glassy membranes. The former are responsible for the separation of hydrogen sulfide and the latter separate carbon dioxide to produce standard-conform natural gas substitute. The evaluation focuses on the most critical upgrading parameters like achievable gas purity, methane recovery and specific energy consumption. The obtained results indicate that the evaluated hybrid membrane configuration is a potentially efficient system for the biogas processing tasks that do not require high methane recoveries, and allows effective desulfurization for medium and high hydrogen sulfide concentrations without additional process steps.

  18. LIFAC flue gas desulfurization process an alternative SO{sub 2} control strategy

    SciTech Connect

    Patel, J.G.; Vilala, J.

    1995-12-01

    This paper discusses the results from two recently completed LIFAC flue gas desulfurization plants - 300 MW Shand lignite powered station owned by Saskatchewan Power Corporation and 60 MW Whitewater Valley high sulfur coal fired station owned by Richmond Powerand Light. LIFACis a dry FGD process in which limestone is injected into the upper regions of the boiler furnace and an activation reactor is used to humidify the unreacted limestone to achieve additional sulfur capture. The performance in both plants indicates that 70 to 80% sulfur is removed at a Ca/S ratio of 2. Cost performance data from these plants has shown that LI FAC both on construction cost and $/ton SO{sub 2} removed basis is very cost competitive compared to other SO{sub 2} control technologies. The Richmond plant has been realized under the auspices of the U.S. Department of Energy`s Clean Coal Technology program. The Shand plant is the first commercial installation in North America. The paper also discusses highlights of operating and maintenance experience, availability and handling of the solid waste product.

  19. Ultra-deep desulfurization via reactive adsorption on peroxophosphomolybdate/agarose hybrids.

    PubMed

    Xu, Jian; Li, Huacheng; Wang, Shengtian; Luo, Fang; Liu, Yunyu; Wang, Xiaohong; Jiang, Zijiang

    2014-09-01

    A catalyst system composed of peroxophosphomolybdates as catalytic center and agarose as matrix material had been designed. The [C16H33N(CH3)3]3[PO4{MoO(O2)2}4]/agarose (C16PMo(O2)2/agarose) hybrid was found to be active for oxidation desulfurization (ODS) of dibenzothiophene (DBT) or real fuel into corresponding sulfone by H2O2 as an oxidant, while the sulfur content could be reduced to 5ppm. The higher activity comes from its components including [PO4{MoO(O2)2}4] catalytic sites, the hydrophobic quaternary ammonium cation affinity to low polarity substrates, and agarose matrix affinity to H2O2 and sulfone. During the oxidative reaction, the mass transfer resistance between H2O2 and organic sulfurs could be decreased and the reaction rate could increase by the assistance of agarose and hydrophobic tails of [C16H33N(CH3)3]3[PO4{MoO(O2)2}4]. Meanwhile, the oxidative products could be adsorbed by agarose matrix to give clean fuel avoiding the post-treatment. In addition, the hybrid was easily regenerated to be reused.

  20. Study on a novel semidry flue gas desulfurization with multifluid alkaline spray generator

    SciTech Connect

    Zhou, Y.G.; Zhang, M.C.; Wang, D.F.; Wang, L.

    2005-11-09

    The advantages and disadvantages of the typical semidry flue gas desulfurization (FGD) processes are analyzed, and a novel semidry FGD process with multifluid alkaline spray generator is first proposed to improve the colliding contact efficiency between sorbent particles and spray water droplets, and to form a large amount of aqueous lime slurry. The experimental results show that the colliding contact efficiency between lime particles and water droplets in the prefix alkaline spray generator may reach about 70%, which is significantly higher than the colliding contact efficiency of 25% in duct sorbent injection. The SO{sub 2} removal efficiency can reach 64.5% when the Ca/S molar ratio is 1.5, the approach to the saturation temperature is 10.3{sup o}C, and the flue gas residence time is 2.25 s. It is higher than that of in-duct sorbent injection under similar conditions, and the sorbent utilization is improved to 43%. Therefore, the FGD process with a prefix alkaline spray generator can greatly improve SO{sub 2} removal efficiency and sorbent utilization and it will be a new, simple and efficient semidry FGD process for industrial application in the future.

  1. Sulfite oxidation catalyzed by cobalt ions in flue gas desulfurization processes.

    PubMed

    Karatza, Despina; Prisciandaro, Marina; Lancia, Amedeo; Musmarra, Dino

    2010-06-01

    This paper presents an experimental study of calcium bisulfite oxidation, a key step in the wet limestone-gypsum flue gas desulfurization (FGD) process, in the presence of catalysts (e.g., cobalt ions and a mixture of ferrous and cobalt ions). A fundamental approach is followed, by reproducing a simplified synthetic FGD liquor in which both catalyst ions, alone or mixed together, are present. A laboratory-scale apparatus is used, in which sulfurous solution is contacted with a gas phase at a fixed oxygen partial pressure (21.3 kPa) and at different temperature levels (25, 45, and 55 degrees C). The experimental results are analyzed using the theory of gas-liquid mass transfer with chemical reaction, showing that the slow reaction regime is explored and the transition from the kinetic to the diffusional subregime is identified. The experimental results are compared with those obtained in the presence of other catalytic species (manganese and ferrous ions), showing that cobalt is effective in catalyzing the oxidation of calcium bisulfite to sulfate, but to a minor extent with respect to iron and manganese.

  2. Investigation of a mercury speciation technique for flue gas desulfurization materials.

    PubMed

    Lee, Joo-Youp; Cho, Kyungmin; Cheng, Lei; Keener, Tim C; Jegadeesan, Gautham; Al-Abed, Souhail R

    2009-08-01

    Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl2), mercurous chloride (Hg2Cl2), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO4) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg2Cl2 and HgCl2 could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.

  3. Investigation on mercury reemission from limestone-gypsum wet flue gas desulfurization slurry.

    PubMed

    Chen, Chuanmin; Liu, Songtao; Gao, Yang; Liu, Yongchao

    2014-01-01

    Secondary atmospheric pollutions may result from wet flue gas desulfurization (WFGD) systems caused by the reduction of Hg(2+) to Hg(0) and lead to a damping of the cobenefit mercury removal efficiency by WFGD systems. The experiment on Hg(0) reemission from limestone-gypsum WFGD slurry was carried out by changing the operating conditions such as the pH, temperature, Cl(-) concentrations, and oxygen concentrations. The partitioning behavior of mercury in the solid and liquid byproducts was also discussed. The experimental results indicated that the Hg(0) reemission rate from WFGD slurry increased as the operational temperatures and pH values increased. The Hg(0) reemission rates decreased as the O2 concentration of flue gas and Cl(-) concentration of WFGD slurry increased. The concentrations of O2 in flue gas have an evident effect on the mercury retention in the solid byproducts. The temperature and Cl(-) concentration have a slight effect on the mercury partitioning in the byproducts. No evident relation was found between mercury retention in the solid byproducts and the pH. The present findings could be valuable for industrial application of characterizing and optimizing mercury control in wet FGD systems.

  4. Investigation on Mercury Reemission from Limestone-Gypsum Wet Flue Gas Desulfurization Slurry

    PubMed Central

    Liu, Songtao; Liu, Yongchao

    2014-01-01

    Secondary atmospheric pollutions may result from wet flue gas desulfurization (WFGD) systems caused by the reduction of Hg2+ to Hg0 and lead to a damping of the cobenefit mercury removal efficiency by WFGD systems. The experiment on Hg0 reemission from limestone-gypsum WFGD slurry was carried out by changing the operating conditions such as the pH, temperature, Cl− concentrations, and oxygen concentrations. The partitioning behavior of mercury in the solid and liquid byproducts was also discussed. The experimental results indicated that the Hg0 reemission rate from WFGD slurry increased as the operational temperatures and pH values increased. The Hg0 reemission rates decreased as the O2 concentration of flue gas and Cl− concentration of WFGD slurry increased. The concentrations of O2 in flue gas have an evident effect on the mercury retention in the solid byproducts. The temperature and Cl− concentration have a slight effect on the mercury partitioning in the byproducts. No evident relation was found between mercury retention in the solid byproducts and the pH. The present findings could be valuable for industrial application of characterizing and optimizing mercury control in wet FGD systems. PMID:24737981

  5. Investigation of a mercury speciation technique for flue gas desulfurization materials

    SciTech Connect

    Lee, J.Y.; Cho K.; Cheng L.; Keener, T.C.; Jegadeesan G.; Al-Abed, S.R.

    2009-08-15

    Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method and samples from power plants in Pennsylvania. Potential candidates of pure mercury standards including mercuric chloride, mercurous chloride, mercury oxide, mercury sulfide, and mercuric sulfate were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg{sub 2}Cl{sub 2} and HgCl{sub 2} could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury. 21 refs., 5 figs., 3 tabs.

  6. Development of economical compact type wet-limestone flue gas desulfurization (FGD) process

    SciTech Connect

    Kuroda, Hiroshi; Nozawa, Shigeru; Kaku, Hiroyuki

    1995-06-01

    In the last quarter of this century Environmental Protection has become a major global issue. For the removal of SO{sub 2} emitted from thermal power plants, the wet limestone-gypsum process has widely been adopted. However, a more noteworthly economical method has been desired for its spreading. Under these circumstances, Babcock-Hitachi has developed a new compact type Flue Gas Desulfurization (FGD) system by improving the conventional type wet limestone-gypsum process incorporating its advantages. The compact absorber was realized by increasing its gas velocity and the flue gas duct has been minimized by adopting a horizontal flow spray tower instead of a vertical flow spray tower which is commonly adopted in the conventional type. Through this a considerable reduction in construction costs have been achieved. The design study of this compact type FGD plant shows that it can be applied not only new plants but also existing power plants, Features of this compact type FGD, pilot plant test results and examples of the design study are introduced in this paper.

  7. Experiences concerning the service life of rubber linings applied in flue gas desulfurization plants

    SciTech Connect

    Berger, W.

    1999-11-01

    Since the beginning of the eighties scrubbers and other components in European FGD plants have been protected against corrosion using rubber lining. Extensive experience is available based on service lives of rubber lining of more than 15 years. The paper will consider the various rubber types and curing systems used. While the USA and Japan had already begun retrofitting their existing coal-fired power stations with flue gas desulfurization (FGD) plants in the seventies, Germany followed suit in the eighties as a result of the decree issued for large-scale firing plants. Concurrent with this development retrofitting has also been enhanced in other European countries like Austria and the Netherlands, later followed by Denmark, Finland and England. After the collapse of the Eastern Bloc retrofitting work has been implemented in Eastern Germany, Poland, the Czech Republic and Slovakia. Today FGD plants are being put into operation in Spain, Italy, Turkey and Greece or are on the verge of being put into service. More than 150 plants of this kind are operated by using the wet-scrubbing process with limestone or calcium hydroxide suspensions.

  8. Preparation of manganese dioxide loaded activated carbon adsorbents and their desulfurization performance

    NASA Astrophysics Data System (ADS)

    Zhang, Jiaojing; Wang, Guojian; Wang, Wenyi; Song, Hua; Wang, Lu

    2016-12-01

    Manganese dioxide loaded activated carbon adsorbents (MnO2/AC) were prepared and characterized by N2 adsorption-desorption, BET method, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometry (FT-IR) and scanning electron microscopy (SEM). Effects of preparation conditions and adsorption conditions on desulfurization performance of the adsorbents were studied in a fixed-bed adsorption apparatus. Experimental results show that the surface area and pore volume of MnO2/AC decreased compared with the unmodified activated carbon, but the adsorption capacity to H2S was improved greatly. A suitable H2S removal activity was obtained with manganese dioxide to activated carbon ratio of 1.1: 1 and the calcination temperature of 250°C. At the adsorption temperature of 40°C and gas flow rate of 20 mL/min, the H2S saturation capacity and H2S removal rate reached up to 713.25 mg/g and 89.9%, respectively.

  9. Iron blast furnace slag/hydrated lime sorbents for flue gas desulfurization.

    PubMed

    Liu, Chiung-Fang; Shih, Shin-Min

    2004-08-15

    Sorbents prepared from iron blast furnace slag (BFS) and hydrated lime (HL) through the hydration process have been studied with the aim to evaluate their reactivities toward SO2 under the conditions prevailing in dry or semidry flue gas desulfurization processes. The BFS/HL sorbents, having large surface areas and pore volumes due to the formation of products of hydration, were highly reactive toward SO2, as compared with hydrated lime alone (0.24 in Ca utilization). The sorbent reactivity increased as the slurrying temperature and time increased and as the particle size of BFS decreased; the effects of the liquid/solid ratio and the sorbent drying conditions were negligible. The structural properties and the reactivity of sorbent were markedly affected by the BFS/HL ratio; the sorbent with 30/70 ratio had the highest 1 h utilization of Ca, 0.70, and SO2 capture, 0.45 g SO2/g sorbent. The reactivity of a sorbent was related to its initial specific surface area (Sg0) and molar content of Ca (M(-1)); the 1 h utilization of Ca increased almost linearly with increasing Sg0/M. The results of this study are useful to the preparation of BFS/HL sorbents with high reactivity for use in the dry and semidry processes to remove SO2 from the flue gas.

  10. Effects of salts on limestone dissolution rate in wet limestone flue gas desulfurization

    SciTech Connect

    Ukawa, Naohiko; Takashina, Toru; Oshima, Michio; Oishi, Tsuyoshi )

    1993-11-01

    To understand how the dissolution rate of limestone used for absorbent in a wet flue gas desulfurization plant is affected by the soluble salts formed from hydrogen chloride gas in flue gas as well as from the impurities contained in the used raw material limestone itself, various limestone slurries each supplemented with a single salt of CaCl[sub 2], MgCl[sub 2], NaCl, Na[sub 2]SO[sub 4] and MgSO[sub 4] were titrated with sulfuric acid. From the titration results the dissolution rate was found to vary greatly with the kind and the concentration of the salts with a general tendency to decrease in chloride solution but to increase in sulfate solutions. Based on this finding, the authors proposed a semi-empirical simplified model. The evaluated results using this model closely agreed with the measured values of the limestone dissolution rate both in single-salt solutions and mixed salt solutions. 9 refs., 8 figs., 1 tab.

  11. Flue gas desulfurization by-products additions to acid soil: alfalfa productivity and environmental quality.

    PubMed

    Chen, L; Dick, W A; Nelson, S

    2001-01-01

    Flue gas desulfurization (FGD) by-products are created when coal is burned and SO2 is removed from the flue gases. These FGD by-products are often alkaline and contain many plant nutrients. Land application of FGD by-products is encouraged but little information is available related to plant responses and environmental impacts concerning such use. Agricultural lime (ag-lime) and several new types of FGD by-products which contain either vermiculite or perlite were applied at 0, 0.5, 1.0, and 2.0 times the soil's lime requirement (LR) rate to an acidic soil (Wooster silt loam). The highest FGD by-products application rate was equivalent to 75.2 Mg ha(-1). Growth of alfalfa (Medicago sativa L.) was significantly increased compared to the untreated control in the second year after treatment with yields for the 1 x LR rate of FGD approximately 7-8 times greater compared to the untreated control and 30% greater than for the commercial ag-lime. Concentrations of Mo in alfalfa were significantly increased by FGD by-products application, compared to the untreated control, while compared to the ag-lime treatment, concentrations of B increased and Ba decreased. No soil contamination problems were observed, even at the 2xLR rate, indicating these materials can be safely applied to agricultural soils.

  12. Adsorptive desulfurization with metal-organic frameworks: A density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Chen, Zhiping; Ling, Lixia; Wang, Baojun; Fan, Huiling; Shangguan, Ju; Mi, Jie

    2016-11-01

    The contribution of each fragment of metal-organic frameworks (MOFs) to the adsorption of sulfur compounds were investigated using density functional theory (DFT). The involved sulfur compounds are dimethyl sulfide (CH3SCH3), ethyl mercaptan (CH3CH2SH) and hydrogen sulfide (H2S). MOFs with different organic ligands (NH2-BDC, BDC and NDC), metal centers structures (M, M-M and M3O) and metal ions (Zn, Cu and Fe) were used to study their effects on sulfur species adsorption. The results revealed that, MOFs with coordinatively unsaturated sites (CUS) have the strongest binding strength with sulfur compounds, MOFs with NH2-BDC substituent group ligand comes second, followed by that with saturated metal center, and the organic ligands without substituent group has the weakest adsorption strength. Moreover, it was also found that, among different metal ions (Fe, Zn and Cu), MOFs with unsaturated Fe has the strongest adsorption strength for sulfur compounds. These results are consistent with our previous experimental observations, and therefore provide insights on the better design of MOFs for desulfurization application.

  13. Hot coal gas desulfurization with manganese based sorbents. Quarterly report, June--September 1994

    SciTech Connect

    Hepworth, M.T.; Slimane, R.B.

    1994-11-01

    The focus of work being performed on hot coal gas desulfurization at the Morgantown Energy Technology Center is primarily in the use of zinc titanate sorbents; however, prior studies indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt% ore + 25 wt% Al{sub 2}O{sub 3}) appears to be a strong contender to zinc-based sorbents. Manganese, for example, has a lower vapor pressure in the elemental state than zinc; hence, it is not as likely to undergo zinc-depletion from the sorbent surface upon loading and regeneration cycles. Also manganese oxide is less readily reduced to the elemental state than iron; hence, the range of reduction potentials for oxygen is somewhat greater than for zinc ferrite. In addition, thermodynamic analysis of the manganese-oxygen-sulfur system shows it to be less amenable to sulfation than zinc ferrite. Also manganese chlorides are much less stable and volatile than zinc chlorides. Potential also exists for utilization of manganese at higher temperatures than zinc ferrite or zinc titanate. This Eighth Quarterly Report documents progress in pelletizing and testing via thermo-gravimetric analysis of individual pellet formulations of manganese ore/alumina combinations and also manganese carbonate/alumina with two binders, dextrin and bentonite.

  14. Adsorptive Desulfurization of Model Gasoline by Using Different Zn Sources Exchanged NaY Zeolites.

    PubMed

    Rui, Jingwei; Liu, Fei; Wang, Rijie; Lu, Yanfei; Yang, Xiaoxia

    2017-02-17

    A series of Zn-modified NaY zeolites were prepared by the liquid-phase ion-exchange method with different Zn sources, including Zn(NO₃)₂, Zn(Ac)₂ and ZnSO₄. The samples were tested as adsorbents for removing an organic sulfur compound from a model gasoline fuel containing 1000 ppmw sulfur. Zn(Ac)₂-Y exhibited the best performance for the desulfurization of gasoline at ambient conditions. Combined with the adsorbents' characterization results, the higher adsorption capacity of Zn(Ac)₂-Y is associated with a higher ion-exchange degree. Further, the results demonstrated that the addition of 5 wt % toluene or 1-hexene to the diluted thiophene (TP) solution in cyclohexane caused a large decrease in the removal of TP from the model gasoline fuel. This provides evidence about the competition through the π-complexation between TP and toluene for adsorption on the active sites. The acid-catalyzed alkylation by 1-hexene of TP and the generated complex mixture of bulky alkylthiophenes would adsorb on the surface active sites of the adsorbent and block the pores. The regenerated Zn(Ac)₂-Y adsorbent afforded 84.42% and 66.10% of the initial adsorption capacity after the first two regeneration cycles.

  15. Landfill disposal of limestone dual-alkali flue-gas-desulfurization waste. Final report

    SciTech Connect

    Fox, L.K.; Gibson, E.D.; Pierson, J.F.; Brown, D.M.

    1982-09-01

    A landfill disposal test program was undertaken to demonstrate the addition of fly ash and lime to calcium sulfite-sulfate flue gas desulfurization (FGD) wastes and to establish design and operating guidelines for an environmentally acceptable waste disposal system. A lined, diked landfill disposal site was partially filled with waste mixtures of FGD filter cake, fly ash, and lime. Field samples were assessed in terms of engineering properties and leachate quality. Laboratory mixtures were analyzed for comparison with field samples. Revegetation studies were performed with laboratory mixtures to determine how fly ash and FGD sludge affect plant growth and to identify candidate species for on-site testing. Fixation and stabilization improved the shear strength and reduced the compressibility of the laboratory mixtures tested. Laboratory testing of the properties of fixed filter cake indicated that mixtures of filter cake with a solids content of 56%, a fly ash-to-filter cake ratio of 1:1, and a lime content of 3% have a natural water content below the liquid limit and appear to be suitable for landfill. Lime fixation also reduced steady-state leachate concentrations of major constituents (total solids, sulfate, and calcium) and may help to minimize trace metal concentrations. Grasses were identified as the preferred species for vegetating landfills.

  16. Reclamation of acid, toxic coal spoils using wet flue gas desulfurization by-product, fly ash and sewage sludge. Final report

    SciTech Connect

    Kost, D.A.; Vimmerstedt, J.P.; Stehouwer, R.C.

    1997-03-01

    Establishment of vegetation on acid abandoned minelands requires modification of soil physical and chemical conditions. Covering the acid minesoil with topsoil or borrow soil is a common practice but this method may be restricted by availability of borrow soil and cause damage to the borrow site. An alternative approach is to use waste materials as soil amendments. There is a long history of using sewage sludge and fly ash as amendments for acid minesoils. Flue gas desulfurization (FGD) by-products are newer materials that are also promising amendments. Most flue gas sludges are mixtures of Calcium sulfate (CaSO{sub 4}), calcium sulfite (CaSO{sub 3}), calcium carbonate (CaCO{sub 3}), calcium hydroxide [Ca(OH){sub 2}], and fly ash. Some scrubbing processes produce almost pure gypsum (CaSO{sub 4}2H{sub 2}O). The primary purpose of the project is to evaluate two wet FGD by-products for effects on vegetation establishment and surface and ground water quality on an acid minesoil. One by-product from the Conesville, OH power plant (American Electric Power Service Corporation) contains primarily calcium sulfite and fly ash. The other by-product (Mg-gypsum FGD) from an experimental scrubber at the Zimmer power plant (Cincinnati Gas and Electric Company) is primarily gypsum with 4% magnesium hydroxide. These materials were compared with borrow soil and sewage sludge as minesoil amendments. Combinations of each FGD sludge with sewage sludge were also tested. This report summarizes two years of measurements of chemical composition of runoff water, ground water at two depths in the subsoil, soil chemical properties, elemental composition and yield of herbaceous ground cover, and elemental composition, survival and height of trees planted on plots treated with the various amendments. The borrow soil is the control for comparison with the other treatments.

  17. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Volume 2, Single particle kinetic studies of sulfidation and regeneration reactions of candidate zinc ferrite sorbents

    SciTech Connect

    Silaban, A.; Harrison, D.P.

    1989-05-02

    AMAX Research & Development Center (AMAX R&D) has been investigating methods for enhancing the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hot coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. For the present program, the reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point and at saturation in a bench-scale, fixed-bed reactor. Durability may be defined as the ability of the sorbent to maintain important physical characteristics such as size, strength, and specific surface area during 10 cycles of sulfidation and oxidation.

  18. Effects of surface acidities of MCM-41 modified with MoO3 on adsorptive desulfurization of gasoline

    NASA Astrophysics Data System (ADS)

    Shao, Xinchao; Zhang, Xiaotong; Yu, Wenguang; Wu, Yuye; Qin, Yucai; Sun, Zhaolin; Song, Lijuan

    2012-12-01

    A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N2 adsorption-desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO3 can be highly dispersed up to 0.2 g g-1 in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO3 contents of 0.26 and 0.32 g g-1 with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO3 particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO3 species is related to the abundant surface hydroxy of MCM-41. The host species and guest species undergo solid-state reaction to form Sisbnd Osbnd Mo bonds in the mixtures which enhance both the Lewis acid and Brönsted acid of the samples. It has been concluded that the surface acidities of the sorbents contributes to the desulfurization performance which has also been investigated in this study. The octahedral coordinated species (Mo7O246-) are the adsorptive active species for desulfurization compared with the tetrahedral coordinated ones (MoO42-).

  19. Pilot testing of sodium thiosulfate for oxidation/scaling inhibition in lime/limestone flue gas desulfurization systems

    SciTech Connect

    Chang, J.C.S.; Brna, T.G.

    1985-01-01

    Pilot plant tests have been conducted to evaluate sodium thiosulfate as an oxidation inhibition additive in five lime/limestone slurry flue gas desulfurization processes. It was found that the oxidation rate of absorbed sulfur dioxide (SO/sub 2/) was reduced by more than 50 percent in the presence of 100 to 200 ppm of thiosulfate ion in the scrubbing slurry. Calcium sulfate dihydrate (gypsum) scaling was eliminated and the unsaturated (with respect to gypsum) operation mode was maintained by the addition of sodium thiosulfate. Other benefits of sodium thiosulfate addition observed at the pilot plant included improvement in solids dewatering properties for limestone processes.

  20. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, James A.

    1997-01-01

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.