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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

    SciTech Connect

    Monticello, D.J. )

    1994-02-01

    Biocatalytic desulfurization (BDS) has many advantages compared to traditional refinery desulfurization processes, including: lower capital and operating costs, low-temperature and low-pressure operation and no hydrogen requirement. Biotechnology has developed from an art into a science in recent years. The HPI is familiar with an artful' application of biotechnology in the biotreatment of refinery wastes, and has experimented with other technologies for over 50 years. This paper discusses the following: biorefining, sulfur management, conventional solutions, bioprocessing precedents, new biotechnology tools, microbial desulfurization, biocatalytic desulfurization, specificity, biodesulfurization conceptual design, development issues, and implementation.

  5. 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.

  6. 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.

  7. Philippine refiner completes diesel desulfurization project

    SciTech Connect

    Candido, S.S.; Crisostomo, E.V.

    1997-01-27

    In anticipation of tightening sulfur specifications on diesel fuel, Petron Corp. built a new 18,000 b/sd gas oil desulfurization unit (GODU) at its refinery in Bataan, Philippines. The GODU gives Petron sufficient diesel oil desulfurization capacity to meet demand for lower-sulfur diesel in the country. The project places the refinery in a pacesetter position to comply with the Philippine government`s moves to reduce air pollution, especially in urban centers, by reducing the sulfur specification for diesel to 0.5 wt% in 1996 from 0.7 wt% at the start of the project. Performance tests and initial operations of the unit have revealed a desulfurization efficiency of 91% vs. a guaranteed efficiency of 90%. A feed sulfur content of 1.33 wt% is reduced to 0.12 wt% at normal operating conditions. Operating difficulties during start-up were minimized through use of a detailed prestartup check conducted during the early stages of construction work.

  8. 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.

  9. Enzymes desulfurizing diesel fuel in pilot plant tests

    SciTech Connect

    Rhodes, A.K.

    1995-05-15

    Energy BioSystems Corp., The Woodlands, Texas, is collecting data from a new 5 b/d, continuous-operation, biocatalytic desulfurization (BDS) pilot plant. Hurdles to commercialization are catalyst activity, stability, and fermentation yield. Since 1990, however, Energy BioSystems Corp. (EBC) has made great strides in improving all three of these factors. The BDS process uses enzymes to remove organically bound sulfur from petroleum streams at mild temperatures and atmospheric pressure. Objectives of the pilot plant studies include: validating and refining the computer simulations used to control the process and establishing the process design basis. So far, the results from pilot plant operations have met expectations. The projected 45% desulfurization rate has been achieved, within a few percent. This rate was simply the target for the initial evaluation experiments, and that the process is capable of desulfurizing almost to extinction.

  10. 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.

  11. 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.

  12. 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.

  13. Monticello Unit 3 recovery project: The rebuild of a first generation wet flue gas desulfurization system

    SciTech Connect

    Guletsky, P.W.; Katzberger, S.M.; Jeanes, R.L.

    1995-06-01

    Since November 1993, TU Electric and Sargent & Lundy have been engaged in the repair or replacement of equipment that was damaged by the collapse of the Monticello Unit 3 chimney. In addition to the replacement of the chimney, electrostatic precipitator, and various balance-of-plant systems, the scope of the project includes the demolition, engineering and design, procurement, and construction activities to rebuild major equipment within the wet limestone flue gas desulfurization (FGD) system. This paper reviews and discusses various aspects of the design, procurement and schedule associated with the rebuild of the FGD system. The paper reviews the design selections in the areas of process technology, the absorber island, and technical enhancements to improve the operability of this 1970s-vintage system. Finally, the challenges and solutions in implementing a 17-month schedule for the design, construction, and startup of an FGD system will be discussed.

  14. 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.

  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. PMID:26812494

  16. 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.

  17. New regents for coal desulfurization

    SciTech Connect

    Buchanan, D.H.; Kalembasa, S.; Olson, D.; Wang, S.; Warfel, L.

    1991-01-01

    The primary goal of this project was development and exploration of potential new desulfurization reagents for the removal of organic sulfur'' from Illinois coals by mild chemical methods. Potential new desulfurization reagents were investigated using organic sulfur compounds of the types thought to be present in coals. Reagents included low-valent metal complexes based on nickel and on iron as well as possible Single Electron Transfer reagents. Soluble coal extracts served as second generation model compounds during this reagent development project.

  18. 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.

  19. 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.

  20. Biological desulfurization (BDS) of middle distillates

    SciTech Connect

    Monticello, D.J. )

    1993-01-01

    As implementation of the Clean Air Act Amendment draws near, sulfur management will play a key role for the refining industry. Industry experts have estimated that the petroleum industry will spend billions of dollars to conform to the Clean Air Act and desulfurization capacity will account for a significant portion of those expenditures. The need to limit the sulfur content of finished products is not new, but this dramatic increase in expenditures is the result of the increasingly stringent environmental regulations in the US, Europe and the Far East. These regulations will be implemented over the next ten years and will have serious implications for the refining industry. The purpose of this paper is to describe an alternative approach to desulfurization based on the recent advances in biotechnology and to outline the progress which has been made in recent years in this area. Biocatalytic Desulfurization (BDS) is not a commercial technology, but conceptual engineering and sensitivity analyses have shown that the approach has great promise. Several Government, University and Industrial groups are working now to develop the technology. The recent advances which have resulted from the application of the new tools of biotechnology to the problem have accelerated the development effort, and the first commercial BDS units may be available in 1996.

  1. 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.

  2. 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.

  3. LIFAC Sorbent Injection Desulfurization Demonstration Project. Quarterly report number 14, January--March, 1994

    SciTech Connect

    Not Available

    1994-11-01

    The host site for the $22 million, three-phase project is Richmond Power and Light`s Whitewater Valley Unit No. 2 in Richmond, Indiana. The LIFAC technology uses upper-furnace limestone injection with patented humidification of the flue gas to remove 75--85% of the sulfur dioxide (SO{sub 2}) in the flue gas. During this report period (January--March 1994), long-term testing was initiated. The variable frequency drive was placed back in service, but failed again after only a few days of operation. The Unit No. 2 induced draft (ID) fan motor operates at maximum amperage during peak (65 MW) boiler load. LIFAC increases system pressure drop approximately 4.5 inches of water, causing additional loading on the fan motor. A variable frequency drive (VFD) was installed as a major component of the LIFAC system. The VFD interfaces with the ID fan motor by varying motor current as the pressure drop and flue gas volume change, making the fan more efficient and decreasing the stress on the motor. The VFD has failed several times causing boiler Unit No. 2 to trip. Since the VFD has become unreliable, the LIFAC team decided to perform a test on the ID fan motor with the bypass damper fully closed and the VFD disengaged. The objective of long-term testing is to evaluate the performance and operability of the LIFAC process over a long, continuous operation period. There were a total of two test periods during this quarter. Results are presented.

  4. Improving Enzyme Activity and Broadening Selectivity for Biological Desulfurization and Upgrading of Petroleum Feedstocks

    SciTech Connect

    Abhijeet P. Borole; Choo Y. Hamilton; Karen Miller; Brian Davison; Matthew Grossman; Robert Shong

    2003-05-12

    The objective of this project was to develop improved biocatalysts for desulfurization and upgrading of petroleum feedstocks. The goal was to improve the activity and broaden the selectivity of desulfurization enzymes using directed evolution as a tool as well as to explore the impact of ring-opening on biological desulfurization

  5. 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.

  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. 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.

  8. 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.

  9. Passerini Reactions on Biocatalytically Derived Chiral Azetidines.

    PubMed

    Moni, Lisa; Banfi, Luca; Basso, Andrea; Bozzano, Andrea; Spallarossa, Martina; Wessjohann, Ludger; Riva, Renata

    2016-01-01

    The purpose of this study was to explore a series of Passerini reactions on a biocatalytically derived enantiopure azetidine-2-carboxyaldehyde in order to obtain, in a diastereoselective manner, polyfunctionalised derivatives having the potential to be cyclized to chiral bridged bicyclic nitrogen heterocycles. While diastereoselectivity was poor under classical Passerini conditions, a significant increase of diastereoselectivity (up to 76:24) was gained by the use of zinc bromide as promoter. The methodology has a broad scope and yields are always good. PMID:27589709

  10. Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures.

    PubMed

    Pappas, Charalampos G; Sasselli, Ivan R; Ulijn, Rein V

    2015-07-01

    Structural adaption in living systems is achieved by competing catalytic pathways that drive assembly and disassembly of molecular components under the influence of chemical fuels. We report on a simple mimic of such a system that displays transient, sequence-dependent formation of supramolecular nanostructures based on biocatalytic formation and hydrolysis of self-assembling tripeptides. The systems are catalyzed by α-chymotrypsin and driven by hydrolysis of dipeptide aspartyl-phenylalanine-methyl ester (the sweetener aspartame, DF-OMe). We observed switch-like pathway selection, with the kinetics and consequent lifetime of transient nanostructures controlled by the peptide sequence. In direct competition, kinetic (rather than thermodynamic) component selection is observed.

  11. For fuel desulfurization: Invite a bioengineered bug to dinner

    SciTech Connect

    Shelley, S.

    1995-05-01

    Last March, Energy BioSystems Corp. (EBC; The Woodlands, Tex.) brought online the world`s first biocatalytic desulfurization (BDS) facility. The $1.5-million pilot plant, located at the St. Louis, MO, research and development facility of Petrolite Corp., is designed to process up to 5 bbl/d to high-sulfur diesel fuel. EBC has partnered with Paris-based Total Raffinage S.A., France`s largest refiner, which is supplying the largest refiner, which is supplying the target diesel. The initial pilot plant was designed to desulfurize middle distillates, because of existing US and European regulations that target sulfur in this petroleum fraction. The firm hopes to have a 10,000-bbl/d commercial unit under construction by 1996. Meanwhile, EBC has partnered with Koch Refining (Wichita, KS) to adapt the process for gasoline, and with Texaco, Inc.`s Exploration and Production Division (Houston, TX) to sweeten sour crude before it reaches the refinery.

  12. 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)

  13. Enzymatic desulfurization of coal

    SciTech Connect

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

    1988-10-07

    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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures.

    PubMed

    Pappas, Charalampos G; Sasselli, Ivan R; Ulijn, Rein V

    2015-07-01

    Structural adaption in living systems is achieved by competing catalytic pathways that drive assembly and disassembly of molecular components under the influence of chemical fuels. We report on a simple mimic of such a system that displays transient, sequence-dependent formation of supramolecular nanostructures based on biocatalytic formation and hydrolysis of self-assembling tripeptides. The systems are catalyzed by α-chymotrypsin and driven by hydrolysis of dipeptide aspartyl-phenylalanine-methyl ester (the sweetener aspartame, DF-OMe). We observed switch-like pathway selection, with the kinetics and consequent lifetime of transient nanostructures controlled by the peptide sequence. In direct competition, kinetic (rather than thermodynamic) component selection is observed. PMID:26014441

  19. 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.

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

    PubMed

    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

  2. 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.

  3. 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.

  4. New reagents for coal desulfurization. Final technical report, September 1, 1990--August 31, 1991

    SciTech Connect

    Buchanan, D.H.; Kalembasa, S.; Olson, D.; Wang, S.; Warfel, L.

    1991-12-31

    The primary goal of this project was development and exploration of potential new desulfurization reagents for the removal of ``organic sulfur`` from Illinois coals by mild chemical methods. Potential new desulfurization reagents were investigated using organic sulfur compounds of the types thought to be present in coals. Reagents included low-valent metal complexes based on nickel and on iron as well as possible Single Electron Transfer reagents. Soluble coal extracts served as second generation model compounds during this reagent development project.

  5. 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.

  6. 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.

  7. Biocatalytic Refining of Soybean Oil into Cosmeceutical Ingredients

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Our mission is to develop new, value-added uses for commodity crops and oils. We chose to fulfill this mission while adhering as closely as possible to the tenants of “green” chemistry. We have developed patented, all-natural oils called Feruloyl Soy Glycerols (FSG) from the biocatalytic transester...

  8. Desulfurization apparatus and method

    DOEpatents

    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.

  9. 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.

  10. 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.

  11. 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.

  12. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1987-10-27

    AMAX Research Development Center (AMAX R D) has been investigating methods for improving the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hog coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. The reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point in a bench-scale fixed-bed reactor. The durability may be defined as the ability of the sorbent to maintain its reactivity and other important physical characteristics such as size, strength, and specific surface area during 10 cycles of sulfidation and regeneration. Two base case sorbents, spherical pellets and cylindrical extrudes used in related METC sponsored projects, are being used to provide a basis for the comparison of physical characteristics and chemical reactivity.

  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. Rapid biocatalytic polytransesterification: Reaction kinetics in an exothermic reaction

    SciTech Connect

    Chaudhary, A.K.; Beckman, E.J.; Russell, A.J.

    1998-08-20

    Biocatalytic polytransesterification at high concentrations of monomers proceeds rapidly and is accompanied by an increase in the temperature of the reaction mixture due to liberation of heat of reaction during the initial phase. The authors have used principles of reaction calorimetry to monitor the kinetics of polymerization during this initial phase, thus relating the temperature to the extent of polymerization. Rate of polymerization increases with the concentration of monomers. This is also reflected by the increase in the temperature of the reaction mixture. Using time-temperature-conversion contours, a differential method of kinetic analysis was used to calculate the energy of activation ({approximately} 15.1 Kcal/mol).

  17. 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.

  18. Biochemical and biocatalytic characterization of 17 novel halohydrin dehalogenases.

    PubMed

    Koopmeiners, Julia; Halmschlag, Birthe; Schallmey, Marcus; Schallmey, Anett

    2016-09-01

    Halohydrin dehalogenases are rare but catalytically remarkable enzymes since they are able to form novel C-C, C-O, C-N, or C-S bonds. Very recently, a motif-based sequence database mining approach resulted in the identification of 37 novel halohydrin dehalogenase enzymes, many of them exhibiting only low sequence similarity to previously known halohydrin dehalogenases. In an attempt to explore the biocatalytic potential of these newly identified enzymes, 17 representatives from all six phylogenetic subtypes were heterologously produced in Escherichia coli, purified and characterized to determine their substrate scopes in the dehalogenation and epoxide ring-opening reaction. Several enzymes with broad substrate spectra were identified exhibiting high activities towards a selection of typical substrates. Moreover, four halohydrin dehalogenases were found to be significantly more thermostable than the previously known HheC from Agrobacterium radiobacter AD1. Investigation of the enzymes' stereoselectivity in the dehalogenation of racemic 2-chloro-1-phenylethanol revealed that their stereopreference correlates with the phylogenetic placing of the enzymes in subtypes A through G. Furthermore, the biocatalytic potential of these novel halohydrin dehalogenases was investigated in the preparation of ethyl 4-cyano-3-hydroxybutyrate, a statin side-chain precursor. Though none of the active enzymes selectively formed the required (R)-enantiomer, several halohydrin dehalogenases were identified with significantly higher activity in the conversion compared to HheC, making them promising candidates for this industrially relevant reaction. PMID:27052376

  19. Enzyme-polymer composites with high biocatalytic activity and stability

    SciTech Connect

    Kim, Jungbae; Kosto, Timothy J.; Manimala, Joseph C.; Nauman, E B.; Dordick, Jonathan S.

    2004-08-22

    We have applied vacuum-spraying and electrospinning to incorporate an enzyme into a polymer matrix, creating a novel and highly active biocatalytic composite. As a unique technical approach, enzymes were co-dissolved in toluene with polymers, and the solvent was then rapidly removed by injecting the mixture into a vacuum chamber or by electrospinning. Subsequent crosslinking of the enzyme with glutaraldehyde resulted in stable entrapped enzyme within the polymeric matrices. For example, an amorphous composite of alpha-chymotrypsin and polyethylene showed no significant loss of enzymatic activity in aqueous buffer for one month. Nanofibers of alpha-chymotrypsin and polystyrene also showed no decrease in activity for more than two weeks. The normalized activity of amorphous composite in organic solvents was 3-13 times higher than that of native alpha-chymotrypsin. The activity of nanofibers was 5-7 times higher than that of amorphous composite in aqueous buffer solution. The composites of alpha-chymotrypsin and polymers demonstrate the feasibility of obtaining a wide variety of active and stable biocatalytic materials with many combinations of enzymes and polymers.

  20. 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

    2015-06-01

    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. PMID:25721554

  1. 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

    2015-06-01

    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.

  2. 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.

  3. 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.

  4. 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

  5. Microbial desulfurization of natural gas

    SciTech Connect

    Sublette, K.L.; Sylvester, N.D.

    1987-01-01

    It has been demonstrated that the H/sub 2/S content of a gas can be reduced to very low levels by contact with an aerobic or anaerobic culture of Thiobacillus denitrificans if the reactor is operated under sulfide-limiting conditions. Hydrogen sulfide was observed to be an inhibitory substrate; however, upset conditions produced by excess H/sub 2/S feed were readily detected and reversed. Biomass yield is lower under aerobic conditions than anaerobic conditions presumably because of inhibition of growth by oxygen. However, under aerobic conditions the maximum loading of the biomass is 2-3 times higher than that observed for anaerobic conditions. Heterotrophic contamination was shown to have a negligible effect on reactor performance. The use of mixed cultures (T. denitrification and heterotrophs) could simplify a microbial gas desulfurization process by removing the requirement for aseptic operation of the reactor.

  6. 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.

  7. 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.

  8. 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.

  9. Microbial desulfurization of different coals.

    PubMed

    Acharya, C; Kar, R N; Sukla, L B

    2004-01-01

    Coal is the most important nonrenewable energy source of fossil origin. It is also the most common fuel in thermal power plants. However, during coal incineration in power plants, high sulfur content of coal poses serious environmental problems owing to sulfur dioxide emission. We studied the application of microbial methods for removal of sulfur from three types of high sulfur coals-two samples collected from Assam and Rajasthan in India and one from Libiaz, Poland. These coal samples were desulfurized using indigenous Acidithiobacillus sp. After investigation of the effect of various parameters, the conditions optimized for the maximum removal of total sulfur (91.87% for lignite, 63.13% for Polish coal, and only 9.44% for Assam coal) were as follows: initial pH of 1.5 (2.5 in the case of Assam coal), particle size of 45 micro, pulp density of 2% (w/v), incubation period of 30 d at -35 degrees C in presence of 44.2 g/L of ferrous sulfate in the media with shaking at 140 rpm. Poor removal of sulfur in the case of Assam coal was owing to extensive precipitation of jarosites. In addition, the sulfur in Assam coal is mostly found in organic form, which is difficult to remove with Acidithiobacillus sp. The removal of sulfur from the three coal samples was demonstrated with photomicrographic studies. PMID:15304738

  10. Anion-exchange resin-based desulfurization process

    SciTech Connect

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

    1992-01-01

    Under DOE Grant No. FG22-90PC90309, the University of Tennessee Space Institute (UTSI) is contracted to further develop its anion-exchange, resin-based desulfurization concept to desulfurize alkali metal sulfates. From environmental as well as economic viewpoints, it is necessary to remove soluble sulfates from the wastes created by flue gas desulfurization systems. In order to do this economically, a low-cost desulfurization process for spent sorbents is necessary. UTSI's anion-exchange resin-based desulfurization concept is believed to satisfy these requirements.

  11. Coal desulfurization by low-temperature chlorinolysis

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.; Kalvinskas, J. J.; Ganguli, P. S.; Gavalas, G. R.

    1977-01-01

    Among the three principal methods for precombustion desulfurization of coal, which include physical depyriting, chemical desulfurization, and coal conversion to low-sulfur liquid and gaseous fuels, the potential of chemical methods looks promising in terms of both total sulfur removal and processing cost. The principal chemical methods for coal desulfurization involve treatment with either oxidizing agents or basic media at elevated temperature and pressure. A description is given of some recent experimental results which show the feasibility of removing sulfur, particularly organic sulfur, from high-sulfur coals by a simple method of low-temperature chlorinolysis followed by hydrolysis and dechlorination. The chemical feasibility of sulfur removal by chlorinolysis rather than the detailed engineering process is emphasized.

  12. 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

  13. 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

  14. Use of a batch-stirred reactor to rationally tailor biocatalytic polytransesterification

    SciTech Connect

    Kline, B.J.; Lele, S.S.; Lenart, P.J.; Beckman, E.J.; Russell, A.J.

    2000-02-20

    Despite favorable thermodynamics, high-molecular weight and low-dispersity polyesters are difficult to synthesize biocatalytically in organic solvents. The authors have reported previously that the elimination of solvent can improve the kinetics and apparent equilibrium significantly. The authors now present the design and use of a batch-stirred enzyme reactor to control the biocatalytic polymerization. Using the rector, polyester having a molecular weight of 23,400 Da and a polydispersity of 1.69 was synthesized in only 1 h at 60 C. Additional factors like enzyme-deactivation kinetics, enzyme specificity, and initial exothermicity were investigated to develop a better understanding of this complex reaction system.

  15. Catalytic desulfurization of industrial waste gases

    SciTech Connect

    Dupin, Th.

    1985-07-30

    Industrial waste gases containing objectionable/polluting compounds of sulfur, e.g., H/sub 2/S, SO/sub 2/ and such organosulfur 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.

  16. 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.

  17. 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.

  18. 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.

  19. Microbial desulfurization of organic sulfur compounds in petroleum.

    PubMed

    Ohshiro, T; Izumi, Y

    1999-01-01

    Sulfur removal from petroleum is important from the standpoint of the global environment because the combustion of sulfur compounds leads to the production of sulfur oxides, which are the source of acid rain. As the regulations for sulfur in fuels become more stringent, the existing chemical desulfurizations are coming inadequate for the "deeper desulfurization" to produce lower-sulfur fuels without new and innovative processes. Biodesulfurization is rising as one of the candidates. Several microorganisms were found to desulfurize dibenzothiophene (DBT), a representative of the organic sulfur compounds in petroleum, forming a sulfur-free compound, 2-hydroxybiphenyl. They are promising as biocatalysts in the microbial desulfurization of petroleum because without assimilation of the carbon content, they remove only sulfur from the heterocyclic compounds which is refractory to conventional chemical desulfurization. Both enzymological and molecular genetic studies are now in progress for the purpose of obtaining improved desulfurization activity of organisms. The genes involved in the sulfur-specific DBT desulfurization were identified and the corresponding enzymes have been investigated. From the practical point of view, it has been proved that the microbial desulfurization proceeds in the presence of high concentrations of hydrocarbons, and more complicated DBT analogs are also desulfurized by the microorganisms. This review outlines the progress in the studies of the microbial desulfurization from the basic and practical point of view.

  20. Desulfurization of coal: Enhanced selectivity using phase transfer catalysts. Technical report, September 1--November 30, 1995

    SciTech Connect

    Palmer, S.R.; Hippo, E.J.

    1995-12-31

    Due to environmental problems related to the combustion of high sulfur Illinois coal, there continues to be interest in the development of viable pre-combustion desulfurization processes. Recent studies by the authors have obtained very good sulfur removals but the reagents that are used are too expensive. Use of cheaper reagents leads to a loss of desired coal properties. This study investigates the application of phase transfer catalysts to the selective oxidation of sulfur in coal using air and oxygen as oxidants. The phase transfer catalyst is expected to function as a selectivity moderator by permitting the use of milder reaction conditions than otherwise necessary. This would enhance the sulfur selectivity and help retain the heating value of the coal. The use of certain coal combustion wastes for desulfurization, and the application of cerium (IV) catalyzed air oxidations for selective sulfur oxidation are also being studied. If successful this project could lead to the rapid development of a commercially viable desulfurization process. This would significantly improve the marketability of Illinois coal. During this quarter aliquots of the IBC-101 coal have been ground to various particle sizes in an attempt to find the optimum physical pretreatment for mineral, especially pyrite, removal. Analysis of these various aliquots shows them to be representative of the original coal. In addition, preliminary desulfurization reactions using fly ash and scrubber sludges have been performed on an unoxidized IBC-101 sample. Results will be available next quarter. Also, SEM-EDAX analysis of the fly ash indicates that it contains oxides that have shown activity in base desulfurization reactions.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Anion-exchange resin-based desulfurization process. Annual technical progress report, October 1, 1992--September 30, 1993

    SciTech Connect

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

    1993-11-01

    Under the DOE Grant No. DE-FG22-90PC90309, the University of Tennessee Space Institute (UTSI) has been directed to further develop an anion-exchange, resin-based desulfurization concept that has been developed and tested on a limited scope for feasibility. From environmental as well as the economic viewpoints, it is necessary that the soluble sulfates of alkali metal sorbents be desulfurized (regenerated) and recycled to make regenerative flue gas desulfurization and MHD spent seed regeneration options more attractive. In order to achieve this, a low-temperature, low-cost desulfurization process to reactivate spent alkali metal sorbents is necessary. UTSI`s anion-exchange, resin-based concept uses the available technology and is believed to satisfy this requirement. In this DOE-sponsored project, UTSI, will perform the following investigations: Screening of commercially available resins; process variables study and improving resin performance; optimization of resin-regeneration step; evaluation of performance enhancers; development of Best-Process Schematic and related economics, and planning for proof-of-concept (POC) scale testing. The above activities have been grouped into five major tasks and the entire project is expected to take thirty-six months to complete.

  10. 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.

  11. Desulfurization of coal: enhanced selectivity using phase transfer catalysts. Quarterly report, March 1 - May 31, 1996

    SciTech Connect

    Palmer, S.R.; Hippo, E.J.

    1996-12-31

    Due to environmental problems related to the combustion of high sulfur Illinois coal, there continues to be interest in the development in viable pre-combustion desulfurization processes. Recent studies by the authors have obtained very good sulfur removals but the reagents that are used are too expensive. Use of cheaper reagents leads to a loss of desired coal properties. This study investigated the application phase transfer catalysts to the selective oxidation of sulfur in coal using air and oxygen as oxidants. The phase transfer catalyst is expected to function as a selectivity moderator by permitting the use of milder reaction conditions that otherwise necessary. This would enhance the sulfur selectivity and help retain the heating value of the coal. The use of certain coal combustion wastes for desulfurization, and the application of cerium (IV) catalyzed air oxidation for selective sulfur oxidation are also being studied. If successful, this project could lead to the rapid development of a commercially viable desulfurization process. This would significantly improve the marketability of Illinois coal.

  12. 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. PMID:24721252

  13. 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.

  14. Ultrafine pyrite desulfurization by selective flocculation

    SciTech Connect

    Cai, Z.; Liu, H.; Wu, J.; Wang, X.

    1997-12-31

    Selective flocculation is introduced for the separation of ultrafine pyrite from coal. Selective flocculation refers to the process in which high molecule weight polymer reagents bridge the fine particles of one component in a mixture. According to the differences in physico-chemical properties, the reagent can be adsorbed on one component which can be flocculated but not on others which cannot be flocculated. A number of selective flocculation separation tests under different conditions have been performed and the results are very encouraging. The results also show that desulfurization and deashing can be obtained simultaneously in the selective flocculation process.

  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. Ultrasound-promoted chemical desulfurization of Illinois coals

    SciTech Connect

    Chao, S.S.

    1991-01-01

    The overall objectives of the program were to investigate the use of ultrasound to promote coal desulfurization reactions and to evaluate chemical coal desulfurization schemes under mild conditions through a fundamental understanding of their reaction mechanisms and kinetics. The ultimate goal was to develop an economically feasible mild chemical process to reduce the total sulfur content of Illinois Basin Coals, while retaining their original physical characteristics, such as calorific value and volatile matter content. During the program, potential chemical reactions with coal were surveyed under various ultrasonic irradiation conditions for desulfurization, to formulate preliminary reaction pathways, and to select a few of the more promising chemical processes for more extensive study.

  17. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    SciTech Connect

    John G. Verkade

    1998-08-31

    The nonionic superbase P(MeNCH{sub 2}CH{sub 2}){sub 3}N (A) efficiently desulfurizes trisulfides to disulfides and monosulfides, disulfides to monosulfides, and propylene sulfide to propene. S=P(MeNCH{sub 2}CH{sub 2}){sub 3}N (B) was formed as the sulfur acceptor. P(NMe{sub 2}){sub 3} was a much poorer desulfurizing agent than A under the same reaction conditions. Thiocyanates and triphenylphosphine sulfide were also desulfurized with A, but N-(phenylthio)phthalimide formed [A-SP]{sup +} phthalimide in quantitative yield.

  18. 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.

  19. 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.

  20. 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.

  1. The microbial desulfurization of coal.

    PubMed

    Rossi, Giovanni

    2014-01-01

    The chemical structure of coal macerals is usually characterized by the presence of inorganic and organic sulfur. Inorganic sulfur consists mostly of iron sulfides, the so-called "pyritic sulfur," whereas organic sulfur is covalently bound to the carbon atoms of the coal macromolecule. Comminution of coal to sizes that liberate the iron sulfide grains makes their removal with mineral beneficiation processes theoretically possible, but practically profitless. Microbial removal of pyritic sulfur has been extensively investigated over the last 50 years and the very promising results obtained have encouraged the design and construction of a semi-commercial pilot plant in the framework of Project JOULE 0039 funded by the European Commission. The results of the 1-year operation of this plant are reported here, the most significant being the 90 % pyrite removal achieved in five stirred tank bioreactors operating with a 40 % solids suspension and the pyritic iron solubilization rate of 36 mg dm(-3) h(-1). Taking into account the very high price of the kWh in Italy, a rough estimate of the overall costs is in the range from 25 to 30 per tonne of dry coal. So far the development of a microbial process for organic sulfur removal has shown to be much more difficult and less successful, although significant progress in laboratory research is reported. PMID:23576051

  2. 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.

  3. Alkylated benzothiophene desulfurization by Rhodococcus sp. strain T09.

    PubMed

    Matsui, T; Onaka, T; Tanaka, Y; Tezuka, T; Suzuki, M; Kurane, R

    2000-03-01

    A benzothiophene desulfurizing bacterium was isolated and identified as Rhodococcus sp. strain T09. Growth assays revealed that this strain assimilated, as the sole sulfur source, various organosulfur compounds that cannot be assimilated by the well-studied dibenzothiophene-desulfurizing Rhodococcus sp. IGTS8. The cellular growth rate of strain T09 for the alkylated benzothiophenes depended on the alkylated position and the length of the alkyl moiety.

  4. 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.

  5. Demonstration of the carbon-sulfur bond targeted desulfurization of benzothiophene by thermophilic Paenibacillus sp. strain A11-2 capable of desulfurizing dibenzothiophene.

    PubMed

    Konishi, J; Onaka, T; Ishii, Y; Suzuki, M

    2000-06-15

    Paenibacillus sp. strain A11-2, which had been primarily isolated as a bacterial strain capable of desulfurizing dibenzothiophene to produce 2-hydroxybiphenyl at high temperatures, was found to desulfurize benzothiophene more efficiently than dibenzothiophene. The desulfurized product was identified as o-hydroxystyrene by GC-MS and 1H-NMR analysis. Benzothiophene was assumed to be degraded in a way analogous to the 4S pathway, which has been well-known as a mode of dibenzothiophene degradation. These results suggest that benzothiophene desulfurization may share at least partially the reaction mechanism with dibenzothiophene desulfurization.

  6. Dewatering of flue gas desulfurization sulfite solids

    SciTech Connect

    Garrison, F.C.; Wells, W.L.

    1984-06-12

    The dewatering capabilities of sulfite sludges from flue gas desulfurization facilities are substantially improved by the addition of relatively small amounts of sodium thiosulfate additive, or additives derived from or related to sodium thiosulfate, into the scrubber slurry liquor. As an added embellishment, these predetermined amounts of said additives are greater than those required for effecting substantial scale inhibition in the scrubber innards. Subsequently, conventional dewatering of the sulfite sludge to about 80 to 90 percent solids directly produces a waste product disposable in both an economically and an environmentally acceptable manner, in that the thixotropic characteristics of such sludges which are associated therewith upwards to about 70 percent solids therein are completely eliminated.

  7. 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.

  8. 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.

  9. 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.

  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. Recent advances in flue gas desulfurization technologies

    SciTech Connect

    Pan, Y.S.

    1991-01-01

    Recent advances in flue gas desulfurization (FGD) technologies are reported. The technological advances include conventional wet FGD system improvements, advanced wet FGD system development, spray dryer system operations, technologies for furnace sorbent injections, post-combustion dry technologies, combined SO{sub 2}/NO{sub x} technologies, and several emerging FGD technologies. In addition, progress of by-product utilization that affects the operating cost of FGD systems is described. Economics of some commercially available and nearly maturing FGD technologies is also discussed. The materials included in this report are obtained from technical presentations made through September 1990, at several national and international conferences. This report is intended to document current advances and status of various FGD technologies. 101 refs., 16 figs.

  12. Hot coal-gas desulfurization with manganese-based sorbents

    SciTech Connect

    Berns, J.; Hepworth, M.T.; Slimane, R.B.; Gasper-Galvin, L.D.; Fisher, E.P.; Venkataraman, V.K.

    1996-08-01

    Manganese based hot-gas-desulfurization sorbents are under investigation for use in Integrated Gasification Combined Cycle advanced electric-power-generation systems. The objective of this project is to develop a regenerable Mn-based pellet formulation that can achieve low sulfur partial pressures, has a high capacity for sulfur and sufficient strength for potential use in fluidized beds, and can be regenerated for many cycles. Fifteen different formulations of manganese sesquioxide, each with either titania or alumina, were prepared and characterized at the University of Minnesota. Each formulation was indurated under conditions sufficient to achieve 1 lb/pellet/mm of diameter crush strength. Sulfidation screening was performed in a thermogravimetric analyzer at 500 to 900 C. A sorbent containing MnCO{sub 3} and TiO{sub 2}, which showed superior crush strength and reactivity, was selected for multi-cycle fixed-bed testing at the Morgantown Energy Technology Center. Four cycles of sulfidation showed that the sorbent had excellent efficiency and capacity for sulfur removal. Good regenerability was achieved with air-steam at 871 C.

  13. 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.

  14. 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

  15. PRODUCTION OF CONSTRUCTION AGGREGATES FROM FLUE GAS DESULFURIZATION SLUDGE

    SciTech Connect

    1998-12-01

    Through a cooperative agreement with DOE, the Research and Development Department of CONSOL Inc. (CONSOL R and D) is teaming with SynAggs, Inc. and Duquesne Light to design, construct, and operate a 500 lb/h continuous pilot plant to produce road construction aggregate from a mixture of wet flue gas desulfurization (FGD) sludge, fly ash, and other components. The proposed project is divided into six tasks: (1) Project Management; (2) Mix Design Evaluation; (3) Process Design; (4) Construction; (5) Start-Up and Operation; and (6) Reporting. In this quarter, Tasks 1 and 2 were completed. A project management plan (Task 1) was issued to DOE on October 22, 1998 . The mix design evaluation (Task 2) with Duquesne Light Elrama Station FGD sludge and Allegheny Power Hatfields Ferry Station fly ash was completed. Eight semi-continuous bench-scale tests were conducted to examine the effects of mix formulation on aggregate properties. A suitable mix formulation was identified to produce aggregates that meet specifications of the American Association of State High Transport Officials (AASHTO) as Class A aggregate for use in highway construction. The mix formulation was used in designing the flow sheet of the pilot plant. The process design (Task 3) is approximately 80% completed. Equipment was evaluated to comply with design requirements. The design for the curing vessel was completed by an outside engineering firm. All major equipment items for the pilot plant, except the curing vessel, were ordered. Pilot plant construction (Task 4) was begun in October. The Hazardous Substance Plan was issued to DOE. The Allegheny County (PA) Heat Department determined that an air emission permit is not required for operation of the pilot plant.

  16. 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. PMID:24835096

  17. Towards biochemical filters with a sigmoidal response to pH changes: buffered biocatalytic signal transduction

    NASA Astrophysics Data System (ADS)

    Pita, Marcos; Privman, Vladimir; Arugula, Mary A.; Melnikov, Dmitriy; Bocharova, Vera; Katz, Evgeny

    We realize a biochemical filtering process by introducing a buffer in a biocatalytic signal-transduction logic system based on the function of an enzyme, esterase. The input, ethyl butyrate, is converted into butyric acid-the output signal, which in turn is measured by the drop in the pH value. The developed approach offers a versatile "network element" for increasing the complexity of biochemical information processing systems. Evaluation of an optimal regime for quality filtering is accomplished in the framework of a kinetic rate-equation model.

  18. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Quarterly technical progress report 4, July--September 1987

    SciTech Connect

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

    1987-10-27

    AMAX Research & Development Center (AMAX R&D) has been investigating methods for improving the reactivity and durability of the zinc ferrite desulfurization sorbent. Zinc ferrite sorbents are intended for use in desulfurization of hog coal gas in integrated gasification combined cycle (IGCC) or molten carbonate fuel cell (MCFC) applications. The reactivity of the sorbent may be defined as its sulfur sorption capacity at the breakthrough point in a bench-scale fixed-bed reactor. The durability may be defined as the ability of the sorbent to maintain its reactivity and other important physical characteristics such as size, strength, and specific surface area during 10 cycles of sulfidation and regeneration. Two base case sorbents, spherical pellets and cylindrical extrudes used in related METC sponsored projects, are being used to provide a basis for the comparison of physical characteristics and chemical reactivity.

  19. Coated-wall microreactor for continuous biocatalytic transformations using immobilized enzymes.

    PubMed

    Thomsen, Malene S; Nidetzky, Bernd

    2009-01-01

    Microstructured flow reactors are emerging tools for biocatalytic process development. A compelling design is that of the coated-wall reactor where enzyme is present as a surface layer attached to microchannel walls. However, preparation of a highly active wall biocatalyst remains a problem. Here, a stainless steel microreactor was developed where covalent immobilization of the enzyme in multiple linear flow channels of the reaction plate was supported by a macroporous wash-coat layer of gamma-aluminum oxide. Using surface functionalization with aminopropyl triethoxysilane followed by activation with glutardialdehyde, the thermophilic beta-glycosidase CelB from Pyrococcus furiosus was bound with retention of half of the specific activity of the free enzyme (800 U/mg), yielding a high catalyst loading of about 500 U/mL. This microreactor was employed for the continuous hydrolysis of lactose (100 mM) at 80 degrees C, providing a space-time yield of 500 mg glucose/(mL h) at a stable conversion of > or =70%. The immobilized enzyme displayed a half-life of 15 days under the operational conditions. Due to the absence of hydrophobic solute-material interactions, which limit the scope of microstructures fabricated from poly(dimethylsiloxane) for biocatalytic applications, the new microreactor was fully compatible with the alternate enzyme substrate 2-nitro-phenyl-beta-D-galactoside and the 2-nitro-phenol product resulting from its hydrolysis catalyzed by CelB. PMID:18618472

  20. 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.

  1. 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. PMID:27502414

  2. 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.

  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. 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.

  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. Macroscopic to microscopic studies of flue gas desulfurization byproducts for acid mine drainage mitigation

    SciTech Connect

    Robbins, E.I.; Kalyoncu, R.S.; Finkelman, R.B.; Matos, G.R.; Barsotti, A.F.; Haefner, R.J.; Rowe, G.L. Jr.; Savela, C.E.; Eddy, J.I.

    1996-12-31

    The use of flue gas desulfurization (FGD) systems to reduce SO{sub 2} emissions has resulted in the generation of large quantities of byproducts. These and other byproducts are being stockpiled at the very time that alkaline materials having high neutralization potential are needed to mitigate acid mine drainage (AMD). FGD byproducts are highly alkaline materials composed primarily of unreacted sorbents (lime or limestone and sulfates and sulfites of Ca). The American Coal Ash Association estimated that approximately 20 million tons of FGD material were generated by electric power utilities equipped with wet lime-limestone PGD systems in 1993. Less than 5% of this material has been put to beneficial use for agricultural soil amendments and for the production of wallboard and cement. Four USGS projects are examining FGD byproduct use to address these concerns. These projects involve (1) calculating the volume of flue gas desulfurization (FGD) byproduct generation and their geographic locations in relation to AMD, (2) determining byproduct chemistry and mineralogy, (3) evaluating hydrology and geochemistry of atmospheric fluidized bed combustion byproduct as soil amendment in Ohio, and (4) analyzing microbial degradation of gypsum in anoxic limestone drains in West Virginia.

  7. Hot gas desulfurization with sorbents containing mixed metal oxides

    SciTech Connect

    Akyurtlu, J.F.; Akyurtlu, A.

    1992-12-31

    Advanced power generation systems such as the integrated gasification combined cycle power generators and the molten carbonate fuel cells have stringent fuel gas desulfurization requirements and process economics dictates that this desulfurization be performed near the temperature of the gasification off-gas. The most advanced hot gas desulfurization technology today is based on the zinc ferrite sorbent which has several shortcomings such as zinc loss by evaporation, and incomplete regeneration due to sulfate formation. The objective of this study is to develop an improved sorbent which can reduce H{sub 2}S levels to 1 ppmv or less, which can stabilize zinc, and produce economically recoverable amounts of elemental sulfur during regeneration. For this purpose, the desulfurization performance.of sorbents prepared by the addition of various amounts of V{sub 2}0{sub 5} to the zinc ferrite sorbent is investigated. Preliminary experiments show that the sorbent containing about 4.8 mass % vanadium shows a superior desulfurization performance compared to zinc ferrite. Addition of vanadium suppresses residual sulfate formation and possibly zinc evaporation. significant quantities of elemental sulfur were observed after the regeneration of vanadium containing sorbents.

  8. 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.

  9. Biogas desulfurization using autotrophic denitrification process.

    PubMed

    Bayrakdar, Alper; Tilahun, Ebrahim; Calli, Baris

    2016-01-01

    The aim of this study was to evaluate the performance of an autotrophic denitrification process for desulfurization of biogas produced from a chicken manure digester. A laboratory scale upflow fixed bed reactor (UFBR) was operated for 105 days and fed with sodium sulfide or H2S scrubbed from the biogas and nitrate as electron donor and acceptor, respectively. The S/N ratio (2.5 mol/mol) of the feed solution was kept constant throughout the study. When the UFBR was fed with sodium sulfide solution with an influent pH of 7.7, about 95 % sulfide and 90 % nitrate removal efficiencies were achieved. However, the inlet of the UFBR was clogged several times due to the accumulation of biologically produced elemental sulfur particles and the clogging resulted in operational problems. When the UFBR was fed with the H2S absorbed from the biogas and operated with an influent pH of 8-9, around 98 % sulfide and 97 % nitrate removal efficiencies were obtained. In this way, above 95 % of the H2S in the biogas was removed as elemental sulfur and the reactor effluent was reused as scrubbing liquid without any clogging problem.

  10. 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.

  11. 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.

  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. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1987-05-18

    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.

  14. 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.

  15. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1988-11-14

    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.

  16. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1987-08-28

    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.

  17. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1988-08-19

    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. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

    SciTech Connect

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

    1989-03-06

    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.

  19. Desulfurization of coal: Enhanced selectivity using phase transfer catalysts. Final technical report, September 1, 1995--August 31, 1996

    SciTech Connect

    Palmer, S.R.; Hippo, E.J.

    1997-05-01

    Due to environmental problems related to the combustion of high sulfur Illinois coal, there continues to be interest in the development of viable pre-combustion desulfurization processes. Recent studies by the authors have obtained very good sulfur removals but the reagents that are used are too expensive. Use of cheaper reagents leads to a loss of desired coal properties. This study investigated the application of phase transfer catalysts to the selective oxidation of sulfur in coal using air and oxygen as oxidants. The phase transfer catalyst was expected to function as a selectivity moderator by permitting the use of milder reaction conditions than otherwise necessary. This would enhance the sulfur selectivity and help retain the heating value of the coal. The use of certain coal combustion wastes for desulfurization, and the application of cerium (IV) catalyzed air oxidations for selective sulfur oxidation were also studied. If successful this project would have lead to the rapid development of a commercially viable desulfurization process. This would have significantly improved the marketability of Illinois coal. However, the phase transfer catalysts, the cerium and the scrubber sledge did not catalize the sulfur removal significantly.

  20. Theoretical approach for enhanced mass transfer effects in-duct flue gas desulfurization processes

    SciTech Connect

    Not Available

    1990-08-22

    While developing dry sorbent duct injection flue gas desulfurization processes may offer significant improvement in capital cost and process simplicity compared to wet scrubbing systems, the economics of this technology can be improved significantly by an improvement in sorbent utilization. While a general understanding of the mechanism by which the sorbents operate is known, a much more detailed knowledge of reaction rate-controlling phenomena, the role of inherent reactivity, and mass transfer effects and their interaction in needed. Objectives of this project are threefold: 1. Mass transfer investigation--determine the controlling physical and chemical processes that limit sorbent utilization. In particular, determine whether mass transfer is a controlling factor in in-duct flue gas desulfurization and establish the relative contributions of gas- and liquid-phase mass transfer and inherent sorbent reactivity. 2. Field test support--evaluate various sorbents, operating conditions and process schemes to support large-scale field testings at Meredosia and Beverly. 3. Mass transfer enhancement--examine various techniques that will enable sorbent utilization rates of at least 75 percent to be achieved. Sorbents investigated were Ca(OH){sub 2}, Mississippi hydrate and Mississippi slaked lime. Epsom Salt was investigated as an additive. Agglomeration of Ca(OH){sub 2} solids was also investigated. 3 refs., 92 figs., 23 tabs.

  1. Immobilized biocatalytic process development and potential application in membrane separation: a review.

    PubMed

    Chakraborty, Sudip; Rusli, Handajaya; Nath, Arijit; Sikder, Jaya; Bhattacharjee, Chiranjib; Curcio, Stefano; Drioli, Enrico

    2016-01-01

    Biocatalytic membrane reactors have been widely used in different industries including food, fine chemicals, biological, biomedical, pharmaceuticals, environmental treatment and so on. This article gives an overview of the different immobilized enzymatic processes and their advantages over the conventional chemical catalysts. The application of a membrane bioreactor (MBR) reduces the energy consumption, and system size, in line with process intensification. The performances of MBR are considerably influenced by substrate concentration, immobilized matrix material, types of immobilization and the type of reactor. Advantages of a membrane associated bioreactor over a free-enzyme biochemical reaction, and a packed bed reactor are, large surface area of immobilization matrix, reuse of enzymes, better product recovery along with heterogeneous reactions, and continuous operation of the reactor. The present research work highlights immobilization techniques, reactor setup, enzyme stability under immobilized conditions, the hydrodynamics of MBR, and its application, particularly, in the field of sugar, starch, drinks, milk, pharmaceutical industries and energy generation.

  2. A biocatalytic approach towards synthesis of polymer CdS nanocomposites

    SciTech Connect

    Banerjee, S.; Premchandran, R.; Baumgartner, T.

    1996-10-01

    Copolymers of hydroxythiophenol and ethylphenol have been prepared using a biocatalytic route. Specifically, the method utilizes an oxidative enzyme, horseradish peroxidase, solubilized within the aqueous phase of a AOT/isooctane microemulsion. The monomers are oil soluble and are thus present in the organic phase. High conversions are obtained upto 1:1 molar ratio of the two monomers. The resulting polymers have the overall morphology of interconnected submicron spheres and are soluble in common organic solvents. Following their synthesis these copolymers have been derivatized by attaching Q-sized CdS particles. Though the copolymer itself is nonfluorescent, the CdS nanoclusters within it can be selectively excited and made to fluoresce. The fluorescent properties of the polymer CdS composite are distinctive from underivatized CdS or hydroxythiophenol monomer capped CdS.

  3. Biocatalytic methanation of hydrogen and carbon dioxide in a fixed bed bioreactor.

    PubMed

    Alitalo, Anni; Niskanen, Marko; Aura, Erkki

    2015-11-01

    Biocatalytic methanation of H2 and CO2 was studied in a fixed bed reactor system consisting of two solid state bioreactors in series connected to a recirculation system. Bioreactors were packed with a mixture of vermiculite shales and granular perlite material as a support material. A maximal methane productivity of 6.35l/lreactord was achieved at a hydrogen feed rate of 25.2l/lreactord, while hydrogen conversion rate was 100%. However, stable operation of the reactor at this efficiency remains to be achieved. Very simple reactor design, constructed from low cost materials, and the idea of exploiting waste material as a robust source of nutrients for methanogens makes this study very interesting regarding the overall usability and suitability of the system as part of a decentralized energy system. PMID:26298404

  4. 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

  5. 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.

  6. Process for desulfurization of coal and ores

    SciTech Connect

    Starbuck, A.

    1980-07-22

    A process for desulfurizing ores containing sulfur comprises the steps of: (A) crushing ore containing sulfur to a particle consistency; (B) feeding the crushed ore to a heated continuous-flow processor; (C) introducing pre-heated sulfur dissolving solvent into said processor with the crushed ore; (D) concurrently mixing and force conveying the crushed ore and solvent by augering in the continuous flow processor at an elevated temperature in which sulfur is dissolvable and is dissolved in a heated sulfur-solvent solution with suspended particles and a remaining ore, the processor being oriented for about horizontal augering; (E) separating the sulfur-solvent solution with suspended particles from the remaining ore at an elevated temperature; (F) drying the separated, remaining ore by evaporating remaining solvent from the ore; (G) recovering solvent from the ore drying step by condensing the evaporated solvent; (H) concurrently crystallizing sulfur dissolved in the sulfur-solvent solution and force conveying the sulfur-solvent solution and crystallizing sulfur by augering a continuous flow chilled processor wherein the sulfur-solvent solution and crystallizing sulfur are conveyed together in a concurrent manner as a mixture in a continuous forward direction at controlled reduced temperatures as substantially the entire mixture progresses to a separate separating step, said crystallizing sulfur existing in part as a suspension and in part as a precipitate; (I) separating both crystallized suspension sulfur and crystallized precipitate sulfur from the solvent solution; (J) drying the separated crystallized sulfur by evaporating the solvent from the crystallized sulfur, wherein a fine crystal sulfur product is obtained; and (K) recovering solvent from the crystallized sulfur drying step by condensing the veaporated solvent.

  7. 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)

  8. 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.

  9. Selecting the right pumps and valves for flue gas desulfurization

    SciTech Connect

    Ellis, D.; Ahluwalia, H.

    2006-07-15

    Limestone slurry needs to move efficiently through a complex process, meaning that selecting the right pumps and valves is critical. The article discusses factors to consider in selecting pumps and values for flue gas desulfurization process in coal-fired power plants. 2 photos.

  10. 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...

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Preparation of Biocatalytic Microparticles by Interfacial Self-Assembly of Enzyme-Nanoparticle Conjugates Around a Cross-Linkable Core.

    PubMed

    Andler, S M; Wang, L-S; Goddard, J M; Rotello, V M

    2016-01-01

    Rational design of hierarchical interfacial assembly of reusable biocatalytic microparticles is described in this chapter. Specifically, purified enzymes and functionalized nanoparticles are electrostatically assembled at the interface of cross-linked microparticles which are formed through ring opening metathesis polymerization. The diameters of microparticle assemblies average 10μm, and they show enhanced kinetic efficiency as well as improved stability against heat, pH, and solvent denaturation when compared to stabilities of the corresponding native enzymes.

  17. 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.

  18. 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

    2016-01-01

    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. PMID:26985887

  19. Carbohydrate base co-polymers as an efficient immobilization matrix to enhance lipase activity for potential biocatalytic applications.

    PubMed

    Badgujar, Kirtikumar Chandulal; Bhanage, Bhalchandra Mahadeo

    2015-12-10

    In the present study, we have synthesized biocompatible hybrid blend of cellulosic polymers of hydroxypropyl-methyl-cellulose (HPMC) and chitosan (CHY) for the immobilization of Candida rugosa lipase (CRL). The immobilized biocatalyst HPMC:CHY:CRL was subjected for characterization such as SEM, TGA, water content analysis, lipase activity, specific activity and protein content analysis. The kinetic parameter study (Rmax/Km) demonstrated improved biocatalytic activity of lipase after immobilization on carbohydrate co-polymers of HPMC:CHY. This biocatalyst was then employed to study practical biocatalytic applications for kinetic resolution which provided 50% conversion and >94% enantiomeric excess of substrate/product (ees/eep). The protocol demonstrated excellent recyclability upto five cycles. Finally, we studied influence of immobilization on cellulosic polymers for substrate, structure and reactivity for kinetic resolution. Hence, we investigated R0 (initial reaction rate), E-value (enantioselectivity) and Ea (activation energy). This study confirms that, lipase immobilized on carbohydrate polymers had 3-4 folds higher biocatalytic activity as compared to crude CRL. PMID:26428176

  20. Oxidative desulfurization of fuel oil by pyridinium-based ionic liquids.

    PubMed

    Zhao, Dishun; Wang, Yanan; Duan, Erhong

    2009-01-01

    In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF(4) was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF(4) has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil) /V(H(2)O(2)) = 1:1:0.4, temperature 55 degrees C, the time 30 min. The ratio of desulfurization to thiophene and DBT reached 78.5% and 84.3% respectively, which is much higher than extraction desulfurization with simple ionic liquids. Under these conditions, the effect of desulfurization on gasoline was also investigated. The used ionic liquids can be recycled up to four times after regeneration. PMID:19924069

  1. 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)

  2. Molecular biology of coal bio-desulfurization; Quarterly technical progress report, October 1--December 31, 1990

    SciTech Connect

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

    1991-01-25

    The aim of this project is to use the techniques of molecular genetics to identify, clone, sequence, and enhance the expression of proteins which remove sulfur covalently bound to coal. This includes the movement and expression of these proteins into bacterial species which may be more useful in the industrial application of a biological desulfurization process. This quarter we finalized the initial cloning and sequencing of the dibenzothiophene (DBT) metabolic (``dox``) genes from strain C18. In addition, we constructed several mutations in single dox genes and have begun to dissect the contribution of each gene product in the DBT degradation pathway. Using a probe derived from DNA adjacent to a transposon which inactivated DBT metabolism, the DBT active genes from A15 have been cloned and identified on cosmids. We have also electroporated Thiobacillus ferrooxidans with a plasmid containing a chloramphenicol resistant transposon. Colonies of T. ferrooxidans resistant to chloramphenicol were obtained.

  3. Bench-scale demonstration of hot-gas desulfurization technology. Quarterly report, January 1--March 31, 1998

    SciTech Connect

    1998-12-31

    At the start of the current project, the DSRP (Direct Sulfur Recovery Process) technology was at the bench-scale development stage with a skid-mounted system ready for field testing. The process had been extended to fluidized-bed operation in the Stage 1 reactor. A preliminary economic study for a 100 MW plant in which the two-stage DSRP was compared to conventional processes indicated the economic attractiveness of the DSRP. Through bench-scale development, both fluidized-bed zinc titanate and DSRP technologies have been shown to be technically and economically attractive. The demonstrations prior to the start of this project, however, had only been conducted using simulated (rather than real) coal gas and simulated regeneration off-gas. Thus, the effect of trace contaminants in real coal gases on the sorbent and DSRP catalyst was not known. Also, the zinc titanate desulfurization unit and DSRP had not been demonstrated in an integrated manner. The overall goal of this project is to continue further development of the zinc titanate desulfurization and DSRP technologies by scale-up and field testing (with actual coal gas) of the zinc titanate fluidized-bed reactor system, and the Direct Sulfur Recovery Process.

  4. Natural desulfurization in coal-fired units using Greek lignite.

    PubMed

    Konidaris, Dimitrios N

    2010-10-01

    This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash. PMID:21090555

  5. Introduction to limestone flue gas desulfurization: Videotape workbook

    SciTech Connect

    Not Available

    1988-01-01

    The workbook is designed to accompany the Electric Power Research Institute's (EPRI's) videotape, ''Introduction to Limestone Flue Gas Desulfurization.'' To complement the videotape, the workbook provides additional information on limestone flue gas desulfurization (FGD) and a guide to sources of still more information. The videotape itself presents an introduction to the chemistry involved in a limestone FGD system. Following a description of a typical system, the basic chemical reactions that occur in this process are detailed. The most common operation problems in limestone FGD---low sulfur dioxide removal, low limestone utilization, and scaling---are reviewed with regard to how process chemistry can be controlled to alleviate these problems. This tape is an introduction only; future tapes will cover limestone FGD performance indicators and troubleshooting in more detail.

  6. Natural desulfurization in coal-fired units using Greek lignite.

    PubMed

    Konidaris, Dimitrios N

    2010-10-01

    This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.

  7. Hot coal gas desulfurization with manganese-based sorbents

    SciTech Connect

    Hepworth, M.T.; Ben-Slimane, R.

    1995-11-01

    The primary major deposit of manganese in the US which can be readily mined by an in situ process is located in the Emily district of Minnesota. The US Bureau of Mines Research Centers at both the Twin Cities and Salt Lake City have developed a process for extracting and refining manganese in the form of a high-purity carbonate product. This product has been formulated into pellets by a multi-step process of drying, calcination, and induration to produce relatively high-strength formulations which are capable of being used for hot fuel gas desulfurization. These pellets, which have been developed at the University of Minnesota under joint sponsorship of the US Department of Energy and the US Bureau of Mines, appear superior to other, more expensive, formulations of zinc titanate and zinc ferrite which have previously been studied for multi-cycle loading (desulfurization) and regeneration (evolution of high-strength SO{sub 2} and restoration of pellet reactivity). Although these other formulations have been under development for the past twelve years, their prices still exceed $7 per pound. If manganese pellets perform as predicted in fixed bed testing, and if a significant number of utilities which burn high-sulfur coals incorporate combined-cycle gasification with hot coal gas desulfurization as a viable means of increasing conversion efficiencies, then the potential market for manganese pellets may be as high as 200,000 tons per year at a price not less than $3 per pound. This paper discusses the role of manganese pellets in the desulfurization process with respect to the integrated gasification combined-cycle (IGCC) for power generation.

  8. 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

  9. Coal desulfurization. (Latest citations from the Compendex database). Published Search

    SciTech Connect

    Not Available

    1993-06-01

    The bibliography contains citations concerning physical, chemical, and microbiological methods used in the removal of sulfur from coal. Oxydesulfurization, washing, electrochemical separation, oxidation, molten salts, microwave radiation, biodegradation, supercritical extraction, magnetic techniques, chlorinolysis, and flotation are among the processes considered. Sulfur pollution standards, environmental regulations and considerations, and process analyses and evaluations are discussed. Desulfurization of coal derived liquids and coal liquefaction are examined in separate bibliographies. (Contains 250 citations and includes a subject term index and title list.)

  10. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    SciTech Connect

    John G. Verkade

    1998-02-28

    The reactions of dialkyl mono- and disulfides and functionalized alkylthio compounds with sodium in refluxing hydrocarbon solvent (tetradecane, mesitylene or toluene) resulted in sulfur-free products in very high yields. Greater than 95% sulfur removal was observed when dialkyl mono or polysulfides were treated with Na in liquid ammonia. Polycyclic aromatic sulfur heterocycles were only moderately desulfurized under these conditions while phenylthio derivatives gave thiophenol as the major product and dithiophenols as the minor products.

  11. Hot gas desulfurization with oxides of zinc, iron, and vanadium

    SciTech Connect

    Akyurtlu, J.F.; Akyurtlu, A.

    1992-08-01

    The objective of this study is to develop an improved sorbent which can reduce H{sub 2}S levels up to 1 ppmv or less, which can stabilize zinc, and produce economically recoverable amounts of elemental sulfur during regeneration. For this purpose, the desulfurization performance of sorbents prepared by the addition of various amounts of V{sub 2}O{sub 5} to the zinc ferrite sorbent is investigated.

  12. 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.

  13. 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.

  14. 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. PMID:25434261

  15. Silver Iodide-Chitosan Nanotag Induced Biocatalytic Precipitation for Self-Enhanced Ultrasensitive Photocathodic Immunosensor.

    PubMed

    Gong, Lingshan; Dai, Hong; Zhang, Shupei; Lin, Yanyu

    2016-06-01

    In this work, we first exposed that the application of p-type semiconductor, silver iodide-chitosan nanoparticle (SICNP), acted as peroxidase mimetic to catalyze the bioprecipitation reaction for signal-amplification photocathodic immunosensing of human interleukin-6 (IL-6). After immobilization of captured antibody onto a polyethylenimine-functionalized carbon nitride (CN) matrix, SICNPs as photoactive tags and peroxidase mimetics were labeled on secondary antibodies, which were subsequently introduced onto the sensing interface to construct sandwich immunoassay platform through antigen-antibody specific recognition. Due to the matched energy levels between CN and AgI, the photocurrent intensity and photostability of SICNP were dramatically improved with rapid separation and transportation of photogenerated carriers. Moreover, the insoluble product in effective biocatalytic precipitation reaction served as electron acceptor to scavenge the photoexcited electron, leading to great amplification of the photocurrent signal of SICNP again. With the help of multiamplification processes, this photocathodic immunosensor presented a turn-on photoelectrochemical performance for IL-6, which showed wide linear dynamic range from 10(-6) to 10 pg/mL with the ultralow detection limit of 0.737 ag/mL. This work also performed the promising application of SICNP in developing an ultrasensitive, cost-effective, and enzyme-free photocathodic immunosensor for biomarkers. PMID:27180822

  16. 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. PMID:18478407

  17. Exploiting cell metabolism for biocatalytic whole-cell transamination by recombinant Saccharomyces cerevisiae.

    PubMed

    Weber, Nora; Gorwa-Grauslund, Marie; Carlquist, Magnus

    2014-05-01

    The potential of Saccharomyces cerevisiae for biocatalytic whole-cell transamination was investigated using the kinetic resolution of racemic 1-phenylethylamine (1-PEA) to (R)-1-PEA as a model reaction. As native yeast do not possess any ω-transaminase activity for the reaction, a recombinant yeast biocatalyst was constructed by overexpressing the gene coding for vanillin aminotransferase from Capsicum chinense. The yeast-based biocatalyst could use glucose as the sole co-substrate for the supply of amine acceptor via cell metabolism. In addition, the biocatalyst was functional without addition of the co-factor pyridoxal-5'-phosphate (PLP), which can be explained by a high inherent cellular capacity to sustain PLP-dependent reactions in living cells. In contrast, external PLP supplementation was required when cell viability was low, as it was the case when using pyruvate as a co-substrate. Overall, the results indicate a potential for engineered S. cerevisiae as a biocatalyst for whole-cell transamination and with glucose as the only co-substrate for the supply of amine acceptor and PLP.

  18. 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.

  19. 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

  20. Biocatalytically induced growth of gold nanoshells: using enzyme reaction for the controllable fabrication of nanomaterials.

    PubMed

    Ma, Xiaoyuan; Liu, Liangliang; Liu, Fangjing; Qian, Weiping

    2012-02-01

    In the present work, the enzymatically controlled growth process of gold nanoshells (GNSs) in the presence of O2/glucose/glucose oxidase (GOx) and its chloroaurate ion electron acceptor is described. The biocatalytically stimulated growth process is one of the bio-inspired synthetic procedures directed by biological molecules which occur under ambient conditions. It is found that hydrogen peroxide (H2O2) could enlarge the gold nanoparticles (GNPs) on the surface of GNSs precursor composites, of which the preadsorbed GNPs serve as nucleation sites for further gold deposition. Here, GOx is harnessed for its unparalled level of catalytic activity and substrate specificity while H2O2 is produced as a by-product during the oxidation of D-glucose to gluconic acid by GOx. Then the bio-generated H2O2 is used as the reducing agent in the catalytic deposition process of GNSs formation. During the procedure, the localized surface plasmon resonance peaks range across hundreds of nanometers from visible to near infrared region accompanying by the resultant formation of uniform and continuous core-shell nanostructures. The corresponding optical, morphological and enzyme kinetic properties are all well investigated. The novel protocol offers a new perspective for the bio-directed synthesis method in nanotechnology. PMID:22629867

  1. 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. PMID:26100386

  2. 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. PMID:26462117

  3. Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

    PubMed

    Burkhardt, M; Koschack, T; Busch, G

    2015-02-01

    A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven. PMID:25193088

  4. 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

  5. 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

  6. 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

  7. Silver Iodide-Chitosan Nanotag Induced Biocatalytic Precipitation for Self-Enhanced Ultrasensitive Photocathodic Immunosensor.

    PubMed

    Gong, Lingshan; Dai, Hong; Zhang, Shupei; Lin, Yanyu

    2016-06-01

    In this work, we first exposed that the application of p-type semiconductor, silver iodide-chitosan nanoparticle (SICNP), acted as peroxidase mimetic to catalyze the bioprecipitation reaction for signal-amplification photocathodic immunosensing of human interleukin-6 (IL-6). After immobilization of captured antibody onto a polyethylenimine-functionalized carbon nitride (CN) matrix, SICNPs as photoactive tags and peroxidase mimetics were labeled on secondary antibodies, which were subsequently introduced onto the sensing interface to construct sandwich immunoassay platform through antigen-antibody specific recognition. Due to the matched energy levels between CN and AgI, the photocurrent intensity and photostability of SICNP were dramatically improved with rapid separation and transportation of photogenerated carriers. Moreover, the insoluble product in effective biocatalytic precipitation reaction served as electron acceptor to scavenge the photoexcited electron, leading to great amplification of the photocurrent signal of SICNP again. With the help of multiamplification processes, this photocathodic immunosensor presented a turn-on photoelectrochemical performance for IL-6, which showed wide linear dynamic range from 10(-6) to 10 pg/mL with the ultralow detection limit of 0.737 ag/mL. This work also performed the promising application of SICNP in developing an ultrasensitive, cost-effective, and enzyme-free photocathodic immunosensor for biomarkers.

  8. Cellulose Digestion and Metabolism Induced Biocatalytic Transitions in Anaerobic Microbial Ecosystems

    PubMed Central

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

    2013-01-01

    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. PMID:24958386

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

    PubMed

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

    2016-01-01

    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

  10. Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

    PubMed

    Burkhardt, M; Koschack, T; Busch, G

    2015-02-01

    A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs).

    PubMed

    Lü, Hongying; Li, Pengcheng; Deng, Changliang; Ren, Wanzhong; Wang, Shunan; Liu, Pan; Zhang, Han

    2015-07-01

    An oxalate-based DES with a tetrabutyl ammonium chloride and oxalate acid molar ratio of 1/2 (TBO1 : 2) exhibited high activity in oxidative desulfurization (ODS) of dibenzothiophene (DBT) under mild reaction conditions. It is potentially a promising and highly environmentally friendly approach for desulfurization of fuels. PMID:26051675

  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. Anion-exchange resin-based desulfurization process. Quarterly technical progress report, Januray 1, 1992--March 31, 1992

    SciTech Connect

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

    1992-07-01

    Under DOE Grant No. FG22-90PC90309, the University of Tennessee Space Institute (UTSI) is contracted to further develop its anion-exchange, resin-based desulfurization concept to desulfurize alkali metal sulfates. From environmental as well as economic viewpoints, it is necessary to remove soluble sulfates from the wastes created by flue gas desulfurization systems. In order to do this economically, a low-cost desulfurization process for spent sorbents is necessary. UTSI`s anion-exchange resin-based desulfurization concept is believed to satisfy these requirements.

  18. 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.

  19. Extraction and desulfurization of chemically degraded coal with supercritical fluids. Final report, July 1, 1983-December 1984

    SciTech Connect

    Chen, J.W.; Muchmore, C.B.; Kent, A.C.

    1985-03-01

    This report describes the progress made in the research entitled ''Extraction and Desulfurization of Chemically Degraded Coal with Supercritical Fluids.'' The desulfurization of coal, employing ethanol or methanol as solvent under supercritical conditions, has demonstrated its ability to selectively remove sulfur from the coal matrix. The objectives of the research are these: (1) to obtain rate data for supercritical extraction and desulfurization of coal, and to determine the desulfurization selectivity ratio for various coals; (2) to study the effect of chemical pretreatment of coal on desulfurization potential; and (3) to determine the characteristics of the desulfurized solid char and to measure and evaluate the liquid and gaseous streams. The experimental investigations have been carried out in two reactor systems, a semicontinuous reactor and a batch reactor. Experimental data obtained have indicated the following achievements: (1) the extraction and desulfurization of coal with supercritical ethanol is first order in nature, and the activation energies for coal extracted and sulfur removed are 30.3 and 21.0 Kcal, respectively; (2) the desulfurization selectivity ratio is found to be between 2.96 to 4.38 for four Illinois coal samples studied; (3) the effect of KOH pretreatment indicates an improvement of supercritical desulfurization potential; and (4) the evalution of product streams reveals that supercritical desulfurization generates a high Btu gas and coal-derived liquid in addition to the desulfurized solid product. 2 references, 5 tables, 9 figures.

  20. 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.

  1. Coal desulfurization by leaching involving acidophilic and thermophilic microorganisms

    SciTech Connect

    Murr, L.E.; Mehta, A.P.

    1982-03-01

    It was shown that thermophilic microorganisms can increase the rate and volume of pyrite leaching from pulverized, high-sulfur coal. This occurs not only because of the elevated temperature of operation possible, but also the apparent accelerated catalytic activity of thermophilic microorganisms as compared to autotropic microbes such as T. ferrooxidans. The ability of thermophilic microogranisms to successfully leach pyrite in coal as demonstrated in the study points toward an even greater potential for the develpment of a successful and economically viable large-scale desulfurization process involving biochemical leaching. (JMT)

  2. Sodium-limestone double alkali flue gas desulfurization method

    SciTech Connect

    Wang, K.H.; Biolchini, R.J.; Legatski, L.K.

    1983-10-18

    A flue gas desulfurization method is disclosed for efficiently removing sulfur oxides from a gas stream with an aqueous sodium sulfite- and sodium bisulfite-containing absorption solution, in which absorber effluent solution at a pH of 5.8 to 6.6 and having an active sodium concentration of from 0.5 M to 0.9 M is regenerated with sufficient ground limestone to yield a treated solution with a higher pH of from 6.3 to 7.0 and whose bisulfite concentration is reduced by from 35 to 70%

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

    DOEpatents

    Li, Liyu; King, David L.; Liu, Jun; Huo, Qisheng

    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.

  4. 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.

  5. Branched zinc oxide nanorods arrays modified paper electrode for electrochemical immunosensing by combining biocatalytic precipitation reaction and competitive immunoassay mode.

    PubMed

    Sun, Guoqiang; Yang, Hongmei; Zhang, Yan; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2015-12-15

    Branched zinc oxide nanorods (BZR) arrays, an array with high charge carries collection efficiency and specific surface area, are grown on the reduced graphene oxide-paper working electrode for the first time to construct a paper-based electrochemical (EC) immunosensor. Typically, the BZR are fabricated via a simple hydrothermal process, which can provide abundant sites for antibodies loading. By combining the large surface area of porous zinc oxide (PZS) and good biocompatibility of gold nanoparticles (AuNPs), PZS-AuNPs (PZS@Au) nanocomposites are designed to label horseradish peroxide (HRP) and antigens. After a competitive reaction between antigens and PZS@Au nanocomposites labeled antigens, the signal labels are introduced into the immunosensor, in which, HRP participate in biocatalytic precipitation process. The produced precipitate reduces the electrode surface area and hinders the electron transfer. With the increase of concentration of antigens, the signal labels introduced into the sensor decrease, thus, a signal-on immunoassay for α-fetoprotein detection is constructed. The proposed paper-based EC immunosensor combines enzymatic biocatalytic precipitation reaction and competitive immunoassay mode for the first time, and possesses a wide linear range from 0.2 pg mL(-1) to 500 ng mL(-1) with a detection limit of 0.08 pg mL(-1). In addition, the proposed method is simple, sensitive and specific and can be a promising platform for other protein detection.

  6. Biocatalytic properties of a recombinant Fusarium proliferatum lactonase with significantly enhanced production by optimal expression in Escherichia coli.

    PubMed

    Chen, Bing; Fan, Li-Qiang; Xu, Jian-He; Zhao, Jian; Zhang, Xian; Ouyang, Li-Ming

    2010-10-01

    The levo-lactonase gene of Fusarium proliferatum ECU2002 (EC3.1.1.25) was cloned and expressed in Escherichia coli JM109 (DE3) for biocatalytic resolution of industrially important chiral lactones, including DL-pantoyl lactone which was a key precursor to calcium D-pantothenate. By increasing the biomass concentration and lowering the inducer (isopropyl-beta-D-thiogalactoside) concentration and induction temperature, the lactonase production was significantly enhanced up to 20 kU/L, which was 20 times higher than that of wild-type strain F. proliferatum ECU2002. The recombinant Fusarium lactonase was purified using immobilized metal affinity chromatography, and its SDS-PAGE revealed a molecular mass of 50 kDa for the recombinant protein, suggesting that the enzyme was a simplex protein. Furthermore, biocatalytic properties of the recombinant lactonase were investigated, including kinetic parameters, additive's effect, and substrate specificity. The results reported in this paper provide a feasible method to make the whole cells of E. coli JM109 (DE3) expressing lactonase gene to be a highly efficient and easy-to-make biocatalyst for asymmetric synthesis of chiral compounds. PMID:19876606

  7. 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.

  8. 1,3-Diferuloyl-sn-glycerol from the biocatalytic transesterification of ethyl 4-hydroxy-3-methoxy cinnamic acid (ethyl ferulate) and soybean oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    1,3-Diferuloyl-sn-glycerol is a natural plant component 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 the pilot plant scale packed-bed, biocatalytic...

  9. Influence of addition of alkali metal compounds to calcium carbonate on desulfurization characteristics

    SciTech Connect

    Naruse, Ichiro; Saito, Katsuhiro; Murakami, Takahiro

    1999-07-01

    Limestone is currently supplied as a desulfurizer into bubbling and circulating fluidized bed coal combustors since both combustors are operated at the temperature ranged from 1,073 to 1,173 K, where limestone can be calcined and sulfurized optimally. In the practical boilers, however, the limestone particles are fed to the combustor excessively since the utilization efficiency of CaO produced by the calcination of limestone is low. On the other hand, many kinds of sea-shell are clarified as one of industrial wastes, and also consist of CaCO{sub 3} similar to limestone. Therefore it would be possible for wasted sea-shell to be applied to one of the desulfurizers. In this case the CO{sub 2} produced by calcination of the shell is fixed and recycled naturally in obedience to the ecological law. From this viewpoint, desulfurization characteristics of wasted sea shell have been already studied fundamentally by using a thermobalance as compared with the results obtained by limestone. The results obtained by this study are summarized as follows. (1) The desulfurization activity for wasted sea-shell is much higher than that for limestone. (2) Even if the alkali metal compounds are partially removed from the sea shell, the desulfurization efficiency does not change. (3) The desulfurization activity can be enhanced by adding alkali metal compounds to limestone. Sodium compounds are more effective on the desulfurization efficiency than potassium compounds. Sodium chloride is the best agent among them.

  10. Effect of solids concentration distribution on the flue gas desulfurization process

    SciTech Connect

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

    2006-06-15

    A dry flue gas desulfurization (FGD) process at 600-800{sup o}C was studied in a pilot-scale circulating fluidized bed (CFB) experimental facility. Various fresh sorbent distribution types and internal structures were modeled numerically to investigate their effect on the gas-solid flow and sulfate reaction characteristics. Experimental results show that, after the fresh sorbent supply was stopped, the desulfurization efficiency declined rapidly even though the sorbent recirculation was maintained. Therefore, the fresh sorbent is the main contributor to the desulfurization process and the primary effect of the recirculated sorbent was to evenly distribute the fresh sorbent and to prolong the sorbent particle residence time. The numerical results demonstrate that the desulfurization efficiency varied greatly for the various fresh sorbent bottom injection methods. The desulfurization efficiency of the bottom-even injection method was 1.5 times that of the bottom two-sided injection method. Internal structures effectively improved the fresh sorbent solids concentration distribution and the desulfurization efficiency. Optimized internal structures increased the desulfurization efficiency of the bottom two-sided injection method by 46%, so that it was very close to that of the bottom-even injection method with only a 4.6% difference. 16 refs., 6 figs., 2 tabs.

  11. Kinetic analysis of microbial desulfurization of model and light gas oils containing multiple alkyl dibenzothiophenes.

    PubMed

    Kobayashi, M; Horiuchi, K; Yoshikawa, O; Hirasawa, K; Ishii, Y; Fujino, K; Sugiyama, H; Maruhashi, K

    2001-02-01

    The reaction mechanism of biodesulfurization was investigated using whole cells of Rhodococcus erythropolis KA2-5-1, which have the ability to convert dibenzothiophene (DBT) into 2-hydroxybiphenyl. The desulfurization patterns of alkyl DBTs were represented by the Michaeis-Menten equation. The values of rate constants, the limiting maximal velocity (Vmax) and Michaelis constant (Km), for desulfurization of alkyl DBTs were calculated. The relative desulfurization activities of various alkyl DBTs were reduced in proportion to the total carbon numbers of alkyl substituent groups. Alkyl DBTs that had a total of six carbons of alkyl substituent groups were not desulfurized. The type or position of alkyl substituent groups had little effect on desulfurization activity. The desulfurization activity of each alkyl DBT, when mixed together, was reduced. This phenomenon was caused by apparent competitive inhibition of substrates. Using the apparent competitive inhibition model, the desulfurization pattern of a multiple components system containing alkyl DBTs was elucidated. This model was also applicable for biodesulfurization of light gas oil.

  12. 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.

  13. 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.

  14. 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.

  15. Benzo[b]thiophene desulfurization by Gordonia rubropertinctus strain T08.

    PubMed

    Matsui, T; Onaka, T; Maruhashi, K; Kurane, R

    2001-10-01

    A benzothiophene-desulfurizing bacterium which has a novel desulfurization pathway was isolated and identified as Gordonia rubropertinctus strain T08. Gas chromatography/mass spectroscopy analysis of the ethyl acetate extract of the culture broth detected benzothiophene sulfoxide, benzothiophene sulfone, benzo[e][1,2]oxathiin S-oxide (BT-sultine), benzo[e][1,2]oxathiin S,S-dioxide (BT-sultone), o-hydroxystyrene, and 2-coumaranone, but not 2-(2'-hydroxyphenyl)ethan-1-al, which has been reported to be a desulfurized product of mesophilic nocardioforms.

  16. 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

  17. 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.

  18. Desulfurization Activated Phosphorothioate DNAzyme for the Detection of Thallium.

    PubMed

    Huang, Po-Jung Jimmy; Vazin, Mahsa; Liu, Juewen

    2015-10-20

    Thallium (Tl) is a highly toxic heavy metal situated between mercury and lead in the periodic table. While its neighbors have been thoroughly studied for DNA-based sensing, little is known about thallium detection. In this work, in vitro selection of RNA-cleaving DNAzymes is carried out using Tl(3+) as the target metal cofactor. Both normal DNA and phosphorothioate (PS)-modified DNA are tested for this purpose. While no Tl(3+)-dependent DNAzymes are obtained, a DNA oligonucleotide containing a single PS-modified RNA nucleotide is found to cleave by ∼7% by Tl(3+) at the RNA position. The remaining 93% are desulfurized. By hybridization of this PS-modified oligonucleotide with the Tm7 DNAzyme, the cleavage yield increases to ∼40% in the presence of Tl(3+) and Er(3+). Tm7 is an Er(3+)-dependent RNA-cleaving DNAzyme. It cleaves only the normal substrate but is completely inactive using the PS-modified substrate. Tl(3+) desulfurizes the PS substrate to the normal substrate to be cleaved by Tm7 and Er(3+). This system is engineered into a catalytic beacon for Tl(3+) with a detection limit of 1.5 nM, which is below its maximal contamination limit defined by the U.S. Environmental Protection Agency (10 nM). PMID:26393365

  19. Desulfurization Activated Phosphorothioate DNAzyme for the Detection of Thallium.

    PubMed

    Huang, Po-Jung Jimmy; Vazin, Mahsa; Liu, Juewen

    2015-10-20

    Thallium (Tl) is a highly toxic heavy metal situated between mercury and lead in the periodic table. While its neighbors have been thoroughly studied for DNA-based sensing, little is known about thallium detection. In this work, in vitro selection of RNA-cleaving DNAzymes is carried out using Tl(3+) as the target metal cofactor. Both normal DNA and phosphorothioate (PS)-modified DNA are tested for this purpose. While no Tl(3+)-dependent DNAzymes are obtained, a DNA oligonucleotide containing a single PS-modified RNA nucleotide is found to cleave by ∼7% by Tl(3+) at the RNA position. The remaining 93% are desulfurized. By hybridization of this PS-modified oligonucleotide with the Tm7 DNAzyme, the cleavage yield increases to ∼40% in the presence of Tl(3+) and Er(3+). Tm7 is an Er(3+)-dependent RNA-cleaving DNAzyme. It cleaves only the normal substrate but is completely inactive using the PS-modified substrate. Tl(3+) desulfurizes the PS substrate to the normal substrate to be cleaved by Tm7 and Er(3+). This system is engineered into a catalytic beacon for Tl(3+) with a detection limit of 1.5 nM, which is below its maximal contamination limit defined by the U.S. Environmental Protection Agency (10 nM).

  20. 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}.

  1. 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}.

  2. 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.

  3. 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.

  4. 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. PMID:24456468

  5. 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.

  6. Molecular biology of coal bio-desulfurization

    SciTech Connect

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

    1991-07-18

    The aim of this project is to use the techniques of molecular genetics to identify, clone, sequence, and enhance the expression of proteins which remove sulfur covalently bound to coal. The cloned dox genes from strain C18 were more fully characterized. Another gene, doxG, is almost identical with the nahC gene, also involved in the naphthalene pathway. These results lead us to believe that dibenzothiophene (DBT) is degraded by the oxidative route along the naphthalene degradative pathway. At least one other gene, doxI, is implicated in the formation of the unidentified fluorescent product from DBT. The Rhodococcus rhodochrous isolate IGTS8 was mutated to produce a variant (strain UV1) that was negative for DBT utilization. This mutant was exposed to further rounds of UV mutagenesis and was used as the host for attempts to introduce various plasmid DNAs. Two plasmids could be introduced into UV1: pRF29 and pLAFR5. A cosmid library of IGTS8 DNA was constructed in pLAFR5 and was electroporated into UV1. Of over 2000 colonies tested three bulk batches, one flask of about 600 clones produced a fluorescent product from DBT. These are being screened to determine if one of these represents a clone that complements the DBT negative phenotype of the UV1 mutant. We obtained chloramphenicol resistant Thiobacillus ferrooxidans after electroporation but these transformants contained no plasmid or transposon sequences, so that insertion of DNA into T. ferrooxidans had not occurred.

  7. 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.

  8. Isolation of carotenoid-deficient mutant from alkylated dibenzothiophene desulfurizing nocardioform bacteria, Gordonia sp. TM414.

    PubMed

    Matsui, Toru; Maruhashi, Kenji

    2004-02-01

    The dibenzothiophene-desulfurizing nocardioform bacteria, Gordonia sp. TM414, was isolated from oil-contaminated soil. To avoid coloration of the oil layer after the desulfurization reaction, which could decrease the quality of the oil, two colorless knock-out mutants, TPc and TPd, were isolated by using a broad-host-range transposon complex. Genomic sequence analysis revealed that the same gene was disrupted in these mutants and that the transposon-inserted gene was assigned as the gene for phytoene desaturase, crt I. The crt I mutants also showed desulfurization activity comparable to that of the parent strain in a model-oil/aqueous bi-phasic reaction, suggesting that the carotenoid production is not responsible for the bi-phasic desulfurization reaction that requires hydrophobic substrate incorporation from the organic phase.

  9. Desulfurization of 2,4,6,8-tetraethyl dibenzothiophene by recombinant Mycobacterium sp. strain MR65.

    PubMed

    Watanabe, Kimiko; Noda, Ken-ichi; Konishi, Jin; Maruhashi, Kenji

    2003-09-01

    Recombinant Mycobacterium sp. strain MR65 harboring dszABCD genes was used to desulfurize alkyl dibenzothiophenes (Cx-DBTs) in n-hexadecane. The specific desulfurization activity for 2,4,6,8-tetraethyl DBT (C8-DBT) by DszC enzyme was about twice that for 4,6-dipropyl DBT (C6-DBT). However, the degradation rate of 2,4,6,8-tetraethyl DBT in n-hexadecane by resting cells of strain MR65 was only about 40% of that of 4,6-dipropyl DBT. These results indicated that the desulfurization ability for Cx-DBTs by resting cells depends on carbon number substituted at positions 4 and 6 and that the rate-limiting step in the desulfurization reaction of highly alkylated Cx-DBTs is the transfer process from the oil phase into the cell.

  10. Enhanced desulfurization in a transposon-mutant strain of Rhodococcus erythropolis.

    PubMed

    Watanabe, Kimiko; Noda, Ken-ichi; Maruhashi, Kenji

    2003-08-01

    The dsz desulfurization gene cluster from Rhodococcus erythropolis strain KA2-5-1 was transferred into R. erythropolis strain MC1109, unable to desulfurize light gas oil (LGO), using a transposon-transposase complex. As a result, two recombinant strains, named MC0203 and MC0122, were isolated. Resting cells of strain MC0203 decreased the sulfur concentration of LGO from 120 mg l(-1) to 70 mg l(-1) in 2 h. The LGO-desulfurization activity of strain MC0203 was about twice that of strain MC0122 and KA2-5-1. The 10-methyl fatty acids of strain MC0203 were about 28%-41% that of strain MC1109. It is likely that strain MC0203 had a mutation involving alkylenation or methylation of delta9-unsaturated fatty acids caused by the transposon inserted in the chromosome, which increased the fluidity of cell membranes and enhanced the desulfurization activity.

  11. 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.

  12. 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.

  13. Petrographical characteristics of calcium based absorbent and its effect on grinding and calcination/desulfurization property

    SciTech Connect

    Xiong, Y.; Sun, X.

    1998-07-01

    This paper discussed the relationship between the petrographical characteristics and grinding, calcination/desulfurization properties of calcium based absorbent. Optical microscopy, XRD analysis, TGS-DTGA-DTA and thermal microscopy analyses were carried out on carbonate rocks. It was found that petrographical characteristics, such as grain size and cleavages developing degree have great effect on grinding, calcination/desulfurization properties. The choice of calcium based adsorbent should be based on the petrographical characteristics.

  14. 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.

  15. Key factor in rice husk Ash/CaO sorbent for high flue gas desulfurization activity.

    PubMed

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

    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 factorfor 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, x1 (6-16 h), amount of RHA, x2 (5-15 g), amount of CaO, x3 (2-6 g), amount of water, x4 (90-110 mL), and hydration temperature, x5 (150-250 degrees C). The mathematical model developed was subjected to statistical tests and the model is adequate for predicting the SO2 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.

  16. Analyses of microbial desulfurization reaction of alkylated dibenzothiophenes dissolved in oil phase.

    PubMed

    Okada, Hideki; Nomura, Nobuhiko; Nakahara, Tadaatsu; Saitoh, Koichi; Uchiyama, Hiroo; Maruhashi, Kenji

    2003-08-20

    The kinetics of the oil/water two-phase reaction system was analyzed, and the reaction was carried out with the desulfurization of alkylated dibenzothiophenes (Cx-DBTs) using the desulfurizing microorganism Mycobacterium sp. G3. In the water-phase reaction system, the desulfurization activities were constant with respect to species of Cx-DBTs as substrates. However, the desulfurization activities in the oil/water two-phase reaction system against DBT, 4,6-dimethyl DBT, 4,6-diethyl DBT, 4,6-dipropyl DBT, and 4,6-dibutyl DBT were 49.0, 45.9, 11.5, 1.35, and 0.00 micromol g DCW(-1) h(-1), respectively. The kinetic parameters for the degradation of DBT, 4,6-dimethyl DBT, and 4,6-diethyl DBT were also obtained (V(max) values 90.0, 68.7, and 22.7 micromol g DCW(-1) h(-1) and K(m) values 0.21, 0.70, and 3.03 mM, respectively). The reason for the decrease in activity against Cx-DBTs of high molecular weight was a decrease in the V(max) value and an increase in the K(m) value, the latter being a particularly serious problem. Furthermore, the hydrophobicity of the substrate was evaluated as the capacity factor measured by high-performance liquid chromatography (HPLC). The correlation between substrate hydrophobicity and desulfurization activity indicated that the desulfurization reaction in the oil/water two-phase reaction system is greatly influenced by the hydrophobicity of the substrates. In addition, the influence of the solvent on desulfurization activity was examined, and it was found that not only the hydrophobicity of substrates, but also that of solvents, affected the desulfurization reaction.

  17. 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

  18. Biocatalytic self-assembly of supramolecular charge-transfer nanostructures based on n-type semiconductor-appended peptides.

    PubMed

    Nalluri, Siva Krishna Mohan; Berdugo, Cristina; Javid, Nadeem; Frederix, Pim W J M; Ulijn, Rein V

    2014-06-01

    The reversible in situ formation of a self-assembly building block (naphthalenediimide (NDI)-dipeptide conjugate) by enzymatic condensation of NDI-functionalized tyrosine (NDI-Y) and phenylalanine-amide (F-NH2) to form NDI-YF-NH2 is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di-hydroxy/alkoxy naphthalene donors, efficient charge-transfer complexes are produced. The dynamic formation of NDI-YF-NH2 and electronic and H-bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free-energy minimization, are inherently self-healing and provide opportunities for the development of aqueous adaptive nanotechnology. PMID:24788665

  19. 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

  20. 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)

  1. Performance of titanium in flue gas desulfurization scrubber systems

    SciTech Connect

    Schutz, R.W.; Young, C.S.

    1985-09-01

    Findings of a continuing in situ flue gas desulfurization (FGD) scrubber exposure test program used to assess the performance of specific titanium alloys in corrosive inlet quench and outlet duct areas of FGD systems are reported and discussed. Spool rack exposures of four to nine months in power plant FGD and particulate scrubbers provided corrosion data for titanium alloys relative to the corrosion resistant alloys commonly considered for this service. Overall, Titanium Grade 2 and Grade 12 equalled or exceeded the corrosion resistance of the stainless steel and nickel base alloys tested. Titanium Grade 7 exhibited the best corrosion resistance in the wet/dry zone of the inlet quench of a closed-loop FGD scrubber. This performance is correlated with laboratory studies in the literature, and a mechanism is proposed to explain titanium's corrosion resistance.

  2. Recovery and recycling of limestone in LEC flue gas desulfurization

    SciTech Connect

    Gardner, N.C.; Adler, R.J.; Lin, Y.C.; Unger, M.E.; Lux, K.W. )

    1992-03-01

    Prudich et al. have proposed an attractive technology called Limestone Emission Control (LEC) for removing sulfur dioxide from flue gases. Beds of 1/8 inch wet limestone particles absorb the sulfur dioxide from the gases. Sulfates and sulfites deposit on the surfaces of the particles, limiting their utilization to about 20%. The unreacted portion of the limestone can be recovered by mechanical grinding and recycling, enabling high overall sorbent utilization. Favorable economic costs derive from small equipment, simplicity, and low sorbent cost. Our research concentrates on selecting and testing on a laboratory scale suitable candidate dry and wet grinding methods for recovering limestone in LEC flue from desulfurization. A wet grinding method based on the impeller fluidizer, a new type of slurry processor, receives special attention. The impeller fluidizer is a dosed cylindrical vessel with an impeller at one end. It combines the operations of wet grinding, washing, and transporting the spent and recovered limestone as an aqueous slurry.

  3. Oxidative desulfurization of Tufanbeyli coal by hydrogen peroxide solution

    SciTech Connect

    Guru, M.; Sarioz, B.V.; Cakanyildirim, C.

    2008-07-01

    It is becoming popular to use fossil fuels efficiently since the necessary energy is mostly supplied from fossil fuels. Altough there are high lignite reserves, high sulfur content limits the efficient use of them. In this article, we aimed to convert combustible sulfur in coal to non-combustible sulfate form in the ash by oxidizing it with a hydrogen peroxide solution. The parameters affecting the sulfur conversion were determined to be: hydrogen peroxide concentration, reaction time, mean particle size at constant room temperature and shaking rate. The maximum desulfurization efficiency reached was 74% of the original combustible sulfur with 15% (w/w) hydrogen peroxide solution, 12 hours of reaction time, and 0.25 mm mean particle size.

  4. 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.

  5. Recovery and recycling of limestone in LEC flue gas desulfurization. Final report, third year

    SciTech Connect

    Gardner, N.C.; Boo, J.Y.

    1993-12-20

    A potentially attractive flue gas desulfurization method called Limestone Emission Control (LEC) is currently being investigated by Prudich at Ohio University. In this process, beds of 1/8 inch limestone gravel particles absorb sulfur dioxide from flue gas. This forms sulfite and sulfate salts which coat limestone, blinding the surface and limiting utilization to 20%. Favorable economics can be generating when the unreacted portion of the limestone is recovered by mechanical grinding. This project is a wet method for grinding and recovering the spent limestone from the LEC process, utilizing an impeller fluidizer, a new type of slurry processor. It consists of a cylindrical vessel with an impeller at one end. The impeller generates sufficient pressure head to serve as a slurry pump. It combines the operation of wet grinding, washing, and transporting the spent and recovered limestone as an aqueous slurry. The objectives of the first two years were to operate fluidizer in a batch mode to carry grinding experiments, and to determine the removal of the sulfur coatings from the limestone when operating the fluidizer in a continuous mode. The main thrusts of the third year were to complete the grinding data and coordinate the data with reactivity determinations of the recovered limestone. Direct measurement of power requirements, operation of single impeller fluidizer, grinding of surface deposits and other methods of removing surface deposits have also been investigated along with sorption characteristics of recovered limestone, microscopic examination of the limestone surface, and limestone attrition.

  6. 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.

  7. Hybrid membrane with TiO2 based bio-catalytic nanoparticle suspension system for the degradation of bisphenol-A.

    PubMed

    Hou, Jingwei; Dong, Guangxi; Luu, Belinda; Sengpiel, Robert G; Ye, Yun; Wessling, Matthias; Chen, Vicki

    2014-10-01

    The removal of micropollutant in wastewater treatment has become a key environmental challenge for many industrialized countries. One approach is to use enzymes such as laccase for the degradation of micropollutants such as bisphenol-A. In this work, laccase was covalently immobilized on APTES modified TiO2 nanoparticles, and the effects of particle modification on the bio-catalytic performance were examined and optimized. These bio-catalytic particles were then suspended in a hybrid membrane reactor for BPA removal with good BPA degradation efficiency observed. Substantial improvement in laccase stability was achieved in the hybrid system compared with free laccase under simulated harsh industrial wastewater treatment conditions (such as a wide range of pH and presence of inhibitors). Kinetic study provided insight of the effect of immobilization on the bio-degradation reaction. PMID:25084046

  8. Stereoselective introduction of two chiral centers by a single diketoreductase: an efficient biocatalytic route for the synthesis of statin side chains.

    PubMed

    Wu, Xuri; Wang, Lili; Wang, Shuzhen; Chen, Yijun

    2010-06-01

    Statins, including atorvastatin (Lipitor), are the top-selling drugs in the world. The biocatalytic production of chiral side chains of statin drugs is of great interest to academia and industry. Stereoselective double reduction of a beta,delta-diketo ester catalyzed by a diketoreductase offers a simple and efficient route for the preparation of statin side chains. Comparison of different cofactor regeneration systems resulted in an easy and cost-effective process for this enzymatic reduction.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

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

    PubMed

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

    2008-03-01

    Semidry flue gas desulfurization with a rapidly hydrated sorbent was studied in a pilot-scale circulating fluidized bed (CFB) experimental facility. 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)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)2 particles and the fly ash particles, and the low cyclone separation efficiency for the fine Ca(OH)2 particles that fell off the sorbent particles. Therefore the actual recirculation rates of the active sorbent with Ca(OH)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.

  14. Adhesive carrier particles for rapidly hydrated sorbent for moderate-temperature dry flue gas desulfurization.

    PubMed

    Li, Yuan; You, Changfu; Song, Chenxing

    2010-06-15

    A rapidly hydrated sorbent for moderate-temperature dry flue gas desulfurization was prepared by rapidly hydrating adhesive carrier particles and lime. The circulation ash from a circulating fluidized bed boiler and chain boiler ash, both of which have rough surfaces with large specific surface areas and specific pore volumes, can improve the adhesion, abrasion resistance, and desulfurization characteristics of rapidly hydrated sorbent when used as the adhesive carrier particles. The adhesion ability of sorbent made from circulation ash is 67.4% higher than that of the existing rapidly hydrated sorbent made from fly ash, the abrasion ratio is 76.2% lower, and desulfurization ability is 14.1% higher. For sorbent made from chain boiler ash, the adhesion ability is increased by 74.7%, the desulfurization ability is increased by 30.3%, and abrasion ratio is decreased by 52.4%. The abrasion ratios of the sorbent made from circulation ash having various average diameters were all about 9%, and their desulfurization abilities were similar (approximately 150 mg/g). PMID:20481549

  15. Analyses of substrate specificity of the desulfurizing bacterium Mycobacterium sp. G3.

    PubMed

    Okada, Hideki; Nomura, Nobuhiko; Nakahara, Tadaatsu; Maruhashi, Kenji

    2002-01-01

    The substrate specificity of Mycobacterium sp. G3 with desulfurization activity against dibenzothiophene (DBT) was investigated. Desulfurization reactions were carried out using a concentrated cell suspension of G3. The conversion from 4,6-dipropyl DBT, one of the sulfur-containing compounds that is difficult to desulfurize in diesel oil, to 2-hydroxy-3,3'-dipropylbiphenyl as an end -product of the desulfurization reaction was found in the water reaction system and in the oil/water two-phase reaction system. 4,6-Dibutyl DBT and 4,6-dipentyl DBT were metabolized to the hydroxybiphenyl form via the sulfone form in the water reaction system. These results indicate that G3 has high membrane permeability and superior substrate specificity for high molecular weight alkyl DBTs, which are represented by 4,6-dipentyl DBT as C10-DBT. Furthermore, G3 could desulfurize diesel oil, and the sulfur concentration was decreased from 116 mg l(-1) to 48 mg l(-1) within 24 h.

  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. 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.

  18. Kinetics of hot-gas desulfurization sorbents for transport reactors

    SciTech Connect

    K.C. Kwon

    2000-01-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at elevated temperatures. Various metal oxide sorbents are formulated with metal oxides such as Fe, Co, Zn, and Ti. Initial reaction kinetics of formulated sorbents with hydrogen sulfide is studied in the presence of various amounts of moisture and hydrogen at various reaction temperatures. The objectives of this research are to study initial reaction kinetics for a sorbent-hydrogen sulfide heterogeneous reaction system, to investigate effects of concentrations of hydrogen sulfide, hydrogen, and moisture on dynamic absorption of H{sub 2}S into sorbents, to understand effects of space time of reaction gas mixtures on initial reaction kinetics of the sorbent-hydrogen sulfide system, and to evaluate effects of temperature and sorbent amounts on dynamic absorption of H{sub 2}S into sorbents. Experimental data on initial reaction kinetics of hydrogen sulfide with metal oxide sorbents were obtained with a 0.83-cm{sup 3} differential reactor. The reactivity of MCRH-67 sorbent and AHI-1 was examined. These sorbents were obtained from the Research Triangle Institute (RTI). The sorbents in the form of 70 {micro}m particles are reacted with 1,000--4,000 ppm hydrogen sulfide at 450--600 C. The range of space time of reaction gas mixtures is 0.03--0.09 s. The range of reaction duration is 4--14,400 s.

  19. Flue gas desulfurization (FGD) chemistry and analytical methods handbook

    SciTech Connect

    Noblett, J.G.; Burke, J.M.

    1990-08-01

    The purpose of this handbook is to provide a comprehensive guide to sampling, analytical, and physical test methods essential to the operation, maintenance, and understanding of flue gas desulfurization (FGD) system chemistry. EPRI sponsored the first edition of this three-volume report in response to the needs of electric utility personnel responsible for establishing and operating commercial FGD analytical laboratories. The second, revised editions of Volumes 1 and 2 were prompted by the results of research into various non-standard aspects of FGD system chemistry. Volume 1 of the handbook explains FGD system chemistry in the detail necessary to understand how the processes operate and how process performance indicators can be used to optimize system operation. Volume 2 includes 63 physical-testing and chemical-analysis methods for reagents, slurries, and solids, and information on the applicability of individual methods to specific FGD systems. Volume 3 contains instructions for FGD solution chemistry computer program designated by EPRI as FGDLIQEQ. Executable on IBM-compatible personal computers, this program calculates the concentrations (activities) of chemical species (ions) in scrubber liquor and can calculate driving forces for important chemical reactions such as S0{sub 2} absorption and calcium sulfite and sulfate precipitation. This program and selected chemical analyses will help an FGD system operator optimize system performance, prevent many potential process problems, and define solutions to existing problems. 22 refs., 17 figs., 28 tabs.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. Revegetation of flue gas desulfurization sludge pond disposal sites

    SciTech Connect

    Artiola, J.F.

    1994-12-01

    A comprehensive search of published literature was conducted to summarize research undertaken to date on revegetation of flue gas desulfurization (FGD) waste disposal ponds. A review of the physical and chemical properties of FGD sludges and wastes with similar characteristics is also included in order to determine the advantages and limitations of FGD sludge for plant growth. No specific guidelines have been developed for the revegetation of FGD sludge disposal sites. Survey studies showed that the wide-ranging composition of FGD wastes was determined primarily by the sulfur dioxide and other flue gas scrubbing processes used at powerplants. Sulfate rich (>90%CaSO{sub 4}) FGD sludges are physically and chemically more stable, and thus more amenable to revegetation. Because of lack of macronutrients and extremely limited microbial activity, FBD sludge ponds presented a poor plant growth environment without amendment. Studies showed the natural process of inoculation of the FGD sludge with soil microbes that promote plant growth be can after disposal but proceeded slowly. Revegetation studies reviewed showed that FGD sludges amended with soils supported a wider variety of plant species better and longer than abandoned FGD ponds. Two major types of plants have been successful in revegetation of FGD waste ponds and similar wastes: salt-tolerant plants and aquatic plants. A comprehensive list of plant species with potential for regetation of FGD sludge disposal pond sites is presented along with successful revegetation techniques.

  6. Hot coal gas desulfurization with manganese-based sorbents

    SciTech Connect

    Hepworth, M.T.; Ben-Slimane, R.

    1994-12-01

    The focus of work being performed on Hot Coal Gas Desulfurization at the Morgantown Energy Technology Center is primarily in the use of zinc ferrite and 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}) may be a viable alternative 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 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. Potential also exists for utilization of manganese at higher temperatures than zinc ferrite or zinc titanate. This annual topical 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.

  7. Hot coal gas desulfurization with manganese-based sorbents

    SciTech Connect

    Lynch, D.; Hepworth, M.T.

    1993-09-01

    The focus of work being performed on Hot Coal Gas Desulfurization is primarily in the use of zinc ferrite and zinc titanate sorbents; however, prior studies at the US Steel Fundamental Research Laboratories in Monroeville, PA, by E.T. Turkdogan indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt % ore + 25 wt % Al{sub 2}/O{sub 3}) may be a viable alternative 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 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. Potential also exists for utilization of manganese higher temperatures than zinc ferrite or zinc titanate. This presentation gives the thermodynamic background for consideration of manganese-based sorbents as an alternative to zinc ferrite. To date the work which has been in progress for nine months is limited at this stage to thermogravimetric testing of four formulations of manganese-alumina sorbents to determine the optimum conditions of pelletization and induration to produce reactive pellets.

  8. Hot coal gas desulfurization with manganese-based sorbents

    SciTech Connect

    Hepworth, M.T.

    1993-06-01

    The focus of work being performed on Hot Coal Gas Desulfurization is primarily in the use of zinc ferrite and zinc titanate sorbents; however, prior studies at the U.S. Steel Fundamental Research Laboratories in Monroeville, PA, by E.T. Turkdogan indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt% ore + 25 wt% Al{sub 2}O{sub 3}) may be a viable alternative 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 depletion for 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. Potential also exists for utilization of manganese higher temperatures than zinc ferrite or zinc titanate. This presentation give the thermodynamic background for consideration of manganese-based sorbents as an alternative to zinc ferrite. To date the work which has been in progress for nine months is limited at this stage to thermogravimetric testing of four formulations of manganese-alumina sorbents to determine the optimum conditions of pelletization and induration to produce reactive pellets.

  9. 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. PMID:23226147

  10. 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.

  11. 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.

  12. 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. PMID:23538118

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

    SciTech Connect

    Sotirchos, S.V.

    1989-01-01

    A research program is proposed for the investigation of the dependence of the sorptive capacity of metal/metal oxide desulfurization sorbents on their pore size distribution and their intraparticle diffusivity. Integrated reaction/adsorption systems, chromatographic and gravimetric, will be used for successive reactivity, adsorption, and well as diffusivity, measurements. Single particle models that have been developed by our research group for gas-solid reactions with solid product will be used as basis for experimental data analysis and development of a general mathematical model for fixed-bed desulfurization and sorbent regeneration.

  14. 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.

  15. Desulfurization of benzothiophene by the Gram-negative bacterium, Sinorhizobium sp. KT55.

    PubMed

    Tanaka, Y; Onaka, T; Matsui, T; Maruhashi, K; Kurane, R

    2001-09-01

    Sinorhizobium sp. KT55 was the first Gram-negative isolate to be capable of utilizing benzothiophene as the sole source of sulfur. By GC-MS analysis of metabolites of benzothiophene by this strain, benzothiophene sulfone, benzo[e][1,2]oxathiin S-oxide and o-hydroxystyrene were detected, suggesting that the benzothiophene desulfurization pathway of this strain is benzothiophene-->benzothiophene sulfoxide-->benzothiophene sulfone-->benzo[e][1,2]oxathiin S-oxide-->o-hydroxystyrene. Desulfurization activity of this strain was significantly repressed by methionine, cysteine, sulfate, dimethyl sulfoxide, and Casamino acids.

  16. 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.

  17. One-step synthesis of 2-keto-3-deoxy-d-gluconate by biocatalytic dehydration of d-gluconate.

    PubMed

    Matsubara, Kohei; Köhling, Rudi; Schönenberger, Bernhard; Kouril, Theresa; Esser, Dominik; Bräsen, Christopher; Siebers, Bettina; Wohlgemuth, Roland

    2014-12-10

    2-Keto-3-deoxy-sugar acids are key intermediates of central metabolism and integral constituents of bacterial (lipo)polysaccharides and cell wall components and are therefore continuously and highly demanded in related research fields. The stereospecific chemical synthesis of chiral 2-keto-deoxy-sugar acids involves a multitude of reaction steps, while in metabolic pathways only few conversions lead to the same 2-keto-3-deoxy sugar acids from easily available carbohydrate precursors. Here we present a straightforward and highly economic one-step biocatalytic synthesis procedure of 2-keto-3-deoxy-d-gluconate (KDG) from d-gluconate using recombinant gluconate dehydratase (GAD) from the hyperthermophilic crenarchaeon Thermoproteus tenax. This method is highly advantageous to KDG production schemes described so far for several reasons: (i) the d-gluconate is completely converted to stereochemically pure D-KDG without side-product formation, (ii) the final KDG yield is approximately 90%, (iii) the newly developed quantitative and qualitative LC-MS analysis method enabled the simultaneous detection of d-gluconate and KDG and (iv) the T. tenax GAD as biocatalyst can be provided by a simple and rapid procedure involving only two precipitation steps. The described utilization of dehydratases for 2-keto-3-deoxy sugar acid syntheses represents a highly resource-efficient one-step preparation and offers potential short synthetic routes toward a broad range of 2-keto-3-deoxy sugar acids and their derivatives.

  18. Cofactor Specificity Engineering of Streptococcus mutans NADH Oxidase 2 for NAD(P)(+) Regeneration in Biocatalytic Oxidations.

    PubMed

    Petschacher, Barbara; Staunig, Nicole; Müller, Monika; Schürmann, Martin; Mink, Daniel; De Wildeman, Stefaan; Gruber, Karl; Glieder, Anton

    2014-01-01

    Soluble water-forming NAD(P)H oxidases constitute a promising NAD(P)(+) regeneration method as they only need oxygen as cosubstrate and produce water as sole byproduct. Moreover, the thermodynamic equilibrium of O2 reduction is a valuable driving force for mostly energetically unfavorable biocatalytic oxidations. Here, we present the generation of an NAD(P)H oxidase with high activity for both cofactors, NADH and NADPH. Starting from the strictly NADH specific water-forming Streptococcus mutans NADH oxidase 2 several rationally designed cofactor binding site mutants were created and kinetic values for NADH and NADPH conversion were determined. Double mutant 193R194H showed comparable high rates and low K m values for NADPH (k cat 20 s(-1), K m 6 µM) and NADH (k cat 25 s(-1), K m 9 µM) with retention of 70% of wild type activity towards NADH. Moreover, by screening of a SeSaM library S. mutans NADH oxidase 2 variants showing predominantly NADPH activity were found, giving further insight into cofactor binding site architecture. Applicability for cofactor regeneration is shown for coupling with alcohol dehydrogenase from Sphyngobium yanoikuyae for 2-heptanone production.

  19. Biocatalytic Properties and Structural Analysis of Eugenol Oxidase from Rhodococcus jostii RHA1: A Versatile Oxidative Biocatalyst.

    PubMed

    Nguyen, Quoc-Thai; de Gonzalo, Gonzalo; Binda, Claudia; Rioz-Martínez, Ana; Mattevi, Andrea; Fraaije, Marco W

    2016-07-15

    Eugenol oxidase (EUGO) from Rhodococcus jostii RHA1 had previously been shown to convert only a limited set of phenolic compounds. In this study, we have explored the biocatalytic potential of this flavoprotein oxidase, resulting in a broadened substrate scope and a deeper insight into its structural properties. In addition to the oxidation of vanillyl alcohol and the hydroxylation of eugenol, EUGO can efficiently catalyze the dehydrogenation of various phenolic ketones and the selective oxidation of a racemic secondary alcohol-4-(1-hydroxyethyl)-2-methoxyphenol. EUGO was also found to perform the kinetic resolution of a racemic secondary alcohol. Crystal structures of the enzyme in complexes with isoeugenol, coniferyl alcohol, vanillin, and benzoate have been determined. The catalytic center is a remarkable solvent-inaccessible cavity on the si side of the flavin cofactor. Structural comparison with vanillyl alcohol oxidase from Penicillium simplicissimum highlights a few localized changes that correlate with the selectivity of EUGO for phenolic substrates bearing relatively small p-substituents while tolerating o-methoxy substituents. PMID:27123962

  20. Non-water miscible ionic liquid improves biocatalytic production of geranyl glucoside with Escherichia coli overexpressing a glucosyltransferase.

    PubMed

    Schmideder, Andreas; Priebe, Xenia; Rubenbauer, Mark; Hoffmann, Thomas; Huang, Fong-Chin; Schwab, Wilfried; Weuster-Botz, Dirk

    2016-09-01

    Whole cells of Escherichia coli overexpressing a glucosyltransferase from Vitis vinifera were used for the glucosylation of geraniol to geranyl glucoside. A high cell density cultivation process for the production of whole-cell biocatalysts was developed, gaining a dry cell mass concentration of up to 67.6 ± 1.2 g L(-1) and a glucosyltransferase concentration of up to 2.7 ± 0.1 g protein L(-1) within a process time of 48 h. Whole-cell batch biotransformations in milliliter-scale stirred-tank bioreactors showed highest conversion of geraniol at pH 7.0 although the pH optimum of the purified glucosyltransferase was at pH 8.5. The biocatalytic batch process performance was improved significantly by the addition of a water-immiscible ionic liquid (N-hexylpyridinium bis(trifluoromethylsulfonyl)imid) for in situ substrate supply. The so far highest final geranyl glucoside concentration (291 ± 9 mg L(-1)) and conversion (71 ± 2 %) reported for whole-cell biotransformations of geraniol were achieved with 5 % (v/v) of the ionic liquid. PMID:27142377

  1. Biocatalytic potential of lipase from Staphylococcus sp. MS1 for transesterification of jatropha oil into fatty acid methyl esters.

    PubMed

    Sharma, Monika; Singh, Shelley Sardul; Maan, Pratibha; Sharma, Rohit

    2014-11-01

    An extracellular lipase producing isolate Staphylococcus sp. MS1 was optimized for lipase production and its biocatalytic potential was assessed. Medium with tributyrin (0.25 %) and without any exogenous inorganic nitrogen source was found to be optimum for lipase production from Staphylococcus sp. MS1. The optimum pH and temperature for lipase production were found to be pH 7 and 37 °C respectively, showing lipase activity of 37.91 U. It showed good lipase production at pH 6-8. The lipase was found to be stable in organic solvents like hexane and petroleum ether, showing 98 and 88 % residual activity respectively. The biotransformation using the concentrated enzyme in petroleum ether resulted in the synthesis of fatty acid methyl esters like methyl oleate, methyl palmitate and methyl stearate. Thus, the lipase under study has got the potential to bring about transesterification of oils into methyl esters which can be exploited for various biotechnological applications. PMID:25115850

  2. 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

  3. Adsorption of enzymes to stimuli-responsive polymer brushes: Influence of brush conformation on adsorbed amount and biocatalytic activity.

    PubMed

    Koenig, Meike; Bittrich, Eva; König, Ulla; Rajeev, Bhadra Lakshmi; Müller, Martin; Eichhorn, Klaus-Jochen; Thomas, Sabu; Stamm, Manfred; Uhlmann, Petra

    2016-10-01

    Polyelectrolyte brushes can be utilized to immobilize enzymes on macroscopic surfaces. This report investigates the influence of the pH value of the surrounding medium on the amount and the activity of enzymes adsorbed to poly(2-vinylpyridine) and poly(acrylic acid) brushes, as well as the creation of thermoresponsive biocatalytically active coatings via the adsorption of enzymes onto a mixed brush consisting of a polyelectrolyte and temperature-sensitive poly(N-isopropylacryl amide). Spectroscopic ellipsometry and attenuated total reflection-Fourier transform infrared spectroscopy are used to monitor the adsorption process. Additionally, infrared spectra are evaluated in terms of the secondary structure of the enzymes. Glucose oxidase is used as a model enzyme, where the enzymatic activity is measured after different adsorption conditions. Poly(acrylic acid) brushes generally adsorb larger amounts of enzyme, while less glucose oxidase is found on poly(2-vinylpyridine), which however exhibits higher specific activity. This difference in activity could be attributed to a difference in secondary structure of the adsorbed enzyme. For glucose oxidase adsorbed to mixed brushes, switching of enzymatic activity between an active state at 20°C and a less active state at 40°C as compared to the free enzyme in solution is observed. However, this switching is strongly depending on pH in mixed brushes of poly(acrylic acid) and poly(N-isopropylacryl amide) due to interactions between the polymers.

  4. Ultrasensitive photoelectrochemical immunoassay of antibody against tumor-associated carbohydrate antigen amplified by functionalized graphene derivates and enzymatic biocatalytic precipitation.

    PubMed

    Zhang, Xiaoru; Liu, Mingshuai; Mao, Yaning; Xu, Yunpeng; Niu, Shuyan

    2014-09-15

    Tumor-associated carbohydrate antigens (TACAs) are often found on the surface of cancer cells. The determination of the carbohydrate components of glycoconjugates is challenging because of the chemical complexity of glycan chains. Through monitoring corresponding antibody, we can get a good solution for clinical diagnosis. Here breast tumor-associated carbohydrate antigens Tn were used as a model and a new photoelectrochemical biosensor for ultrasensitive detection of antibody against Tn was developed. To enhance the sensitivity, both graphene oxide and graphene were used during the construction of biosensor. Through the formation of immunocomplex and the insoluble biocatalytic precipitation (BCP) product, photocurrent intensity was decreased greatly and the antibody could be detected from 0.5 to 500 pg/mL with a detection limit of 1.0×10(-13) g/mL. At the same time, the developed biosensor showed acceptable selectivity and could be used in the complex matrix. Compared with the traditional glycoarray method, this PEC method is more sensitive (5 orders of magnitude), and thus provides another platform to monitor the immune response to carbohydrate epitopes at different stages during differentiation, metastasis, or treatment.

  5. Adsorption of enzymes to stimuli-responsive polymer brushes: Influence of brush conformation on adsorbed amount and biocatalytic activity.

    PubMed

    Koenig, Meike; Bittrich, Eva; König, Ulla; Rajeev, Bhadra Lakshmi; Müller, Martin; Eichhorn, Klaus-Jochen; Thomas, Sabu; Stamm, Manfred; Uhlmann, Petra

    2016-10-01

    Polyelectrolyte brushes can be utilized to immobilize enzymes on macroscopic surfaces. This report investigates the influence of the pH value of the surrounding medium on the amount and the activity of enzymes adsorbed to poly(2-vinylpyridine) and poly(acrylic acid) brushes, as well as the creation of thermoresponsive biocatalytically active coatings via the adsorption of enzymes onto a mixed brush consisting of a polyelectrolyte and temperature-sensitive poly(N-isopropylacryl amide). Spectroscopic ellipsometry and attenuated total reflection-Fourier transform infrared spectroscopy are used to monitor the adsorption process. Additionally, infrared spectra are evaluated in terms of the secondary structure of the enzymes. Glucose oxidase is used as a model enzyme, where the enzymatic activity is measured after different adsorption conditions. Poly(acrylic acid) brushes generally adsorb larger amounts of enzyme, while less glucose oxidase is found on poly(2-vinylpyridine), which however exhibits higher specific activity. This difference in activity could be attributed to a difference in secondary structure of the adsorbed enzyme. For glucose oxidase adsorbed to mixed brushes, switching of enzymatic activity between an active state at 20°C and a less active state at 40°C as compared to the free enzyme in solution is observed. However, this switching is strongly depending on pH in mixed brushes of poly(acrylic acid) and poly(N-isopropylacryl amide) due to interactions between the polymers. PMID:27447452

  6. 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.

  7. 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...

  8. 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...

  9. 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...

  10. 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.

  11. Enhancement and stabilization of desulfurization activity of Rhodococcus erythropolis KA2-5-1 by feeding ethanol and sulfur components.

    PubMed

    Yoshikawa, Osamu; Ishii, Yoshitaka; Koizumi, Ken-Ichi; Ohshiro, Takashi; Izumi, Yoshikazu; Maruhashi, Kenji

    2002-01-01

    We developed a fed-batch culture system fed with ethanol and restricted amounts of sulfur compounds to enhance and stabilize the desulfurizing activity in bacterial cells. In this system using dibenzothiophene (DBT) as the sole sulfur source, a desulfurizing bacterium Rhodococcus erythropolis KA2-5-1 cultivated with small amounts of sulfur showed stable desulfurizing activity and a low rate of growth. However, the cells cultured with excess amounts of sulfur showed unstable activity and a high growth rate. DBT had disadvantages as a sulfur source for cultivation because it is immiscible with water and toxic to cells. We then investigated water-soluble sulfur compounds for use as the sole sulfur source for the cultivation of R. erythropolis KA2-5-1 with desulfurizing activity, and found 2-aminoethanesulfonic acid to be the most effective. When 2-aminoethanesulfonic acid was used instead of DBT as the sole sulfur source in the fed-batch fermentation system, R. erythropolis KA2-5-1 showed the highest desulfurizing activity, 111 mmol of 2-HBP/kg-cells/h, a high growth rate (mu = 0.37/h) and a final cell concentration of 20.0 g-dry cells/l during 89 h of cultivation. The production levels of the desulfurizing enzymes in the bacterial cells cultivated with DBT or 2-aminoethanesulfonic acid were evaluated by immunoblot analysis with specific antisera, indicating that the same quantity of desulfurizing enzymes was expressed in both cases.

  12. Dibenzothiophene desulfurization capability and evolutionary divergence of newly isolated bacteria.

    PubMed

    Akhtar, Nasrin; Ghauri, Muhammad A; Akhtar, Kalsoom

    2016-08-01

    Metabolically microorganisms are diverse, and they are capable of transforming almost every known group of chemical compounds present in coal and oil in various forms. In this milieu, one of the important microbial metabolic processes is the biodesulfurization [cleavage of carbon-sulfur (C-S) bond] of thiophenic compounds, such as dibenzothiophene (DBT), which is the most abundant form of organic sulfur present in fossil fuels. In the current study, ten newly isolated bacterial isolates, designated as species of genera Gordonia, Amycolatopsis, Microbacterium and Mycobacterium, were enriched from different samples in the presence of DBT as a sole source of organic sulfur. The HPLC analysis of the DBT grown cultures indicated the consumption of DBT and accumulation of 2-hydroxybiphenyl (2-HBP). Detection of 2-HBP, a marker metabolite of 4S (sulfoxide-sulfone-sulfinate-sulfate) pathway, suggested that the newly isolated strains harbored metabolic activity for DBT desulfurization through the cleavage of C-S bond. The maximum 2-HBP formation rate was 3.5 µmol/g dry cell weight (DCW)/h. The phylogenetic analysis of the new isolates showed that they had diverse distribution within the phylogenetic tree and formed distinct clusters, suggesting that they might represent strains of already reported species or they were altogether new species. Estimates of evolutionary divergence showed high level of nucleotide divergence between the isolates within the same genus. The new isolates were able to use a range of heterocyclic sulfur compounds, thus making them suitable candidates for a robust biodesulfurization system for fossil fuels. PMID:26973057

  13. 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.

  14. Adsorptive desulfurization and denitrogenation using metal-organic frameworks.

    PubMed

    Ahmed, Imteaz; Jhung, Sung Hwa

    2016-01-15

    With the increasing worldwide demand for energy, utilization of fossil fuels is increasing proportionally. Additionally, new and unconventional energy sources are also being utilized at an increasing rate day-by-day. These sources, along with some industrial processes, result in the exposal of several sulfur- and nitrogen-containing compounds (SCCs and NCCs, respectively) to the environment, and the exposure is one of the greatest environmental threats in the recent years. Although, several methods were established for the removal of these pollutants during the last few decades, recent advancements in adsorptive desulfurization and denitrogenation (ADS and ADN, respectively) with metal-organic frameworks (MOFs) make this the most promising and remarkable method. Therefore, many research groups are currently involved with ADS and ADN with MOFs, and the results are improving gradually by modifying the MOF adsorbents according to several specific adsorption mechanisms. In this review, ADS and ADN studies are thoroughly discussed for both liquid-phase and gas-phase adsorption. The MOF modification procedures, which are important for improved adsorption, are also described. To improve the knowledge among the scientific community, it is very important to understand the detailed chemistry and mechanism involved in a chemical process, which also creates the possibility and pathway for further developments in research and applications. Therefore, the mechanisms related to the adsorption procedures are also discussed in detail. From this review, it can be expected that the scientific community will obtain an understanding of the current state of ADS and ADN, their importance, and some encouragement and insight to take the research knowledge base to a higher level. PMID:26368800

  15. Regeneration of sodium wastes from flue gas desulfurization processes

    SciTech Connect

    Haynes, H.W. Jr.; Ukidwe, A.A.

    1995-12-31

    The damaging effects that sulfur dioxide emissions are having on the environment are well documented and acknowledged by most scientists, policy makers, and the public at large. These emissions stem primarily from electric utilities and industrial plants with relatively little contribution from the transportation sector. In order to prevent additional environmental damage, clean air legislation has been passed by Congress culminating in the Clean Air Act Amendments of 1990. Ultimately, this legislation will cut sulfur dioxide emissions in half from 1980 levels, and substantially reduce nitrogen oxides emissions from electric utility plants. This legislation should therefore result in a cleaner environment than we have today. Title IV of the Clean Air Act sets as its primary goal the reduction of annual SO{sub 2} emissions by 10 million tons below 1980 levels. Phase I of the program, which begins this year, will affect 110 utility plants in mostly Midwestern and eastern states. Phase II, which begins in the year 2000, tightens the annual emissions allowances on these large, higher emitting plants and also sets controls on smaller units with capacities of greater than 25 megawatts and on all new utility plants. It is estimated that 2,200 plants nationwide will be affected by Phase II. In many cases, Phase I compliance can be met by coupling allowance trading with the blending of low sulfur western coals and regional coals. But there will be other cases in which stack gas cleanup will be the economically most attractive option. Phase II compliance will require virtually all utilities to install some form of flue gas desulfurization equipment. Retrofitting will therefore become of increasing importance as Phase II is implemented.

  16. Adsorptive desulfurization and denitrogenation using metal-organic frameworks.

    PubMed

    Ahmed, Imteaz; Jhung, Sung Hwa

    2016-01-15

    With the increasing worldwide demand for energy, utilization of fossil fuels is increasing proportionally. Additionally, new and unconventional energy sources are also being utilized at an increasing rate day-by-day. These sources, along with some industrial processes, result in the exposal of several sulfur- and nitrogen-containing compounds (SCCs and NCCs, respectively) to the environment, and the exposure is one of the greatest environmental threats in the recent years. Although, several methods were established for the removal of these pollutants during the last few decades, recent advancements in adsorptive desulfurization and denitrogenation (ADS and ADN, respectively) with metal-organic frameworks (MOFs) make this the most promising and remarkable method. Therefore, many research groups are currently involved with ADS and ADN with MOFs, and the results are improving gradually by modifying the MOF adsorbents according to several specific adsorption mechanisms. In this review, ADS and ADN studies are thoroughly discussed for both liquid-phase and gas-phase adsorption. The MOF modification procedures, which are important for improved adsorption, are also described. To improve the knowledge among the scientific community, it is very important to understand the detailed chemistry and mechanism involved in a chemical process, which also creates the possibility and pathway for further developments in research and applications. Therefore, the mechanisms related to the adsorption procedures are also discussed in detail. From this review, it can be expected that the scientific community will obtain an understanding of the current state of ADS and ADN, their importance, and some encouragement and insight to take the research knowledge base to a higher level.

  17. 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.

  18. Efficient biocatalytic synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol by a newly isolated Trichoderma asperellum ZJPH0810 using dual cosubstrate: ethanol and glycerol.

    PubMed

    Li, Jun; Wang, Pu; He, Jun-Yao; Huang, Jin; Tang, Jun

    2013-08-01

    (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol is a crucial intermediate for the synthesis of Aprepitant. An efficient biocatalytic process for (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol was developed via the asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone, catalyzed by whole cells of newly isolated Trichoderma asperellum ZJPH0810 using ethanol and glycerol as dual cosubstrate for cofactor recycling. A fungal strain ZJPH0810, showing asymmetric biocatalytic activity of 3,5-bis(trifluoromethyl) acetophenone to its corresponding (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol, was isolated from a soil sample. Based on its morphological and physiological characteristics and internal transcribed spacer sequence, this isolate was identified as T. asperellum ZJPH0810, which afforded an NADH-dependent (R)-stereospecific carbonyl reductase and was a promising biocatalyst for the synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol. Some key reaction parameters involved in the bioreduction catalyzed by T. asperellum ZJPH0810 were subsequently optimized. The effectiveness of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol production was significantly enhanced by employing a novel dual cosubstrate-coupled system for cofactor recycling. The established efficient bioreduction system contained 50 mM of 3,5-bis(trifluoromethyl) acetophenone and 60 g l(-1) of resting cells, employing ethanol (6.0 %, v/v) and glycerol (0.5 %, v/v) as dual cosubstrate. The bioreduction was performed in distilled water medium, at 30 °C and 200 rpm. Under the above conditions, a best yield of 93.4 % was obtained, which is nearly a 3.5-fold increase in contrast to no addition of cosubstrate. The ee value of the product reached above 98 %. This biocatalytic process shows great potential in the production of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol, a valuable chiral building block in the pharmaceutical industry.

  19. Ultrasound-promoted chemical desulfurization of Illinois coals. Final technical report, September 1, 1990--August 31, 1991

    SciTech Connect

    Chao, S.S.

    1991-12-31

    The overall objectives of the program were to investigate the use of ultrasound to promote coal desulfurization reactions and to evaluate chemical coal desulfurization schemes under mild conditions through a fundamental understanding of their reaction mechanisms and kinetics. The ultimate goal was to develop an economically feasible mild chemical process to reduce the total sulfur content of Illinois Basin Coals, while retaining their original physical characteristics, such as calorific value and volatile matter content. During the program, potential chemical reactions with coal were surveyed under various ultrasonic irradiation conditions for desulfurization, to formulate preliminary reaction pathways, and to select a few of the more promising chemical processes for more extensive study.

  20. 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.

  1. Recombinant Pseudomonas putida carrying both the dsz and hcu genes can desulfurize dibenzothiophene in n-tetradecane.

    PubMed

    Noda, Ken-ichi; Watanabe, Kimiko; Maruhashi, Kenji

    2003-07-01

    Pseudomonas putida IFO13696, a recombinant strain with dsz desulfurization genes, desulfurized dibenzothiophene (DBT) in water but not in n-tetradecane. By introducing into this recombinant strain the hcuABC genes that take part in the uptake of DBT in the oil phase into the cell, 82% of 1 mM DBT in n-tetradecane was degraded in 24 h by resting cells. The products of hcuABC genes thus acted in the uptake of DBT in n-tetradecane into the cells and were effective in desulfurization of DBT in the hydrocarbon phase.

  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. Integration and testing of hot desulfurization and entrained-flow gasification for power generation systems

    SciTech Connect

    Robin, A.M.; Kassman, J.S.; Leininger, T.F.; Wolfenbarger, J.K.; Wu, C.M.; Yang, P.P.

    1991-09-01

    This second Topical Report describes the work that was completed between January 1, 1989 and December 31, 1990 in a Cooperative Agreement between Texaco and the US Department of Energy that began on September 30, 1987. During the period that is covered in this report, the development and optimization of in-situ and external desulfurization processes were pursued. The research effort included bench scale testing, PDU scoping tests, process economic studies and advanced instrument testing. Two bench scale studies were performed at the Research Triangle Institute with zinc titanate sorbent to obtain data on its cycle life, sulfur capacity, durability and the effect of chlorides. These studies quantify sulfur capture during simulated air and oxygen-blown gasification for two zinc titanate formulations. Eight PDU runs for a total of 20 days of operation were conducted to evaluate the performance of candidate sorbents for both in-situ and external desulfurization. A total of 47 tests were completed with oxygen and air-blown gasification. Candidate sorbents included iron oxide for in-situ desulfurization and calcium based and mixed metal oxides for external desulfurization. Gasifier performance and sorbent sulfur capture are compared for both air-blown and oxygen-blown operation.

  4. Deep Desulfurization of Extensively Hydrodesulfurized Middle Distillate Oil by Rhodococcus sp. Strain ECRD-1

    PubMed Central

    Grossman, M. J.; Lee, M. K.; Prince, R. C.; Minak-Bernero, V.; George, G. N.; Pickering, I. J.

    2001-01-01

    Dibenzothiophene (DBT), and in particular substituted DBTs, are resistant to hydrodesulfurization (HDS) and can persist in fuels even after aggressive HDS treatment. Treatment by Rhodococcus sp. strain ECRD-1 of a middle distillate oil whose sulfur content was virtually all substituted DBTs produced extensive desulfurization and a sulfur level of 56 ppm. PMID:11282654

  5. 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.

  6. Catalyst for the desulfurization of industrial waste gases and process for its preparation

    SciTech Connect

    Dupin, T.

    1984-11-27

    Industrial waste gases containing objectionable/polluting compounds of sulfur, e.g., H/sub 2/S, SO/sub 2/ and such organosulfur 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.

  7. Effects of fluidized gas desulfurization (FGD) gypsum on non-target freshwater and sediment dwelling organims

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fluidized gas desulfurization gypsum is a popular agricultural soil amendment used to increase calcium and sulfur contents, and reduce aluminum toxicity. Due to its surface application in conservation tillage systems and high solubility, the soluble components of gypsum may be transferred with agri...

  8. 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....

  9. 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...

  10. o-Iodoxybenzoic acid mediated oxidative desulfurization initiated domino reactions for synthesis of azoles.

    PubMed

    Chaudhari, Pramod S; Pathare, Sagar P; Akamanchi, Krishnacharaya G

    2012-04-20

    A systematic exploration of thiophilic ability of o-iodoxybenzoic acid (IBX) for oxidative desulfurization to trigger domino reactions leading to new methodologies for synthesis of different azoles is described. A variety of highly substituted oxadiazoles, thiadiazoles, triazoles, and tetrazoles have been successfully synthesized in good to excellent yields, starting from readily accessible thiosemicarbazides, bis-diarylthiourea, 1,3-disubtituted thiourea, and thioamides.

  11. DEVELOPMENT OF INFRARED METHODS FOR CHARACTERIZATION OF INORGANIC SULFUR SPECIES RELATED TO INJECTION DESULFURIZATION PROCESSES

    EPA Science Inventory

    Current methods designed to control and reduce the amount of sulfur dioxide emitted into the atmosphere from coal-fired power plants and factories rely upon the reaction between SO2 and alkaline earth compounds and are called flue gas desulfurization (FGD) processes. Of these met...

  12. 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.

  13. Localized corrosion of stainless steels and nickel alloys in flue gas desulfurization environments

    SciTech Connect

    Phull, B.S.; Lee, T.S.

    1986-08-01

    The results of a planned interval test of 90 days duration in a model flue gas desulfurization system are discussed. Tests were conducted in a high chloride, limestone slurry-based environment containing fluoride and flyash. Corrosion in absorber and outlet duct zones is outlined in terms of relative tendencies of localized corrosion propagation for six alloys.

  14. 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...

  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. Isolation of a recombinant desulfurizing 4,6-diproply dibenzothiophene in n-tetradecane.

    PubMed

    Noda, Ken-Ichi; Watanabe, Kimiko; Maruhashi, Kenji

    2003-01-01

    Rhodococcus erythropolis strain KA2-5-1 is unable to desulfurize 4,6-dipropyl dibenzothiophene (DBT) in the oil phase. The dsz desulfurization gene cluster from R. erythropolis strain KA2-5-1 was transferred into 22 rhodococcal and mycobacterial strains using a transposon-transposase complex. The recombinant strain MR65, from Mycobacterium sp. NCIMB10403, was able to grow on a minimal medium supplemented with 1.0 mM 4,6-dipropyl DBT in n-tetradecane (50%, v v ) as the sole sulfur source. Resting cells of recombinant strain MR65 could desulfurize 68 mg l- of sulfur in light gas oil (LGO) containing 126 mg sulfur l-. Strain MR65 had about 1.5-times the LGO desulfurization activity of R. erythropolis strain KA2-5-1. The application of a recombinant, which is able to utilize 4,6-dipropyl DBT in the oil phase, was effective in enhancing LGO biodesulfurization.

  17. Improvement of desulfurization activity in Rhodococcus erythropolis KA2-5-1 by genetic engineering.

    PubMed

    Hirasawa, K; Ishii, Y; Kobayashi, M; Koizumi, K; Maruhashi, K

    2001-02-01

    Rhodococcus erythropolis KA2-5-1 can desulfurize dibenzothiophene (DBT) into 2-hydroxybiphenyl. A cryptic plasmid, pRC4, which was derived from R. rhodochrous IFO3338, was combined with an Escherichia coli vector to construct an E. coli-Rhodococcus shuttle vector. The complete nucleotide sequence of 2582-bp pRC4 was analyzed. Based on the characteristics of its putative replication genes, pRC4 was assigned to the family of pAL5000-related replicons. The desulfurization gene cluster, dszABC, and the related reductase gene, dszD, cloned from KA2-5-1, were reintroduced into KA2-5-1 and efficiently expressed. The DBT desulfurization ability of the transformant carrying two dszABC clusters and one dszD on the vector was about 4-fold higher than that of the parent strain, and the transformant also showed improved desulfurization activity for light gas oil (LGO). Sulfur components in LGO before and after the reaction were analyzed with gas chromatography-atomic emission detection.

  18. A cyclic (alkyl)(amido)carbene: synthesis, study and utility as a desulfurization reagent.

    PubMed

    McCarty, Zachary R; Lastovickova, Dominika N; Bielawski, Christopher W

    2016-04-01

    The synthesis and study of a cyclic (alkyl)(amido)carbene is described. The carbene was found to undergo C-H insertion at low temperatures, formed cyclopropenes upon exposure to alkynes, and facilitated desulfurization reactions. Spectroscopic studies revealed that the carbene is strongly π-accepting but retains a complimentary degree of σ-donating properties. PMID:27010415

  19. 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...

  20. 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.

  1. Cofactor recycling mechanism in asymmetric biocatalytic reduction of carbonyl compounds mediated by yeast: which is the efficient electron donor?

    PubMed

    Zhang, Ben-Li; Pionnier, Sébastien

    2003-08-01

    In asymmetric reduction of carbonyl compounds mediated by microorganisms, the cofactors that transfer hydride should be regenerated by using a recycling system. In most cases, this recycling system consists of carbohydrate molecules, especially glucose or sucrose. Other molecules such as ethanol and acetate have been used as electron donors too. The reduction can even be conducted without added electron donors. To improve biocatalytic synthesis, it is important to understand the cofactor recycling mechanism. In this work, the hydride-transfer mechanism in cofactor regeneration, which takes place in bioreduction mediated by yeast, was studied by means of an isotope tracing technique. The results show that, when glucose was used, the NADH involved in the glycolysis was consumed directly in the formation of ethanol and was not used in the bioreduction. Hence, the regeneration of cofactors in the reduction is not coupled with glycolysis. Nevertheless, glucose is an efficient electron donor that transfers hydride through the hexose monophosphate (HMP) pathway in which the main hydrogen source is C-1 and C-3 hydrogen of glucose. Ethanol is not a good electron donor, since, when it was used, only a small quantity of hydrogen was transferred from this molecule, and the main hydrogen source was water. Therefore, the ethanol oxidation pathway may not be efficient. In the absence of added auxiliary substrates, the yeast cells may use electron donors stored in its cellules. However, in this case we observed that the main hydrogen source for cofactor recycling was water, while only very few hydrogen atoms were from unexchangeable sites. This is similar to the case in which ethanol is used, and is in contradiction with the HMP pathway if stored glucose was the electron donor. The question that remains to be investigated is "what is the efficient electron donor recycling mechanism in the yeast cellules?" PMID:12898687

  2. 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.

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Permitting and solid waste management issues for the Bailly Station wet limestone Advanced Flue Gas Desulfurization (AFGD) system

    SciTech Connect

    Bolinsky, F.T. ); Ross, J. ); Dennis, D.S. . Stearns-Roger Div.); Huston, J.S. )

    1991-01-01

    Pure Air (a general partnership between Air Products and Chemicals, Inc., and Mitsubishi Heavy Industries America, Inc.). is constructing a wet limestone co-current advanced flue gas desulfurization (AFGD) system that has technological and commercial advantages over conventional FGD systems in the United States. The AFGD system is being installed at the Northern Indiana Public Service Company's Bailly Generating Station near Gary, Indiana. The AFGD system is scheduled to be operational by the Summer, 1992. The AFGD system will remove at least 90 percent of the sulfur dioxide (SO{sub 2}) in the flue gas from Boilers 7 and 8 at the Station while burning 3.2 percent sulfur coal. Also as part of testing the AFGD system, 95 percent removal of SO{sub 2} will be demonstrated on coals containing up to 4.5 percent sulfur. At the same time that SO{sub 2} is removed from the flue gas, a gypsum by-product will be produced which will be used for wallboard manufacturing. Since the AFGD system is a pollution control device, one would expect its installation to be received favorably by the public and regulatory agencies. Although the project was well received by regulatory agencies, on public group (Save the Dunes Council) was initially concerned since the project is located adjacent to the Indiana Dunes National Lakeshore. The purpose of this paper is to describe the project team's experiences in obtaining permits/approvals from regulatory agencies and in dealing with the public. 1 ref., 1 fig., 2 tabs.

  13. 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

  14. Hydrogen sulfide removal from livestock biogas by a farm-scale bio-filter desulfurization system.

    PubMed

    Su, J-J; Chang, Y-C; Chen, Y-J; Chang, K-C; Lee, S-Y

    2013-01-01

    A farm-scale biogas desulfurization system was designed and tested for H2S removal efficiency from livestock biogas. This work assesses the H2S removal efficiency of a novel farm-scale biogas bio-desulfurization system (BBS) operated for 350 days on a 1,000-head pig farm. Experimental data demonstrated that suitable humidity and temperature can help sulfur-oxidizing bacteria to form active bio-films on the bio-carriers. The daily average removal rate increased to 879.16 from 337.75 g-H2S/d with an average inlet H2S concentration of 4,691 ± 1,532 mg/m(3) in biogas. Thus, the overall (0-350 days) average H2S removal efficiency exceeded 93%. The proposed BBS overcomes limitations of H2S in biogas when utilizing pig farm biogas for power generation and other applications.

  15. Radiation-induced desulfurization of Arabian crude oil and straight-run diesel

    NASA Astrophysics Data System (ADS)

    Basfar, A. A.; Mohamed, K. A.

    2011-11-01

    Radiation-induced desulfurization of four types of Arabian crude oils (heavy, medium, light and extra light) and straight-run diesel (SRD) was investigated over the range of 10-200 kGy. Results show that gamma radiation processing at absorbed doses up to 200 kGy without further treatment is not sufficient for desulfurization. However, the combination of gamma-irradiation with other physical/chemical processes (i.e. L/L extraction, adsorption and oxidation) may be capable of removing considerable levels of sulfur compounds in the investigated products. Currently, this approach of combined radiation/physical/chemical processes is under investigation. The findings of these attempts will be reported in the future.

  16. Process for drying calcium chloride generated in high chloride flue gas desulfurization systems

    SciTech Connect

    Gleason, R.J.; Sui, C.T.

    1982-03-30

    Some flue gas desulfurization processes applied to fuels containing high chloride concentrations are utilizing, or plan to utilize, by-product gypsum from the process stream. The utilization of such a process results in a calcium chloride buildup in the flue gas desulfurization system from fuels or water resource containing significant chlorides which interferes with the absorption and utilization of the lime or limestone reagent. In this invention, a method is used to convert the calcium chloride to a dry material by utilizing flue gas at elevated temperatures, normally found before an air preheater on steam generators used to produce power or any other conventional large size steam boilers. The monohydrate is produced at temperatures above 3500 F. By applying this drying process with a power plant system, energy consumed for this drying operation is very efficient.

  17. A New Dry Flue Gas Desulfurization Process-Underfeed Circulating Spouted Bed

    NASA Astrophysics Data System (ADS)

    Tao, M.; Jin, B. S.; Yang, Y. P.

    Applying an underfeed system, the underfeed circulating spouted bed was designed as a desulfurization reactor. The main objective of the technology is to improve the mixing effect and distribution uniformity of solid particles, and therefore to advance the desulfurization efficiency and calcium utility. In this article, a series of experimental studies were conducted to investigate the fluidization behavior of the solid-gas two-phase flow in the riser. The results show that the technology can distinctly improve the distribution of gas velocity and particle flux on sections compared with the facefeed style. Analysis of pressure fluctuation signals indicates that the operation parameters have significant influence on the flow field in the reaction bed. The existence of injecting flow near the underfeed nozzle has an evident effect on strengthening the particle mixing.

  18. Desulfurization process for dibenzothiophenes from light oil by photochemical reaction and liquid-liquid extraction

    SciTech Connect

    Hirai, Takayuki; Ogawa, Ken; Komasawa, Isao

    1996-02-01

    A desulfurization process for dibenzothiophene (DBT) and its derivatives such as 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) by combination of photochemical reaction and liquid-liquid extraction has been investigated. In this, the DBTs dissolved in tetradecane were quantitatively photodecomposed by the use of a high-pressure mercury lamp and were removed to the water phase as SO{sub 4}{sup 2{minus}} at conditions of room temperature and atmospheric pressure. The order of reactivity for the DBTs was DBT < 4-MDBT < 4,6-DMDBT, thus indicating a different tendency from that reported for the hydrodesulfurization method. The desulfurization yield of commercial light oil, however, by the proposed method was only 22% following 30 h irradiation and was caused mainly by the depression of the photoreaction of DBT by the presence of aromatic compounds in the light oil.

  19. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid.

    PubMed

    Lü, Hongying; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

    2014-08-30

    A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and (1)H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50°C in 3h under conditions of VPIL/Vmodel oil=1:10 and H2O2/DBT (O/S, molar ratio)=5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT>4,6-dimethyldibenzothiophene (4,6-DMDBT)>benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity. PMID:25064259

  20. Desulfurization behavior in rapid pyrolysis of coal treated by KOH solution

    SciTech Connect

    Sugawara, Katsuyasu; Abe, Keiko; Tozuka, Yasuhito; Sugawara, Takuo; Sholes, M.A.

    1994-12-31

    Three kinds of subbituminous and bituminous coals containing potassium hydroxide were heated at 523 K in a nitrogen atmosphere in an attempt to transform thermally stable forms of organic sulfur to reactive ones. Desulfurization extents were 27--52% by alkali leaching while weight loss was observed to be 8-10%. The desulfurization extents were proportional linearly to internal surface area of the parent coals. The parent coals and alkali leached samples were pyrolyzed rapidly by using a free fall reactor in a nitrogen stream up to 1,233K. The alkali-leached samples provided higher extents of reduction for organic sulfur than the parent coals. The combined process of rapid pyrolysis with alkali leaching was effective for reduction of organic sulfur except for a high range coal having small internal surface area.

  1. 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.

  2. Enzymatic desulfurization of coal. First quarterly report, May 5--September 30, 1988

    SciTech Connect

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

    1988-10-07

    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.

  3. 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.

  4. 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.

  5. 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.

  6. Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

    PubMed

    Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

    2015-07-21

    Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content. PMID:26096231

  7. o-Iodoxybenzoic acid mediated oxidative desulfurization initiated domino reactions for synthesis of azoles.

    PubMed

    Chaudhari, Pramod S; Pathare, Sagar P; Akamanchi, Krishnacharaya G

    2012-04-20

    A systematic exploration of thiophilic ability of o-iodoxybenzoic acid (IBX) for oxidative desulfurization to trigger domino reactions leading to new methodologies for synthesis of different azoles is described. A variety of highly substituted oxadiazoles, thiadiazoles, triazoles, and tetrazoles have been successfully synthesized in good to excellent yields, starting from readily accessible thiosemicarbazides, bis-diarylthiourea, 1,3-disubtituted thiourea, and thioamides. PMID:22423599

  8. Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

    PubMed

    Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

    2011-03-21

    Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. PMID:21394927

  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. Microbial Desulfurization of Coals in a Slurry Pipeline Reactor Using. Thiobacillus ferrooxidans.

    PubMed

    Rai, C

    1985-09-01

    Microbial desulfurization of Illinois #6 and Indiana #3 bituminous coal having a total sulfur content of 2 to 8% has been investigated using acidophilic microorganism, Thiobacillus ferrooxidans, in laboratory shake flash experiments and in a two-inch pipeline loop. The results indicate that about 80 to 85% pyritic sulfur removal was achieved with 10 to 25% coal/water slurry recirculated at 6-7 ft/sec at room temperature in 7 to 14 days. The experimental conditions have been optimized for maximum desulfurization. Results from this study show that the rates of bacterial desulfurization from coal samples are higher in the pipeline loop under turbulent flow conditions as compared to the shake-flask experiments for particle sizes ranging from 43 to 200 mum. It is visualized that the proposed coal slurry pipelines could be used as biological plug flow reactors under aerobic conditions. The laboratory corrosion studies under dynamic test conditions show that use of a corrosion inhibitor will limit the pipeline corrosion rate to acceptable levels.

  11. Bioprocessing of crude oils and desulfurization using electro-spray reactors

    SciTech Connect

    Kaufman, E.N.; Borole, A.P.

    1998-07-01

    Biological removal of organic sulfur from petroleum feedstocks offers an attractive alternative to conventional thermochemical treatment due to the mild operating conditions afforded by the biocatalyst. Electro-spray bioreactors were investigated for use in desulfurization due to their reported operational cost savings relative to mechanically agitated reactors and their capability of forming emulsions < 5 {micro}m. Here, the rates dibenzothiophene (DBT) oxidation to 2-hydroxybiphenyl (2-HBP) in hexadecane, by Rhodococcus sp. IGTS8 are compared in the two reactor systems. Desulfurization rates ranged from 1.0 and 5.0 mg 2-HBP/(dry g cells-h), independent of the reactor employed. The batch stirred reactor was capable of forming a very fine emulsion in the presence of the biocatalyst IGTS8, similar to that formed in the electro-spray reactors, presumably due to the fact that the biocatalyst produces its own surfactant. While electro-spray reactors did not prove to be advantageous for the IGTS8 desulfurization system, it may prove advantageous for systems which do not produce surface-active bioagents in addition to being mass transport limited.

  12. Surface acidity effects of Al-SBA-15 mesoporous materials on adsorptive desulfurization.

    PubMed

    Meng, Xiuhong; Wang, Yuan; Duan, Linhai; Qin, Yucai; Yu, Wenguang; Wang, Qiang; Dong, Shiwei; Ruan, Yanjun; Wang, Haiyan; Song, Lijuan

    2014-09-01

    SBA-15 and Aluminum-substituted SBA-15 with Si/Al molar ratio 10 (Al-SBA-15(10)) mesoporous materials were directly synthesized by a hydrolysis approach and characterized by a powder X-ray diffraction (XRD), N2 physisorption analysis and Fourier transform infrared (FTIR) etc. The relative number of hydroxyl groups was investigated by in situ FTIR systematically. The acid type and acid strength of the adsorbents were monitord by FTIR at 423 K and 673 K, respectively, utilizing pyridine as a probe. Desulfurization performances of the adsorbents were investigated via static adsorption experiment. Gas chromatography-sulfur chemiluminescence detector (GC-SCD) was employed to detect the sulfur compounds in model fuels before and after treated by the adsorbents. The calcined Al-SBA-15(10) material shows well-ordered hexagonal mesostructure and strong Lewis acid sites (L acid) and weak Brönsted acid sites (B acid). The number of hydroxy on the surface of the Al-SBA-15(10) is more than that of SBA-15, which is beneficial to further modifications such as spontaneous monolayer dispersion. Desulfurization performance of the adsorbents is affected by surface acidity of adsorbents and the constituent of model fuels (olefins, arene, etc.). The thiophene and olefins adsorbed on the B acid site of the adsorbent may occur subsequently alkylation reactions, which may block the pores of the adsorbents and thus cause the reduction of desulfurization capacity. PMID:25924387

  13. Controlling Peptide Self-Assembly through a Native Chemical Ligation/Desulfurization Strategy.

    PubMed

    Rasale, Dnyaneshwar B; Konda, Maruthi; Biswas, Sagar; Das, Apurba K

    2016-03-18

    Self-assembled peptides were synthesized by using a native chemical ligation (NCL)/desulfurization strategy that maintained the chemical diversity of the self-assembled peptides. Herein, we employed oxo-ester-mediated NCL reactions to incorporate cysteine, a cysteine-based dipeptide, and a sterically hindered unnatural amino acid (penicillamine) into peptides. Self-assembly of the peptides resulted in the formation of self-supporting gels. Microscopy analysis indicated the formation of helical nanofibers, which were responsible for the formation of gel matrices. The self-assembly of the ligated peptides was governed by covalent and non-covalent interactions, as confirmed by FTIR, CD, fluorescence spectroscopy, and MS (ESI) analyses. Peptide disassembly was induced by desulfurization reactions with tris(2-carboxyethyl)phosphine (TCEP) and glutathione at 80 °C. Desulfurization reactions of the ligated peptides converted the Cys and penicillamine functionalities into Ala and Val moieties, respectively. The self-supporting gels showed significant shear-thinning and thixotropic properties.

  14. [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.

  15. 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.

  16. 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.

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

    PubMed

    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

  18. 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.

  19. 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.

  20. 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.

  1. 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. PMID:27552418

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    M2(PcAN)2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M2(PcAN)2-W-HZSM-5) or the M2(PcTN)2 doping W-HZSM-5 (M2(PcTN)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 Cu2(PcAN)2-W-HZSM-5 and Cu2(PcTN)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 Cu2(PcTN)2/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N2 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.

  3. 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.

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

    PubMed

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

    2016-05-20

    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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  7. 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

  8. 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. PMID:25325555

  9. 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. PMID:22835768

  10. 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

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

    PubMed

    Bordoloi, Naba K; Bhagowati, Pabitra; Chaudhuri, Mihir K; Mukherjee, Ashis 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 growth

  12. 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

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

    PubMed

    Bordoloi, Naba K; Bhagowati, Pabitra; Chaudhuri, Mihir K; Mukherjee, Ashis 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 growth

  14. High-volume, high-value usage of flue gas desulfurization (FGD) by-products in underground mines - Phase I: Laboratory investigations. Quarterly report, October 1993--December 1993

    SciTech Connect

    Not Available

    1994-03-01

    This project proposes to use pneumatically or hydraulically emplaced dry-flue gas desulfurization (FGD) by-products to backfill the adits left by highwall mining. Backfilling highwall mine adits with dry-FGD materials is technically attractive. The use of an active highwall mine would allow the dry-FGD material to be brought in using the same transportation network used to move the coal out, eliminating the need to recreated the transportation infrastructure, thereby saving costs. Activities during the period included the negotiations leading to the final cooperative agreement for the project and the implementation of the necessary instruments at the University of Kentucky to administer the project. Early in the negotiations, a final agreement on a task structure was reached and a milestone plan was filed. A review was initiated of the original laboratory plan as presented in the proposal, and tentative modifications were developed. Selection of a mine site was made early; the Pleasant Valley mine in Greenup County was chosen. Several visits were made to the mine site to begin work on the hydrologic monitoring plan. The investigation of the types of permits needed to conduct the project was initiated. Considerations concerning the acceptance and implementation of technologies led to the choice of circulating fluidized bed ash as the primary material for the study. Finally, the membership of a Technical Advisory Committee for the study was assembled.

  15. Biocatalytic preparation and absolute configuration of enantiomerically pure fungistatic anti-2-benzylindane derivatives. Study of the detoxification mechanism by Botrytis cinerea.

    PubMed

    Pinedo-Rivilla, Cristina; Aleu, Josefina; Grande Benito, Manuel; Collado, Isidro G

    2010-08-21

    Enantiomerically pure 2-benzylindane derivatives were prepared using biocatalytic methods and their absolute configuration determined. (1R,2S)-2-Benzylindan-1-ol ((1R,2S)-2) and (S)-2-benzylindan-1-one ((S)-3) were produced by fermenting baker's yeast. Lipase-mediated esterifications and hydrolysis of the corresponding racemic substrates gave rise to the enantiopure compounds (1S,2R)-2-benzylindan-1-ol ((1S,2R)-2) and (1R,2S)-2-benzylindan-1-ol ((1R,2S)-2), respectively. The antifungal activity of these products against two strains of the plant pathogen Botrytis cinerea was tested. The metabolism of anti-(+/-)-2-benzylindan-1-ol (anti-(+/-)-2) by B. cinerea as part of the fungal detoxification mechanism is also described and revealed interesting differences in the genome of both strains.

  16. Fructophilic behaviour of Gordonia alkanivorans strain 1B during dibenzothiophene desulfurization process.

    PubMed

    Alves, Luís; Paixão, Susana M

    2014-01-25

    Biodesulfurization (BDS) aims at the removal of recalcitrant sulfur from fossil fuels at mild operating conditions with the aid of microorganisms. These microorganisms can remove sulfur from dibenzothiphene (DBT), a model compound, or other polycyclic aromatic used as sulfur source, making BDS an easy and environmental friendly process. Gordonia alkanivorans strain 1B has been described as a desulfurizing bacterium, able to desulfurize DBT to 2-hydroxybiphenyl (2-HBP), the final product of the 4S pathway, using d-glucose as carbon source. However, both cell growth and desulfurization can be largely affected by the nutrient composition of the growth medium, due to cofactor requirements of many enzymes involved in the BDS biochemical pathway. In this study, the main goal was to investigate the influence of several sugars, as carbon source, on the growth and DBT desulfurization ability of G. alkanivorans strain 1B. The results of desulfurization tests showed that the lowest values for the growth rate (0.025 hour(-1)) and for the overall 2-HBP production rate (1.80 μm/hour) by the strain 1B were obtained in glucose grown cultures. When using sucrose, the growth rate increase exhibited by strain 1B led to a higher biomass productivity, which induced a slightly increase in the 2-HBP production rate (1.91 μm/hour), conversely in terms of 2-HBP specific production rate (q2-HBP) the value obtained was markedly lower (0.718 μmol/g/hour in sucrose versus 1.22 μmol/g/hour in glucose). When a mixture of glucose and fructose was used as carbon source, strain 1B reached a value of q2-HBP=1.90 μmol/g/hour, close to that in fructose (q2-HBP=2.12 μmol/g/hour). The highest values for both cell growth (μ=0.091 hour(-1)) and 2-HPB production (9.29μm/hour) were obtained when strain 1B was desulfurizing DBT in the presence of fructose as the only carbon source, indicating a fructophilic behaviour by this bacterium. This fact is in agreement with the highest value of biomass

  17. Anion-exchange resin-based desulfurization process. Quarterly technical progress report, January 1, 1993--March 31, 1993

    SciTech Connect

    Sheth, A.C.; Dharmapurikar, R.

    1993-06-01

    Under DOE Grant No. FG22-90PC90309, the University of Tennessee Space Institute (UTSI) is contracted to further develop its anion-exchange, resin-based desulfurization concept to desulfurize alkali metal sulfates. From environmental as well as economic viewpoints, it is necessary to remove soluble sulfates from the wastes created by flue gas desulfurization systems. In order to do this economically, a low-cost desulfurization process for spent sorbents is necessary. UTSI`s anion-exchange resin-based desulfurization concept is believed to satisfy these requirements. UTSI has completed the batch mode experiments to locate the position of the CO{sub 3}{sup 2} and SO{sub 4}{sup 2} ions in the affinity chart. Also, the reviews of the ASPEN Code`s capabilities and EPRI-TAG document`s methodology are in progress for developing the Best Process Schematic and related economics. The fixed-bed experiments are also in progress to evaluate the cycle efficiency of the candidate resins. So far we have completed ten consecutive cycles of exhaustion/carbonation and regeneration for IRA-35 resin. Because of the past problems (now resolved) with the fixed-bed system, the addition of batch mode screening experiments, Christmas holidays and spring break, and the moving of UTSI`s Chemistry Laboratory to a new location, the program is about 6--8 weeks behind schedule, but well within the budget.

  18. 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.

  19. 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. PMID:25474503

  20. Biocatalytic Single Enzyme Nanoparticles

    SciTech Connect

    Grate, Jay W.; Kim, Jungbae

    2004-03-31

    As an innovative way of enzyme stabilization, we recently developed a new enzyme composite of nano-meter scale that we call "single-enzyme nanoparticles (SENs)" (9). Each enzyme molecule is surrounded with a porous composite organic/inorganic network of less than a few nanometers think. This approach represents a new type of enzyme-containing nanostructure. In experiments with perotease (chymotrypsin, CT), the activity of single enzyme nanoparticle form of the enzyme was greatly stabilized compared to the free form, without imposing a serious mass transfer limitation of substrates. In this chapter we will describe the synthesis, characterization and catalytic activity of the new SENs.

  1. 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

  2. LIFAC sorbent injection desulfurization demonstration project. Quarterly report No. 3, April--June 1991

    SciTech Connect

    Not Available

    1991-12-31

    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.

  3. A recyclable ionic liquid-oxomolybdenum(vi) catalytic system for the oxidative desulfurization of model and real diesel fuel.

    PubMed

    Julião, Diana; Gomes, Ana C; Pillinger, Martyn; Valença, Rita; Ribeiro, Jorge C; Gonçalves, Isabel S; Balula, Salete S

    2016-10-14

    The oxidative desulfurization of model and real diesel has been studied using the complex [MoO2Cl2(4,4'-di-tert-butyl-2,2'-bipyridine)] as (pre)catalyst, aq. H2O2 as oxidant, and an ionic liquid as extraction solvent. Under moderate conditions (50 °C) and short reaction times (<3 h), dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene could be completely removed from the model diesel. The (pre)catalyst 1 was transformed in situ to the active catalyst [MoO(O2)2(di-tBu-bipy)]. By sequentially performing extractive desulfurization and ECODS steps, 76% sulfur removal was achieved for a real diesel (Sinitial = 2300 ppm). For both the model and real diesels, the catalyst/IL phase could be easily recycled and reused with no loss of desulfurization efficiency. PMID:27603728

  4. 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.

  5. A recyclable ionic liquid-oxomolybdenum(vi) catalytic system for the oxidative desulfurization of model and real diesel fuel.

    PubMed

    Julião, Diana; Gomes, Ana C; Pillinger, Martyn; Valença, Rita; Ribeiro, Jorge C; Gonçalves, Isabel S; Balula, Salete S

    2016-10-14

    The oxidative desulfurization of model and real diesel has been studied using the complex [MoO2Cl2(4,4'-di-tert-butyl-2,2'-bipyridine)] as (pre)catalyst, aq. H2O2 as oxidant, and an ionic liquid as extraction solvent. Under moderate conditions (50 °C) and short reaction times (<3 h), dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene could be completely removed from the model diesel. The (pre)catalyst 1 was transformed in situ to the active catalyst [MoO(O2)2(di-tBu-bipy)]. By sequentially performing extractive desulfurization and ECODS steps, 76% sulfur removal was achieved for a real diesel (Sinitial = 2300 ppm). For both the model and real diesels, the catalyst/IL phase could be easily recycled and reused with no loss of desulfurization efficiency.

  6. Synthesis of l- and d-Ubiquitin by One-Pot Ligation and Metal-Free Desulfurization.

    PubMed

    Huang, Yi-Chao; Chen, Chen-Chen; Gao, Shuai; Wang, Ye-Hai; Xiao, Hua; Wang, Feng; Tian, Chang-Lin; Li, Yi-Ming

    2016-05-23

    Native chemical ligation combined with desulfurization has become a powerful strategy for the chemical synthesis of proteins. Here we describe the use of a new thiol additive, methyl thioglycolate, to accomplish one-pot native chemical ligation and metal-free desulfurization for chemical protein synthesis. This one-pot strategy was used to prepare ubiquitin from two or three peptide segments. Circular dichroism spectroscopy and racemic protein X-ray crystallography confirmed the correct folding of ubiquitin. Our results demonstrate that proteins synthesized chemically by streamlined 9-fluorenylmethoxycarbonyl (Fmoc) solid-phase peptide synthesis coupled with a one-pot ligation-desulfurization strategy can supply useful molecules with sufficient purity for crystallographic studies.

  7. 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.

  8. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Quarterly technical progress report 2, January--March 1987

    SciTech Connect

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

    1987-05-18

    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.

  9. Pore structure and reactivity changes in hot coal gas desulfurization sorbents. Technical progress report, October--December 1988

    SciTech Connect

    Sotirchos, S.V.

    1989-01-01

    A research program is proposed for the investigation of the dependence of the sorptive capacity of metal/metal oxide desulfurization sorbents on their pore size distribution and their intraparticle diffusivity. Integrated reaction/adsorption systems, chromatographic and gravimetric, will be used for successive reactivity, adsorption, and well as diffusivity, measurements. Single particle models that have been developed by our research group for gas-solid reactions with solid product will be used as basis for experimental data analysis and development of a general mathematical model for fixed-bed desulfurization and sorbent regeneration.

  10. 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.

  11. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Quarterly technical progress report No. 3, April--June 1987

    SciTech Connect

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

    1987-08-28

    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. Quarterly technical progress report 8, July--September 1988

    SciTech Connect

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

    1988-11-14

    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. Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Quarterly technical progress report 7, April--June 1988

    SciTech Connect

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

    1988-08-19

    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.

  14. 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.

  15. 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).

  16. Air pollution and infant mortality: a natural experiment from power plant desulfurization.

    PubMed

    Luechinger, Simon

    2014-09-01

    The paper estimates the effect of SO2 pollution on infant mortality in Germany, 1985-2003. To avoid endogeneity problems, I exploit the natural experiment created by the mandated desulfurization at power plants and power plants' location and prevailing wind directions, which together determine treatment intensity for counties. Estimates translate into an elasticity of 0.07-0.13 and the observed reduction in pollution implies an annual gain of 826-1460 infant lives. There is no evidence for disproportionate effects on neonatal mortality, but for an increase in the number of infants with comparatively low birth weight and length.

  17. 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.

  18. 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.

  19. Air pollution and infant mortality: a natural experiment from power plant desulfurization.

    PubMed

    Luechinger, Simon

    2014-09-01

    The paper estimates the effect of SO2 pollution on infant mortality in Germany, 1985-2003. To avoid endogeneity problems, I exploit the natural experiment created by the mandated desulfurization at power plants and power plants' location and prevailing wind directions, which together determine treatment intensity for counties. Estimates translate into an elasticity of 0.07-0.13 and the observed reduction in pollution implies an annual gain of 826-1460 infant lives. There is no evidence for disproportionate effects on neonatal mortality, but for an increase in the number of infants with comparatively low birth weight and length. PMID:25105867

  20. 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.

  1. 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.

  2. 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.

  3. Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

    SciTech Connect

    Dipu Borah

    2006-02-01

    The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

  4. Numerical Simulation of Desulfurization Behavior in Gas-Stirred Systems Based on Computation Fluid Dynamics-Simultaneous Reaction Model (CFD-SRM) Coupled Model

    NASA Astrophysics Data System (ADS)

    Lou, Wentao; Zhu, Miaoyong

    2014-10-01

    A computation fluid dynamics-simultaneous reaction model (CFD-SRM) coupled model has been proposed to describe the desulfurization behavior in a gas-stirred ladle. For the desulfurization thermodynamics, different models were investigated to determine sulfide capacity and oxygen activity. For the desulfurization kinetic, the effect of bubbly plume flow, as well as oxygen absorption and oxidation reactions in slag eyes are considered. The thermodynamic and kinetic modification coefficients are proposed to fit the measured data, respectively. Finally, the effects of slag basicity and gas flow rate on the desulfurization efficiency are investigated. The results show that as the interfacial reactions (Al2O3)-(FeO)-(SiO2)-(MnO)-[S]-[O] simultaneous kinetic equilibrium is adopted to determine the oxygen activity, and the Young's model with the modification coefficient R th of 1.5 is adopted to determine slag sulfide capacity, the predicted sulfur distribution ratio LS agrees well with the measured data. With an increase of the gas blowing time, the predicted desulfurization rate gradually decreased, and when the modification parameter R k is 0.8, the predicted sulfur content changing with time in ladle agrees well with the measured data. If the oxygen absorption and oxidation reactions in slag eyes are not considered in this model, then the sulfur removal rate in the ladle would be overestimated, and this trend would become more obvious with an increase of the gas flow rate and decrease of the slag layer height. With the slag basicity increasing, the total desulfurization ratio increases; however, the total desulfurization ratio changes weakly as the slag basicity exceeds 7. With the increase of the gas flow rate, the desulfurization ratio first increases and then decreases. When the gas flow rate is 200 NL/min, the desulfurization ratio reaches a maximum value in an 80-ton gas-stirred ladle.

  5. 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.

  6. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs.

  7. 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.

  8. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs. PMID:26575418

  9. 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}.

  10. 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.

  11. 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. PMID:22056885

  12. 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.

  13. [Simultaneous desulfurization and denitrification by TiO2/ACF under different irradiation].

    PubMed

    Han, Jing; Zhao, Yi

    2009-04-15

    The supported TiO2 photocatalysts were prepared in laboratory, and the experiments of simultaneous desulfurization and denitrification were carried out by self-designed photocatalysis reactor. The optimal experimental conditions were achieved, and the efficiencies of simultaneous desulfurization and denitrification under two different light sources were compared. The results show that the oxygen content of flue gas, reaction temperature, flue gas humidity and irradiation intensity are most essential factors to photocatalysis. For TiO2/ACF, the removal efficiencies of 99.7% for SO2 and 64.3% for NO are obtained respectively at optimal experimental conditions under UV irradiation. For TiO2/ACF, the removal efficiencies of 97.5% for SO2 and 49.6% for NO are achieved respectively at optimal experimental conditions under the visible light irradiation. The results of five times parallel experiments indicate standard deviation S of parallel data is little. The mechanism of removal for SO2 and NO is proposed under two light sources by ion chromatography analysis of the absorption liquid.

  14. Optimizing the specific surface area of fly ash-based sorbents for flue gas desulfurization.

    PubMed

    Lee, K T; Bhatia, S; Mohamed, A R; Chu, K H

    2006-01-01

    High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a neural network was used to model the relationship between the three hydration variables and the sorbent surface area. A genetic algorithm was used in the last step to optimize the input space of the resulting neural network model. According to this integrated modeling and optimization approach, an optimum sorbent surface area of 62.2m(2)g(-1) could be obtained by mixing 13.1g of coal fly ash and 5.5 g of calcium sulfate in a hydration process containing 100ml of water and 5 g of calcium oxide for a fixed hydration time of 10 h.

  15. Novel preparation method of macroporous lime from limestone for high-temperature desulfurization

    SciTech Connect

    Sasaoka, Eiji; Uddin, M.A.; Nojima, Shigeru

    1997-09-01

    Limestone is a very important material as a high temperature desulfurization sorbent: limestone is used for in-bed SO{sub 2} capture in fluidized bed combustors of coal and can be used in coal gasifiers for the in-bed removal of H{sub 2}S. In order to develop a highly active calcium oxide high-temperature desulfurization sorbent, macroporous calcium oxides were directly prepared from limestone. This method is composed of two steps: swelling of the limestone in the gas phase followed by drying and calcination of the swelled samples. The swelling was found when limestone was exposed to a vapor of aqueous acetic acid. The swelling of the sample resulted from an increase of calcium acetate formation in the sample. It was then converted to macroporous calcium oxides by heating the sample to 850 C. The reactivity of the macroporous calcium oxide for the removal of SO{sub 2} or H{sub 2}S under coexisting H{sub 2}O vapor was higher than that of the calcined raw limestone. In particular, its SO{sub 2} removal capacity and oxidative character of CaS to CaSO{sub 4} and CaO were greatly improved by the swelling method.

  16. Performance and characterization of a newly developed self-agitated anaerobic reactor with biological desulfurization.

    PubMed

    Kobayashi, Takuro; Li, Yu-You

    2011-05-01

    The continuous operation of a newly developed methane fermentation reactor, which requires no electricity for the agitation of the fermentation liquid was investigated, and the extent of the biological desulfurization was monitored. Inside the reactor, the continual change in the liquid level and the self-agitation, occurring between 5 and 16 times every day, distributed the organic load near the inlet port of the reactor, as well as providing a nutrient supply to the hydrogen sulfide oxidizing bacteria. At different COD(Cr) loading rates (5, 7, 10 kg m(3)d(-1)), the reactor achieved a biogas production yield of 0.72-0.82 m(3)g(-1)-TS, a COD(Cr) reduction of 79.4-85.5% and an average of 99% hydrogen sulfide removal. This investigation demonstrated that the self-agitated reactor is comparable in digestion performance to the completely stirred tank reactor (CSTR) investigated in a previous study, and that the desulfurization performance was significantly enhanced compared to the CSTR.

  17. Ionic liquids in refinery desulfurization: comparison between biphasic and supported ionic liquid phase suspension processes.

    PubMed

    Kuhlmann, Esther; Haumann, Marco; Jess, Andreas; Seeberger, Andreas; Wasserscheid, Peter

    2009-01-01

    The desulfurization of fuel compounds in the presence of ionic liquids is reported. For this purpose, the desulfurization efficiency of a variety of imidazolium phosphate ionic liquids has been tested. Dibenzothiophene/dodecane and butylmercaptan/decane mixtures were used as model systems. Single-stage extractions reduced the sulfur content from 500 ppm to 200 ppm. In multistage extractions the sulfur content could be lowered to less than 10 ppm within seven stages. Regeneration of the ionic liquid was achieved by distillation or re-extraction procedures. Supported ionic liquid phase (SILP) materials, obtained by dispersing the ionic liquid as a thin film on highly porous silica, exhibited a significantly higher extraction performance owing to their larger surface areas, reducing the sulfur content to less than 100 ppm in one stage. Multistage extraction with these SILP materials reduced the sulfur level to 50 ppm in the second stage. The SILP technology offers very efficient utilization of ionic liquids and circumvents mass transport limitations because of the small film thickness and large surface area, and allows application of the simple packed-bed column extraction technique. PMID:19798713

  18. 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.

  19. An investigation into Cu-Mn based sorbent for hot gas desulfurization

    SciTech Connect

    Wan Chen; Sha Xingzhong; Shen Wenqin; Xiong Lihong

    1998-12-31

    In the integrated gasification combined cycle for generation of electricity from coal, the efficient removal of sulfur is essential for improvement in thermal efficiency and process simplification. A family of copper manganese oxide sorbents has been studied. They show better strength and higher sulfur capacity than zinc based sorbents. The integrated gasification combined cycle (IGCC) is one of the most attractive technologies for advanced electricity generation. The coal gas cleanup process is necessary not only for the protection of gas turbine hardware, but also in compliance with the environmental requirements. In order to improve the efficiency of the overall cycle and simplify the process, the coal gas is purified at high temperature. For removal of hydrogen sulfide, the focus of much current work on hot coal gas desulfurization is primarily on the usage of zinc ferrite and zinc titanate sorbents. Zinc titanate is a promising sorbent and displays better strength than zinc ferrite, but its sulfur capacity is low. Therefore novel sorbents are still being searched for which can show improved properties. A family of copper manganese oxide sorbents has been studied and then their desulfurization properties are introduced here.

  20. Ultrasound-assisted oxidative desulfurization of liquid fuels and its industrial application.

    PubMed

    Wu, Zhilin; Ondruschka, Bernd

    2010-08-01

    Latest environmental regulations require a very deep desulfurization to meet the ultra-low sulfur diesel (ULSD, 15 ppm sulfur) specifications. Due to the disadvantages of hydrotreating technology on the slashing production conditions, costs and safety as well as environmental protection, the ultrasound-assisted oxidative desulfurization (UAOD) as an alternative technology has been developed. UAOD process selectively oxidizes sulfur in common thiophenes in diesel to sulfoxides and sulfones which can be removed via selective adsorption or extractant. SulphCo has successfully used a 5000 barrel/day mobile "Sonocracking" unit to duplicate on a commercial scale its proprietary process that applies ultrasonics at relatively low temperatures and pressures. The UAOD technology estimate capital costs less than half the cost of a new high-pressure hydrotreater. The physical and chemical mechanisms of UAOD process are illustrated, and the effective factors, such as ultrasonic frequency and power, oxidants, catalysts, phase-transfer agent, extractant and adsorbent, on reaction kinetics and product recovery are discussed in this review. PMID:20022546

  1. 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.

  2. 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. PMID:19699584

  3. Desulfurization characteristics of thermophilic Paenibacillus sp. strain A11-2 against asymmetrically alkylated dibenzothiophenes.

    PubMed

    Onaka, T; Konishi, J; Ishii, Y; Maruhashi, K

    2001-01-01

    The thermophilic bacterium Paenibacillus sp. A11-2, which can utilize dibenzothiophene (DBT) as the sole sulfur source at high temperature (45-55 degrees C), was investigated for its ability to cleave carbon-sulfur bonds in the dibenzothiophene (DBT) ring with asymmetrical alkyl substitution, such as methyl, dimethyl, trimethyl, ethyl and propyl DBTs. The biodesulfurization products of each of these alkylated DBTs (Cx-DBTs) were identified and quantitatively determined. The results suggested that each of the Cx-DBTs was desulfurized at a low rate, then converted to alkylated hydroxybiphenyls containing the isomers, and molar ratios of these metabolic isomers were altered in terms of not only the positions but also the numbers and lengths of the alkyl substituents. Moreover, these ratios were compared with those obtained using the mesophilic desulfurizing bacterium Rhodococcus erythropolis KA2-5-1. Consequently, biodesulfurization reactions of these microbes could be characterized using asymmetrically Cx-DBTs and their molecular shape parameters (length and length-to-breadth ratio), indicating differences in the selectivity of the microbial enzymic systems between the two bacterial strains.

  4. Characterization of the desulfurization genes from Rhodococcus sp. strain IGTS8.

    PubMed Central

    Denome, S A; Oldfield, C; Nash, L J; Young, K D

    1994-01-01

    Rhodococcus sp. strain IGTS8 possesses an enzymatic pathway that can remove covalently bound sulfur from dibenzothiophene (DBT) without breaking carbon-carbon bonds. The DNA sequence of a 4.0-kb BstBI-BsiWI fragment that carries the genes for this pathway was determined. Frameshift and deletion mutations established that three open reading frames were required for DBT desulfurization, and the genes were designated soxABC (for sulfur oxidation). Each sox gene was subcloned independently and expressed in Escherichia coli MZ1 under control of the inducible lambda pL promoter with a lambda cII ribosomal binding site. SoxC is an approximately 45-kDa protein that oxidizes DBT to DBT-5,5'-dioxide. SoxA is an approximately 50-kDa protein responsible for metabolizing DBT-5,5'-dioxide to an unidentified intermediate. SoxB is an approximately 40-kDa protein that, together with the SoxA protein, completes the desulfurization of DBT-5,5'-dioxide to 2-hydroxybiphenyl. Protein sequence comparisons revealed that the predicted SoxC protein is similar to members of the acyl coenzyme A dehydrogenase family but that the SoxA and SoxB proteins have no significant identities to other known proteins. The sox genes are plasmidborne and appear to be expressed as an operon in Rhodococcus sp. strain IGTS8 and in E. coli. Images PMID:7961424

  5. 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.

  6. 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.

  7. [Diversity analysis of desulfuration bacterium from the oxidation ditch of city sewage treatment plant with SO2 gas].

    PubMed

    Huang, Bing; Zhang, Shi-Ling; Zhang, Jiang-Hong; Ao, Yong; Shi, Zhe

    2011-07-01

    A group of removing SO2 bacterium was obtained from the oxidation ditch of city sewage treatment plant by inductive domestication over 6 d with low concentration SO2 gas, and they have an ability with biodegradation rate of 888 mg x (L x h)(-1) and a degradation efficiency of 85% during 1.5 h for SO2 dissolved in water with their synergy. The clone library and two phylogenetic trees of the removing SO2 bacterium communities were obtained based on 16S rRNA DNA comparison by DNA extraction of the sample and in situ polymerase chain reaction (PCR). The phylogenetic analysis showed that 8 dominant desulfuration bacterium occupy about 69% of all removing SO2 bacterium, and some of them have a kindred with discovered desulfuration bacterium but not homogeneity, and there are four belong to alpha-Proteobacteria, another four belong to beta-Proteobacteria in them. The gene information about 16S rRNA sequence of the dominant desulfuration bacteria and domestication method provide a basic of looking for or domesticating removing SO2 bacterium for development microbial desulfurization technology of contained SO2 tail gas.

  8. 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

  9. 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.

  10. Experimental study on the reuse of spent rapidly hydrated sorbent for circulating fluidized bed flue gas desulfurization.

    PubMed

    Li, Yuan; Zheng, Kai; You, Changfu

    2011-11-01

    Rapidly hydrated sorbent, prepared by rapidly hydrating adhesive carrier particles and lime, is a highly effective sorbent for moderate temperature circulating fluidized bed flue gas desulfurization (CFB-FGD) process. The residence time of fine calcium-containing particles in CFB reactors increases by adhering on the surface of larger adhesive carrier particles, which contributes to higher sorbent calcium conversion ratio. The circulation ash of CFB boilers (α-adhesive carrier particles) and the spent sorbent (β and γ-adhesive carrier particles) were used as adhesive carrier particles for producing the rapidly hydrated sorbent. Particle physical characteristic analysis, abrasion characteristics in fluidized bed and desulfurization characteristics in TGA and CFB-FGD systems were investigated for various types of rapidly hydrated sorbent (α, β, and γ-sorbent). The adhesion ability of γ-sorbent was 50.1% higher than that of α-sorbent. The abrasion ratio of β and γ-sorbent was 16.7% lower than that of α-sorbent. The desulfurization abilities of the three sorbent in TGA were almost same. The desulfurization efficiency in the CFB-FGD system was up to 95% at the bed temperature of 750 °C for the β-sorbent. PMID:21928832

  11. 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...

  12. 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

    2016-01-01

    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. PMID:26502800

  13. 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. PMID:26881277

  14. 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 ...

  15. 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. PMID:23398211

  16. Recovery and recycling of limestone in LEC flue gas desulfurization

    SciTech Connect

    Gardner, N.C.; Boo, J.Y.; Culver, L. )

    1992-09-01

    Prudich et. al. have proposed an attractive technology called Limestone Emission Control (LEC) for removing sulfur dioxide from flue gases. Beds of 1/8 inch wet limestone particles absorb the sulfur dioxide from the gases on contact. Sulfite and sulfate salts deposit on the surface of the particles; however, the gas never reaches the interior, limiting the limestone utilization to approximately 20% or less. The unreacted portion of the limestone can be recovered by mechanical grinding and recycling, enabling high overall sorbent utilization. Favorable economics are derived from small equipment, simplicity, and low sorbent costs. This project is a wet method for grinding and recovering the spent limestone from the LEC process, utilizing an impeller fluidizer, a new type of slurry processor. It consists of a cylindrical vessel with an impeller at one end. The impeller, driven at high rpm, concentrates the gravel size limestone in a rotating torus at the top of the cylinder, where the coating is abraded off by particle-particle impaction. The impeller generates sufficient pressure head to serve as a slurry pump. It combines the operation of wet grinding, washing, and transporting the spent and recovered limestone as an aqueous slurry. The fluidizer may be advantageous over dry grinding in the aspects of sharpness of separation, transport convenience, equipment erosion, and sorption bed cementation.

  17. Operon structure and functional analysis of the genes encoding thermophilic desulfurizing enzymes of Paenibacillus sp. A11-2.

    PubMed

    Ishii, Y; Konishi, J; Okada, H; Hirasawa, K; Onaka, T; Suzuki, M

    2000-04-01

    Paenibacillus A11-2 can efficiently cleave two carbon&bond;sulfur bonds in dibenzothiophene (DBT) and alkyl DBTs, which are refractory by conventional petroleum hydrodesulfurization, to remove sulfur atom at high temperatures. An 8.7-kb DNA fragment containing the genes for the DBT desulfurizing enzymes of A11-2 was cloned in Escherichia coli and characterized. Heterologous expression analysis of the deletion mutants identified three open reading frames that were required for the desulfurization of DBT to 2-hydroxybiphenyl (2-HBP). The three genes were designated tdsA, tdsB, and tdsC (for thermophilic desulfurization). Both the nucleotide sequences and the deduced amino acid sequences show significant homology to dszABC genes of Rhodococcus sp. IGTS8, but there are several local differences between them. Subclone analysis revealed that the product of tdsC oxidizes DBT to DBT-5,5'-dioxide via DBT-5-oxide, the product of tdsA converts DBT-5,5'-dioxide to 2-(2-hydroxyphenyl) benzene sulfinate, and the product of tdsB converts 2-(2-hydroxyphenyl)benzene sulfinate to 2-HBP. Cell-free extracts of a recombinant E. coli harboring all the three desulfurization genes converted DBT to 2-HBP at both 37 and 50 degrees C. In vivo and in vitro exhibition of desulfurization activity of the recombinant genes derived from a Paenibacillus indicates that an E. coli oxidoreductase can be functionally coupled with the monooxygenases of a gram-positive thermophile.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Hot Coal Gas Desulfurization With Manganese-Based Sorbents

    SciTech Connect

    Berns, J.J.; Hepworth, M.T.

    1996-12-31

    The objective of this project is to develop a pellet formulation which is capable of achieving low sulfur partial pressures and a high capacity for sulfur, loaded from a hot fuel gas and which is readily regenerable. Furthermore the pellet must be strong for potential use in a fluidized and regenerable over many cycles of loading and regeneration. Regeneration should be in air or oxygen-depleted air to produce a high-concentration sulfur dioxide. Fixed-bed tests were conducted with several formulations of manganese sesquioxide and titania, and alumina. They were subject to a simplified fuel gas of the oxygen-blown Shell type spiked with a 30,000 ppmv concentration of H{sub 2}S. Pellet crush strengths for 4 and 2 mm diameter pellets was typically 12 lbs per pellet and 4 lbs per pellet, respectively. For the most favorable of the formulations tested and under the criteria of break-through at less than 100 ppmv H{sub 2}S and loading temperatures of 5000 {degrees}C and an empty-bed space velocity of 4, 000 per hour, breakthrough occurred an effective loading of sulfur of 27 to 29% over 5 loading and regeneration cycles. At 90% of this saturation condition, the observed level of H{sub 2}S was below 10 ppmv. For regeneration, a temperature of 9000 {degrees}C is required to dissociate the sulfide into sulfur dioxide using air at atmospheric pressure. The mean sulfur dioxide concentration which is achieved during regeneration is 8% with empty-bed space velocities of 700/hr. TGA tests on individual pellets indicate that bentonite is not desirable as a bonding material and that Mn/Ti ratios higher than 7:1 produce relatively non-porous pellets. Whereas the reactivity is rapid below 12% conversion, the kinetics of conversion decreased significantly above this level. This observation may be the result of plugging of the pellet pores with sulfided product creating inaccessible pore volumes or alternately an increase in diffusional resistance by formation of MnS.

  3. Enhanced biocatalytic production of L-cysteine by Pseudomonas sp. B-3 with in situ product removal using ion-exchange resin.

    PubMed

    Wang, Pu; He, Jun-Yao; Yin, Jiang-Feng

    2015-03-01

    Bioconversion of DL-2-amino-Δ(2)-thiazoline-4-carboxylic acid (DL-ATC) catalyzed by whole cells of Pseudomonas sp. was successfully applied for the production of L-cysteine. It was found, however, like most whole-cell biocatalytic processes, the accumulated L-cysteine produced obvious inhibition to the activity of biocatalyst and reduced the yield. To improve L-cysteine productivity, an anion exchange-based in situ product removal (ISPR) approach was developed. Several anion-exchange resins were tested to select a suitable adsorbent used in the bioconversion of DL-ATC for the in situ removal of L-cysteine. The strong basic anion-exchange resin 201 × 7 exhibited the highest adsorption capacity for L-cysteine and low adsorption for DL-ATC, which is a favorable option. With in situ addition of 60 g L(-1) resin 201 × 7, the product inhibition can be reduced significantly and 200 mmol L(-1) of DL-ATC was converted to L-cysteine with 90.4 % of yield and 28.6 mmol L(-1 )h(-1) of volumetric productivity. Compared to the bioconversion without the addition of resin, the volumetric productivity of L-cysteine was improved by 2.27-fold using ISPR method.

  4. 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

  5. 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

    2014-01-01

    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. PMID:25093983

  6. 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.

  7. 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.

  8. Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell.

    PubMed

    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.

  9. 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...

  10. 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, technologists, and…

  11. 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.

  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. Coal desulfurization by a microwave process. Technical progress report, February 1981-May 1981

    SciTech Connect

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

    1981-01-01

    Desulfurization experiments were carried out using the 6KW, 2450 MHz Flow Reactor System. The program has been directed toward the combination of physical separation and microwave exposure with NaOH to increase sulfur removal. The following treatment sequence has been used with good results: (1) expose 1/4 to 1 in. raw coal to microwaves; (2) crush the treated coal and separate the sample into float/sink fractions; (3) add NaOH to the float fraction and re-expose the sample to microwaves; and (4) wash, add NaOH and expose to microwaves. This procedure has produced up to 89% sulfur removal and as low as 0.31 numberS/10/sup 6/ Btu. Ash analyses on these samples showed as high as 40% reduction. The calorific value was increased in almost all samples. Data on sulfur, ash and calorific values are summarized.

  14. Enhanced durability of high-temperature desulfurization sorbents for moving-bed applications

    SciTech Connect

    Ayala, R.E.

    1991-08-01

    The objective of this contract was to identify and test fabrication methods and sorbent chemical compositions that enhance the long-term chemical reactivity and mechanical strength of zinc ferrite and other novel sorbents for moving-bed, high-temperature desulfurization of coal-derived gases. Desired properties to be enhanced for moving-bed sorbent materials are: (1) high chemical reactivity (sulfur absorption rate and total sulfur capacity), (2) high mechanical strength (pellet crush strength and attrition resistance), and (3) suitable pellet morphology (e.g., pellet size, shape, surface area, and average specific pore volume). In addition, it is desired to maintain the sorbent properties over extended cyclic use in moving- bed systems.

  15. 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.

  16. Surface characterization of adsorbents in ultrasound-assisted oxidative desulfurization process of fossil fuels.

    PubMed

    Etemadi, Omid; Yen, Teh Fu

    2007-09-01

    Surface properties of two different phases of alumina were studied through SEM images. Characterization of amorphous acidic alumina and crystalline boehmite by XRD explains the differences in adsorption capacities of each sample. Data from small angle neutron scattering (SANS) provide further results regarding the ordering in amorphous and crystalline samples of alumina. Quantitative measurements from SANS are used for pore size calculations. Higher disorder provides more topological traps, irregularities, and hidden grooves for higher adsorption capacity. An isotherm model was derived for adsorption of dibenzothiophene sulfone (DBTO) by amorphous acidic alumina to predict and calculate the adsorption of sulfur compounds. The Langmuir-Freundlich model covers a wide range of sulfur concentrations. Experiments prove that amorphous acidic alumina is the adsorbent of choice for selective adsorption in the ultrasound-assisted oxidative desulfurization (UAOD) process to produce ultra-low-sulfur fuel (ULSF).

  17. 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.

  18. 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.

  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. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process.

  2. 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%.

  3. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process. PMID:27433701

  4. Effect of water treatment chemicals on limestone/sulfur dioxide reaction in flue gas desulfurization systems

    SciTech Connect

    Dille, E.R.; Gaikwad, R.P.

    1994-12-31

    A simple laboratory test has been developed which simulates the reaction between limestone/water and sulfur dioxide in flue gas desulfurization systems. By adding various chemicals, in differing concentrations, to the limestone/water mixture, the quantitative impact on the sulfur dioxide/limestone reaction can be qualified and quantified. This paper will present the impact of several water treatment chemicals on the reaction of limestone and sulfur dioxide. An attempt has been made to predict the effect through mathematical correlations. All of the additive chemicals tend to decrease the rate of dissolution of limestone to various degrees. Some of the chemicals retard crystal growth thus adversely impacting solids separation in the thickener. The physical appearance of the crystal growth retarded limestone absorber slurry approaches a colloidal suspension.

  5. 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.

  6. 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.

  7. Method using lime slurry for regenerating sodium sulfite in double alkali flue gas desulfurization process

    SciTech Connect

    Dabbs, J.C.; Dauerman, L.; Delaney, B.; Rao, K.K.

    1981-05-12

    In the process of desulfurizing flue gases in which an alkaline solution of sodium, such as sodium sulfite or sodium hydroxide, is contacted with gases in a scrubber to produce a sodium bisulfite solution, an improved method is provided for substantially reducing the time and equipment required to regenerate the sodium solution. In the method, a lime slurry stream and a sodium bisulfite stream are conflowed into a bifurcated mixing nozzle having a pair of converging inlets and a common outlet. The confluence of the streams in the nozzle creates turbulence which causes the lime slurry to react substantially instantaneously with the sodium bisulfite solution to regenerate the sodium solution which is recycled to the scrubber and a calcium sulfite precipitate which is filtered from the sodium solution and discarded.

  8. Hot gas desulfurization with sorbents containing oxides of zinc, iron, vanadium and copper

    SciTech Connect

    Akyurtlu, A.; Akyurtlu, J.F.

    1992-01-01

    The main objective of this research is to evaluate the desulfurization performance of novel sorbents consisting of different combinations of zinc, iron, vanadium and copper oxides; and to develop a sorbent which can reduce H{sub 2}S levels to less than 1 ppmv, which can stabilize zinc, making operations above 650{degrees}C possible, and which can produce economically recoverable amounts of elemental sulfur during regeneration. This objective will be accomplished by evaluating the sorbent performance using fixed-bed and TGA experiments supported by sorbent characterization at various reaction extents. In the seventh quarter, the screening of the promoted sorbents in the packed bed reactor was continued. The results of this work were presented at the 1992 University Coal Research Contractors, Review Conference at Pittsburgh, PA.

  9. Application of Two Cobalt-Based Metal-Organic Frameworks as Oxidative Desulfurization Catalysts.

    PubMed

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2015-12-01

    Two new porous cobalt-based metal-organic frameworks, [Co6(oba)5(OH)2(H2O)2(DMF)4]n · 5DMF (TMU-10) and [Co3(oba)3(O) (Py)0.5] n · 4DMF · Py (TMU-12) have been synthesized by solvothermal method using a nonlinear dicarboxylate ligand. Under mild reaction conditions, these compounds exhibited good catalytic activity and reusability in oxidative desulfurization (ODS) reaction of model oil which was prepared by dissolving dibenzothiophene (DBT) in n-hexane. FT-IR and Mass analysis showed that the main product of DBT oxidation is its corresponding sulfone, which was adsorbed on the surfaces of catalysts. The activation energy was obtained as 13.4 kJ/mol. PMID:26571113

  10. Surface characterization of adsorbents in ultrasound-assisted oxidative desulfurization process of fossil fuels.

    PubMed

    Etemadi, Omid; Yen, Teh Fu

    2007-09-01

    Surface properties of two different phases of alumina were studied through SEM images. Characterization of amorphous acidic alumina and crystalline boehmite by XRD explains the differences in adsorption capacities of each sample. Data from small angle neutron scattering (SANS) provide further results regarding the ordering in amorphous and crystalline samples of alumina. Quantitative measurements from SANS are used for pore size calculations. Higher disorder provides more topological traps, irregularities, and hidden grooves for higher adsorption capacity. An isotherm model was derived for adsorption of dibenzothiophene sulfone (DBTO) by amorphous acidic alumina to predict and calculate the adsorption of sulfur compounds. The Langmuir-Freundlich model covers a wide range of sulfur concentrations. Experiments prove that amorphous acidic alumina is the adsorbent of choice for selective adsorption in the ultrasound-assisted oxidative desulfurization (UAOD) process to produce ultra-low-sulfur fuel (ULSF). PMID:17543320

  11. 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.

  12. 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.

  13. A DFT study of the extractive desulfurization mechanism by [BMIM](+)[AlCl4](-) ionic liquid.

    PubMed

    Li, Hongping; Chang, Yonghui; Zhu, Wenshuai; Jiang, Wei; Zhang, Ming; Xia, Jiexiang; Yin, Sheng; Li, Huaming

    2015-05-14

    In this work, the interaction nature between [BMIM](+)[AlCl4](-) ionic liquid (IL) and aromatic sulfur compounds (thiophene, benzothiophene, and dibenzothiophene) has been studied by means of density functional theory (M06-2X functional) combined with an implicit solvation model. Although [BMIM](+)[AlCl4](-) is a metal-containing IL, its extractive desulfurization mechanism is different from other metal-containing ILs but similar to non-metal-containing ILs. Important reactions involved in extractive desulfurization (EDS) were systematically studied. Our results have demonstrated that both the cation and the anion play important roles in EDS. On the basis of the structure analysis, reduced density gradient analaysis (RDG), and energy decomposition analysis, [BMIM](+) cation affords a π-π interaction while [AlCl4](-) anion provides a hydrogen bonding interaction. Electrostatic potential analysis implies the dominant π-π interaction and hydrogen bonding interaction are driven by electrostatic interaction between IL and aromatic sulfur compounds. Interaction energy between [BMIM](+)[AlCl4](-) and thiophene (TH), benzothiophene (BT), and dibenzothiophene (DBT) follows the order TH < BT < DBT. Moreover, Al-containing IL with a high molar ratio of AlCl3 ([BMIMCl]/2[AlCl3]) has also been studied. Results show that [Al2Cl7](-) species will be formed with excess AlCl3. However, the [Al2Cl7](-)-based IL cannot improve the EDS performance. Improvement of EDS performance with a high molar ratio of AlCl3 is credited to the Lewis acidity of AlCl3. Charge analysis reveals that there is no obvious charge transfer during the reaction, which is different from Fe-containing ILs as well as solid sorbents. In addition, CH-π interaction is not important for the current system.

  14. 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.

  15. 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.

  16. 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.

  17. Immobilisation and characterisation of biocatalytic co-factor recycling enzymes, glucose dehydrogenase and NADH oxidase, on aldehyde functional ReSyn™ polymer microspheres.

    PubMed

    Twala, Busisiwe V; Sewell, B Trevor; Jordaan, Justin

    2012-05-10

    The use of enzymes in industrial applications is limited by their instability, cost and difficulty in their recovery and re-use. Immobilisation is a technique which has been shown to alleviate these limitations in biocatalysis. Here we describe the immobilisation of two biocatalytically relevant co-factor recycling enzymes, glucose dehydrogenase (GDH) and NADH oxidase (NOD) on aldehyde functional ReSyn™ polymer microspheres with varying functional group densities. The successful immobilisation of the enzymes on this new high capacity microsphere technology resulted in the maintenance of activity of ∼40% for GDH and a maximum of 15.4% for NOD. The microsphere variant with highest functional group density of ∼3500 μmol g⁻¹ displayed the highest specific activity for the immobilisation of both enzymes at 33.22 U mg⁻¹ and 6.75 U mg⁻¹ for GDH and NOD with respective loading capacities of 51% (0.51 mg mg⁻¹) and 129% (1.29 mg mg⁻¹). The immobilised GDH further displayed improved activity in the acidic pH range. Both enzymes displayed improved pH and thermal stability with the most pronounced thermal stability for GDH displayed on ReSyn™ A during temperature incubation at 65 °C with a 13.59 fold increase, and NOD with a 2.25-fold improvement at 45 °C on the same microsphere variant. An important finding is the suitability of the microspheres for stabilisation of the multimeric protein GDH.

  18. Biocatalytic synthesis of flavones and hydroxyl-small molecules by recombinant Escherichia coli cells expressing the cyanobacterial CYP110E1 gene

    PubMed Central

    2012-01-01

    Background Cyanobacteria possess several cytochrome P450s, but very little is known about their catalytic functions. CYP110 genes unique to cyanaobacteria are widely distributed in heterocyst-forming cyanobacteria including nitrogen-fixing genera Nostoc and Anabaena. We screened the biocatalytic functions of all P450s from three cyanobacterial strains of genus Nostoc or Anabaena using a series of small molecules that contain flavonoids, sesquiterpenes, low-molecular-weight drugs, and other aromatic compounds. Results Escherichia coli cells carrying each P450 gene that was inserted into the pRED vector, containing the RhFRed reductase domain sequence from Rhodococcus sp. NCIMB 9784 P450RhF (CYP116B2), were co-cultured with substrates and products were identified when bioconversion reactions proceeded. Consequently, CYP110E1 of Nostoc sp. strain PCC 7120, located in close proximity to the first branch point in the phylogenetic tree of the CYP110 family, was found to be promiscuous for the substrate range mediating the biotransformation of various small molecules. Naringenin and (hydroxyl) flavanones were respectively converted to apigenin and (hydroxyl) flavones, by functioning as a flavone synthase. Such an activity is reported for the first time in prokaryotic P450s. Additionally, CYP110E1 biotransformed the notable sesquiterpene zerumbone, anti-inflammatory drugs ibuprofen and flurbiprofen (methylester forms), and some aryl compounds such as 1-methoxy and 1-ethoxy naphthalene to produce hydroxylated compounds that are difficult to synthesize chemically, including novel compounds. Conclusion We elucidated that the CYP110E1 gene, C-terminally fused to the P450RhF RhFRed reductase domain sequence, is functionally expressed in E. coli to synthesize a robust monooxygenase, which shows promiscuous substrate specificity (affinity) for various small molecules, allowing the biosynthesis of not only flavones (from flavanones) but also a variety of hydroxyl-small molecules

  19. 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.

  20. 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.

  1. Utilization of a By-product Produced from Oxidative Desulfurization Process over Cs-Mesoporous Silica Catalysts

    SciTech Connect

    Kim, Hyeonjoo; Jeong, Kwang Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong Ki

    2011-02-28

    We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were chaeacterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

  2. A novel metabolite (1,3-benzenediol, 5-hexyl) production by Exophiala spinifera strain FM through dibenzothiophene desulfurization.

    PubMed

    Elmi, Fatemeh; Etemadifar, Zahra; Emtiazi, Giti

    2015-05-01

    Sulfur dioxide which is released from petroleum oil combustion causes pollution over the atmosphere and the soil. Biodesulfurization can be used as a complementary method of hydrodesulfurization, the common method of petroleum desulfurization in refineries. Many studies have been carried out to develop biological desulfurization of dibenzothiophene (DBT) with bacterial biocatalysts. However, fungi are capable to metabolize a wide range of aromatic hydrocarbons through cytochrome P450 and their extracellular enzymes. The aim of the present work was isolation and identification of fungi biocatalysts capable for DBT utilization as sulfur source and production of novel metabolites. DBT consumption and the related produced metabolites were analyzed by HPLC and GC-MS respectively. One of the isolated fungi that could utilize DBT as sole sulfur source was identified by both traditional and molecular experiments and registered in NCBI as Exophiala spinifera FM strain (accession no. KC952672). This strain could desulfurize 99 % of DBT (0.3 mM) as sulfur source by co-metabolism reaction with other carbon sources through the same pathway as 4S and produced 2-hydroxy biphenyl (2-HBP) during 7 days of incubation at 30 °C and 180 rpm shaking. However, the isolate was able to transform 2-HBP to 1,3-benzenediol, 5-hexyl. While biphenyl compounds are toxic to leaving cells, biotransformation of them can reduce their toxicity and the fungi will be more tolerant to the final product. These data are the first report about the desulfurization of DBT comparable to 4S-pathway and production of innovative metabolite by E. spinifera FM strain. PMID:25752234

  3. A novel metabolite (1,3-benzenediol, 5-hexyl) production by Exophiala spinifera strain FM through dibenzothiophene desulfurization.

    PubMed

    Elmi, Fatemeh; Etemadifar, Zahra; Emtiazi, Giti

    2015-05-01

    Sulfur dioxide which is released from petroleum oil combustion causes pollution over the atmosphere and the soil. Biodesulfurization can be used as a complementary method of hydrodesulfurization, the common method of petroleum desulfurization in refineries. Many studies have been carried out to develop biological desulfurization of dibenzothiophene (DBT) with bacterial biocatalysts. However, fungi are capable to metabolize a wide range of aromatic hydrocarbons through cytochrome P450 and their extracellular enzymes. The aim of the present work was isolation and identification of fungi biocatalysts capable for DBT utilization as sulfur source and production of novel metabolites. DBT consumption and the related produced metabolites were analyzed by HPLC and GC-MS respectively. One of the isolated fungi that could utilize DBT as sole sulfur source was identified by both traditional and molecular experiments and registered in NCBI as Exophiala spinifera FM strain (accession no. KC952672). This strain could desulfurize 99 % of DBT (0.3 mM) as sulfur source by co-metabolism reaction with other carbon sources through the same pathway as 4S and produced 2-hydroxy biphenyl (2-HBP) during 7 days of incubation at 30 °C and 180 rpm shaking. However, the isolate was able to transform 2-HBP to 1,3-benzenediol, 5-hexyl. While biphenyl compounds are toxic to leaving cells, biotransformation of them can reduce their toxicity and the fungi will be more tolerant to the final product. These data are the first report about the desulfurization of DBT comparable to 4S-pathway and production of innovative metabolite by E. spinifera FM strain.

  4. Mono- to Octachlorinated Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Emissions from Sintering Plants Synergistically Controlled by the Desulfurization Process.

    PubMed

    Wang, Mengjing; Liu, Wenbin; Hou, Meifang; Li, Qianqian; Han, Ying; Li, Haifeng; Yan, Nan; Zheng, Minghui

    2016-05-17

    The influence of desulfurization systems in sintering plants on polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations, profiles, and emission factors was studied. Mono- to tri-CDD/Fs and tetra- to octa-CDD/F concentrations were 4.4 ± 2.3 and 10.5 ± 8.3 ng m(-3), respectively, at the inlets and 0.87 ± 0.48 and 0.47 ± 0.22 ng m(-3), respectively, after desulfurization. The toxic equivalents (TEQs) were 0.95 ± 0.093 and 0.51 ± 0.040 ng of I-TEQ m(-3) at the inlets and after desulfurization, respectively. The congener profiles and homologue distributions were dominated by 2-MoCDF and MoCDF, respectively. The PCDD/F removal efficiencies achieved by desulfurization increased as the chlorination level increased. The PCDD/Fs became adsorbed to gypsum. Annual mono- to tri-CDD/Fs PCDD/F and TEQ (tetra- to octa-CDD/F) emission factors for flue gas and gypsum between 2003 and 2012 were determined. The total amounts of mono- to tri-CDD/Fs emitted in flue gas and gypsum between 2003 and 2012 were 10.7 and 10.2 kg, respectively. The total TEQs emitted in flue gas and gypsum between 2003 and 2012 were estimated to be 15486 and 1878 g of I-TEQ, respectively. PCDD/Fs adsorbed to gypsum are not effectively eliminated. The PCDD/F concentrations increased as the fly ash surface area increased moving through the electrostatic precipitator stages.

  5. Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

    PubMed

    Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

    2011-02-01

    We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process. PMID:21456272

  6. Development of a hydrogen-based annealing process for desulfurization of single crystalline, nickel-based superalloy. Final report

    SciTech Connect

    Smith, M.; Mickle, T.H.; Frazier, W.E.; Waldman, J.

    1994-11-05

    The presence of minor amounts of sulfur (1-10 ppm) in nickel-based superalloys has been associated with reduced oxidation resistance and premature spallation of protective coatings. A hydrogen annealing process has been developed by NAWCADWAR which effectively reduces the sulfur content of superalloys. The conditions which allow effective desulfurization are delineated. Diffusion of sulfur through the superalloy is found to be the rate controlling step for the process.

  7. 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).

  8. Desulfurization of liquid fuels by adsorption on carbon-based sorbents and ultrasound-assisted sorbent regeneration.

    PubMed

    Wang, Yuhe; Yang, Ralph T

    2007-03-27

    Several carbon-based adsorbents, CuCl/AC, PdCl2/AC, and Pd/AC (where AC denotes activated carbon), were studied for desulfurization of a model jet fuel by selective adsorption of thiophenic molecules. Comparisons with gamma-Al2O3 support and desulfurization of a commercial jet fuel were also studied. The results showed that the selective sulfur adsorption capacity of PdCl2 was higher than that of CuCl and Pd(0), in agreement with molecular orbital results. It was also found that the activated carbon is the best support for pi-complexation sorbents to remove sulfur-containing compounds, i.e., benzothiophene and methylbenzothiophene. Among all the adsorbents studied, PdCl2/AC had the highest capacity for desulfurization. A significant synergistic effect was observed between the carbon substrate and the supported pi-complexation sorbent, and this effect was explained by a geometric effect. The saturated sorbent was regenerated by desorption assisted by ultrasound with a solvent of 30 wt % benzene and 70 wt % n-octane. The results showed that the amount of sulfur desorbed was higher with ultrasound, 65 wt % desorption vs 45 wt % without ultrasound in a static system at 50 degrees C.

  9. 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.

  10. Effect of photosensitizer and hydrogen peroxide on desulfurization of light oil by photochemical reaction and liquid-liquid extraction

    SciTech Connect

    Hirai, Takayuki; Shiraishi, Yasuhiro; Ogawa, Ken; Komasawa, Isao

    1997-03-01

    A desulfurization process for dibenzothiophene (DBT) by a combination of photochemical reaction and liquid-liquid extraction has been investigated. The DBT dissolved in tetradecane was photodecomposed by the use of a high-pressure mercury lamp and removed into the water phase at conditions of room temperature and atmospheric pressure. The addition of benzophenone (BZP), a triplet photosensitizer, enhanced the removal of DBT from tetradecane. This reaction, however, hardly proceeded in the presence of naphthalene (NP), probably because of triplet energy transfer from photoexcited DBT or BZP to ground-state NP. The addition of hydrogen peroxide enhanced the desulfurization of commercial light oil as well as the removal of DBT from tetradecane, since H{sub 2}O{sub 2} acted as a weak oxidizing agent for photoexcited DBT and interrupted the energy transfer from excited DBT to NP to some extent. In the case using a 30% H{sub 2}O{sub 2} solution, the desulfurization yield of commercial light oil was 75% following 24 h of photoirradiation and the sulfur content in the light oil was reduced from 0.2 wt % to less than 0.05 wt %.

  11. 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. PMID:25465876

  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. PMID:22230756

  13. 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.

  14. Mechanism of highly efficient in-furnace desulfurization by limestone under O{sub 2}/CO{sub 2} coal combustion atmosphere

    SciTech Connect

    Chen, C.M.; Zhao, C.S.

    2006-07-05

    The desulfurization characteristics of limestone under O{sub 2}/CO{sub 2} atmosphere were studied by a drop-tube furnace test rig. The experimental results show that high CO{sub 2} concentration makes the calcination reaction of limestone slow and that the pore structure of calcined limestone is more suitable for high-temperature desulfurization under O{sub 2}/CO{sub 2} atmosphere. A desulfurization mechanism for limestone under O{sub 2}/CO{sub 2} coal combustion atmosphere is proposed based on the experiments. The system keeps on producing nascent CaO continuously. At the same time, the diffusion resistance through CaSO{sub 4} product layer is reduced because CO{sub 2} is formed at the CaO/CaCO{sub 3} interface before complete limestone decomposition into CaO. The above two factors make CaO keep on a high sulfation rate for a long time under O{sub 2}/CO{sub 2} atmosphere. So the high Ca conversion of limestone can be reached under O{sub 2}/CO{sub 2} atmosphere. There is an optimal desulfurization temperature for limestone in O-2/CO{sub 2} atmosphere as in air. The optimal desulfurization temperature and corresponding desulfurization efficiency increase with the CO{sub 2} concentration in O{sub 2}/CO{sub 2} atmosphere. It is implied that the O{sub 2}/CO{sub 2} atmosphere is beneficial to limestone desulfurization at higher temperature.

  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. 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.

  17. Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge Polarization

    SciTech Connect

    Rodriguez, J.; Liu, P; Takahashi, Y; Nakamura, K; Vines, F; Illas, F

    2009-01-01

    Photoemission and first-principles DF calculations were used to study the interaction of thiophene with TiC(001) and Au/TiC(001) surfaces. The adsorption strength of thiophene on TiC(001) is weak, and the molecule desorbs at temperatures below 200 K. The molecule binds to Ti centers of TiC(001) through its sulfur atom with negligible structural perturbations. In spite of the very poor desulfurization performance of TiC(001) or Au(111), a Au/TiC(001) system displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. The Au?TiC(001) interactions induce a polarization of electron density around Au which substantially increases the chemical reactivity of this metal. Au nanoparticles drastically increase the hydrodesulfurization activity of TiC(001) by enhancing the bonding energy of thiophene and by helping in the dissociation of H{sub 2} to produce the hydrogen necessary for the hydrogenolysis of C-S bonds and the removal of sulfur. H{sub 2} spontaneously dissociates on small two-dimensional clusters of gold in contact with TiC(001). On these systems, the adsorption energy of thiophene is 0.45-0.65 eV larger than that on TiC(001) or Au(111). Thiophene binds in a ?5 configuration with a large elongation ({approx}0.2 {angstrom}) of the C-S bonds.

  18. [Effect of flue gas desulfurization gypsum application on remediation of acidified forest soil].

    PubMed

    Luo, Yao; Kang, Rong-Hua; Yu, De-Xiang; Tan, Bing-Quan; Duan, Lei

    2012-06-01

    Effect of flue gas desulfurization gypsum (FGDG) application on remediation of a typical acidified forest soil was studied through field experiments at Tieshanping, Chongqing in southwest China for one year. To evaluate the effect and risk of FGDG application, pH value, major ions and heavy metal of soil water in different soil layers were observed dynamically, and heavy metal contained in soil and FGDG were measured. Results showed that Ca2+ and SO4(-2) concentration of soil water in FGDG plots increased with time, pH value was elevated slightly, and n(Ca)/n(Al) value of annual average increased from 2.16, 1.35 and 0.88 to 2.58, 1.52 and 1.12 compared with control plots. The concentration of As, Cu, Cr, Ni and Zn in soil water was not elevated significantly. However, slight enrichment of Cr, Ni and Zn in some upper soil layers was observed. Consequently, FGDG application can improve acidified forest soil, without obviously heavy metal increasing in soil water. However, risk for heavy metal enrichment still exists, which is need for further study. PMID:22946189

  19. 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.

  20. Studies involving high temperature desulfurization/regeneration reactions of metal oxides for fuel cell development

    NASA Astrophysics Data System (ADS)

    Jalan, V.

    1983-10-01

    A high temperature regenerable desulfurization process capable of reducing the sulfur content in coal gases from 200 pp to 1 ppm was investigated to provide for the integration of a coal gasifier with a molten carbonate fuel cell, which requires that the sulfur content be below 1 ppm. Results obtained with packed-bed and fluidized-bed reactors have demonstrated that a CuO/ZnO mixed oxide sorbent is regenerble and capable of lowering the sulfur content (as H2s and COS) from 200 ppm in simulated hot coal-derived gases to below 1 ppm level at 600 to 650 C. A comprecipitated CuO/ZnO was elected for further study. A structural reorganization mechanism, unique to mixed oxides, was identified: the creation of relatively fine crystallites of the sulfide components (Cu2S and ZnS) to counteract the loss of surface area due to sintering during regeneration. Studies with 9 to 26% water vapor in simulated coal gases show that sulfur levels below 1 ppm can be achieved in the temperature range of 500 to 650 C. The ability of CuO/ZnO to remove COS, CS2 and CH3SH at these conditions was demonstrated. A previously proposed pore-plugging model was further developed with good success for data treatment of both packed-bed and fluidized-bed reactors.