40 CFR 63.7852 - What definitions apply to this subpart?

Code of Federal Regulations, 2012 CFR

2012-07-01

... hot metal, usually with dry air or nitrogen, to remove sulfur. Deviation means any instance in which... capture and collection of secondary emissions from a basic oxygen process furnace. Sinter cooler means the...

40 CFR 63.7852 - What definitions apply to this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... hot metal, usually with dry air or nitrogen, to remove sulfur. Deviation means any instance in which... capture and collection of secondary emissions from a basic oxygen process furnace. Sinter cooler means the...

40 CFR 63.7852 - What definitions apply to this subpart?

Code of Federal Regulations, 2013 CFR

2013-07-01

... hot metal, usually with dry air or nitrogen, to remove sulfur. Deviation means any instance in which... capture and collection of secondary emissions from a basic oxygen process furnace. Sinter cooler means the...

40 CFR 63.7852 - What definitions apply to this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

... hot metal, usually with dry air or nitrogen, to remove sulfur. Deviation means any instance in which... capture and collection of secondary emissions from a basic oxygen process furnace. Sinter cooler means the...

40 CFR 63.7852 - What definitions apply to this subpart?

Code of Federal Regulations, 2014 CFR

2014-07-01

... hot metal, usually with dry air or nitrogen, to remove sulfur. Deviation means any instance in which... capture and collection of secondary emissions from a basic oxygen process furnace. Sinter cooler means the...

Removal of mercury from coal via a microbial pretreatment process

DOEpatents

Borole, Abhijeet P [Knoxville, TN; Hamilton, Choo Y [Knoxville, TN

2011-08-16

A process for the removal of mercury from coal prior to combustion is disclosed. The process is based on use of microorganisms to oxidize iron, sulfur and other species binding mercury within the coal, followed by volatilization of mercury by the microorganisms. The microorganisms are from a class of iron and/or sulfur oxidizing bacteria. The process involves contacting coal with the bacteria in a batch or continuous manner. The mercury is first solubilized from the coal, followed by microbial reduction to elemental mercury, which is stripped off by sparging gas and captured by a mercury recovery unit, giving mercury-free coal. The mercury can be recovered in pure form from the sorbents via additional processing.

The use of ethanol to remove sulfur from coal. Final report, September 1991--December 1992; Revision

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savage, R.L.; Lazarov, L.K.; Prudich, M.E.

1994-03-10

The initial technical goal in the project was to develop a chemical method for the cost effective removal of both inorganic and organic sulfur from Ohio coals. Verifying and using a process of reacting ethanol vapors with coal under conditions disclosed in U.S. Patent 4,888,029, the immediate technical objectives were to convert a small scale laborative batch process to a larger scale continuous process which can serve as the basis for commercial development of the technology. This involved getting as much information as possible from small scale batch autoclave or fluid bed laboratory reactors for use in pilot plant studies.more » The laboratory data included material balances on the coal and sulfur, temperature and pressure ranges for the reaction, minimum reaction times at different conditions, the effectiveness of different activators such as oxygen and nitric oxide, the amount and nature of by-products such as sulfur dioxide, hydrogen sulfide and acetaldehyde, the effect of coal particle size on the speed and completeness of the reaction, and the effectiveness of the reaction on different Ohio coals. Because the laboratory experiments using the method disclosed in U.S. 4,888,029 were not successful, the objective for the project was changed to develop a new laboratory process to use ethanol to remove sulfur from coal. Using copper as a catalyst and as an H{sub 2}S scavenger, a new laboratory procedure to use ethanol to remove sulfur from coal has been developed at Ohio University and a patent application covering this process was filed in March, 1993. The process is based on the use of copper as a catalyst for the dehydrogenation of ethanol to produce nascent hydrogen to remove sulfur from the coal and the use of copper as a scavenger to capture the hydrogen sulfide formed from the sulfur removed from coal.« less

Integrating a Photocatalyst into a Hybrid Lithium-Sulfur Battery for Direct Storage of Solar Energy.

PubMed

Li, Na; Wang, Yarong; Tang, Daiming; Zhou, Haoshen

2015-08-03

Direct capture and storage of abundant but intermittent solar energy in electrical energy-storage devices such as rechargeable lithium batteries is of great importance, and could provide a promising solution to the challenges of energy shortage and environment pollution. Here we report a new prototype of a solar-driven chargeable lithium-sulfur (Li-S) battery, in which the capture and storage of solar energy was realized by oxidizing S(2-) ions to polysulfide ions in aqueous solution with a Pt-modified CdS photocatalyst. The battery can deliver a specific capacity of 792 mAh g(-1) during 2 h photocharging process with a discharge potential of around 2.53 V versus Li(+)/Li. A specific capacity of 199 mAh g(-1), reaching the level of conventional lithium-ion batteries, can be achieved within 10 min photocharging. Moreover, the charging process of the battery can proceed under natural sunlight irradiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The impact of oil burning on kraft recovery furnace SO sub 2 emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Someshwar, A.V.; Pinkerton, J.E.; Caron, A.L.

1991-04-01

Auxiliary fossil fuel, either natural gas or fuel oil, is burned in kraft recovery furnaces during furnace startups and shutdowns, furnace upsets, and periods of substantially reduced rates of black liquor firing. The efficiency of sulfur capture and retention during normal operation of a kraft recovery furnace is inherently high. Consequently, not all the SO{sub 2} from occasional burning of sulfur-containing fuel oil in the furnace would be expected to end up in the stack gases. However, the extent to which such SO{sub 2} is captured by the alkali fume generation processes has not been well documented. In this paper,more » the authors examines the impact that burning oil in kraft recovery furnaces has on the SO{sub 2} emissions. The work included analyses of long-term SO{sub 2} data from a continuous emission monitoring system (CEMS) obtained for four furnaces that burned medium sulfur fuel oil as auxiliary fuel. It also included tests conducted on four furnaces in which varying amounts of oil were co-fired with black liquor.« less

Nitrogen and sulfur Co-doped microporous activated carbon macro-spheres for CO2 capture.

PubMed

Sun, Yahui; Li, Kaixi; Zhao, Jianghong; Wang, Jianlong; Tang, Nan; Zhang, Dongdong; Guan, Taotao; Jin, Zuer

2018-04-27

Millimeter-sized nitrogen and sulfur co-doped microporous activated carbon spheres (NSCSs) were first synthesized from poly(styrene-vinylimidazole-divinylbenzene) resin spheres through concentrated H 2 SO 4 sulfonation, carbonization and KOH activation. Styrene (ST) and N-vinylimidazole (VIM) were carbon and nitrogen sources, while the sulfonic acid functional groups introduced by the simple concentrated sulfuric acid sulfonation worked simultaneously as cross-linking agent and sulfur source during the following thermal treatments. It was found that the surface chemistries, textural structures, and CO 2 adsorption performances of the NSCSs were significantly affected by the addition of VIM. The NSCS-4-700 sample with a molar ratio of ST: VIM = 1: 0.75 showed the best CO 2 uptake at different temperatures and pressures. An exhaustive adsorption evaluation indicated that CO 2 sorption at low pressures originated from the synergistic effect of surface chemistry and micropores below 8.04 Å, while at the moderate pressure of 8.0 bar, CO 2 uptake was dominated by the volume of micropores. The thermodynamics suggested the exothermic and orderly nature of the adsorption process, which was dominated by a physisorption mechanism. The high CO 2 adsorption capacity, fast kinetic adsorption rate, and great regeneration stability of the nitrogen and sulfur co-doped activated carbon spheres indicated that the as-prepared carbon adsorbents were good candidates for large-scale CO 2 capture. Copyright © 2018 Elsevier Inc. All rights reserved.

Role of RIS/APC for manufacturing RFG/LSD. [Refinery Information Systems/Advanced Process Control, ReFormulated Gasoline/Low Sulfur Diesels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latour, P.R.

Revolutionary changes in quality specifications (number, complexity, uncertainty, economic sensitivity) for reformulated gasolines (RFG) and low-sulfur diesels (LSD) are being addressed by powerful, new, computer-integrated manufacturing technology for Refinery Information Systems and Advanced Process Control (RIS/APC). This paper shows how the five active RIS/APC functions: performance measurement, optimization, scheduling, control and integration are used to manufacture new, clean fuels competitively. With current industry spending for this field averaging 2 to 3 cents/bbl crude, many refineries can capture 50 to 100 cents/bbl if the technology is properly employed and sustained throughout refining operations, organizations, and businesses.

Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

PubMed

Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

2017-11-01

A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howe, Gary; Albritton, John; Denton, David

In September 2010, RTI and the DOE/NETL signed a cooperative agreement (DE-FE000489) to design, build, and operate a pre-commercial syngas cleaning system that would capture up to 90% of the CO 2 in the syngas slipstream, and demonstrate the ability to reduce syngas contaminants to meet DOE’s specifications for chemical production application. This pre-commercial syngas cleaning system is operated at Tampa Electric Company’s (TEC) 250-MWe integrated gasification combined cycle (IGCC) plant at Polk Power Station (PPS), located near Tampa, Florida. The syngas cleaning system consists of the following units: Warm Gas Desulfurization Process (WDP) - this unit processes a syngasmore » flow equivalent of 50 MWe of power (50 MWe equivalent corresponds to about 2.0 MM scfh of syngas on dry basis) to produce a desulfurized syngas with a total sulfur (H 2S+COS) concentration ~ 10 ppmv. Water Gas Shift (WGS) Reactor - this unit converts sufficient CO into CO 2 to enable 90% capture of the CO 2 in the syngas slipstream. This reactor uses conventional commercial shift catalyst technologies. Low Temperature Gas Cooling (LTGC) - this unit cools the syngas for the low temperature activated MDEA process and separates any condensed water. Activated MDEA Process (aMDEA) - this unit employs a non-selective separation for the CO 2 and H 2S present in the raw syngas stream. Because of the selective sulfur removal by the upstream WDP unit, the CO 2 capture target of 90% CO 2 can be achieved with the added benefit that total sulfur concentration in the CO 2 product is < 100 ppmv. An additional advantage of the activated MDEA process is that the non-selective sulfur removal from the treated syngas reduces sulfur in the treated gas to very low sub-ppmv concentrations, which are required for chemical production applications. Testing to date of this pre-commercial syngas cleaning system has shown that the technology has great potential to provide clean syngas from coal and petcoke-based gasification at increased efficiency and at significantly lower capital and operating costs than conventional syngas cleanup technologies. However, before the technology can be deemed ready for scale-up to a full commercial-scale demonstration, additional R&D testing is needed at the site to address the following critical technical risks: WDP sorbent stability and performance; Impact of WDP on downstream cleanup and conversion steps; Metallurgy and refractory; Syngas cleanup performance and controllability; Carbon capture performance and additional syngas cleanup The proposed plan to acquire this additional R&D data involves: Operation of the units to achieve an additional 3,000 hours of operation of the system within the performance period, with a target of achieving 1,000 hours of those hours via continuous operation of the entire integrated pre-commercial demonstration system; Rapid turnaround of repairs and/or modifications required as necessary to return any specific unit to operating status with documentation and lessons learned to support technology maturation, and; Proactive performance of maintenance activities during any unplanned outages and if possible while operating.« less

Polysulfides capture-copper additive for long cycle life lithium sulfur batteries

DOE PAGES

Jia, Lei; Wu, Tianpin; Lu, Jun; ...

2016-10-18

Copper powder was introduced into the lithium sulfur battery system to capture intermediate polysulfides and Cu xS (x = 1 or 2) species was generated depending on the chain length of polysulfides. This phenomenon was verified by X-ray absorption near edge structure technique. The results indicated that copper can be oxidized to CuS by Li 2S x (x ≥ 6), and a mixture of Cu 2S and CuS was obtained when x ranges from 3 to 6. While Cu 2S is eventually formed in the presence of Li 2S 3. After several cycles activation, the polysulfide-shuttle effect and self-discharge phenomenonmore » which hinder the application of lithium sulfur batteries are found nearly eliminated Further experiments demonstrated that in the case of Cu 2S generation, a high specific sulfur capacity of 1300 mAh g –1 could be delivered, corresponding to 77.6% sulfur utilization, while the Coulombic efficiency approximates around 100%. As a result, self-discharge experiment further demonstrated that polysulfides almost disappear in the electrolyte, which verified the polysulfide-capture capability of copper.« less

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-02-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

PubMed Central

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-01-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

Influence of periodically changing oxidizing and reducing environment on sulfur capture under PFBC conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yrjas, P.; Hupa, M.

1997-12-31

In the literature it has been reported that sulfur capture with limestone (CaCO{sub 3}) under atmospheric fluidized bed combustion conditions reaches a maximum at about 850 C. Previously, the maximum has been attributed to the sintering of the sorbent particles which decreases the reactive surface area. Lately, also another explanation has been reported. In this case the sulfur capture decrease at higher temperatures was concluded to be due to fluctuating oxidizing/reducing conditions in the atmospheric combustor. In this paper the influence of alternating oxidizing/reducing conditions on SO{sub 2} capture at atmospheric and elevated pressure (15 bar) is reported. In themore » pressurized case, the CO{sub 2} partial pressure was kept high enough to prevent CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} under reducing conditions. The experiments were done with a pressurized TGA by periodically changing the gas environment between oxidizing (O{sub 2}, SO{sub 2}, CO{sub 2} and N{sub 2}) and slightly reducing (CO, SO{sub 2}, CO{sub 2} and N{sub 2}) gas mixtures at different temperatures. The results showed that under normal pressure and slightly reducing conditions CaO formation from CaSO{sub 4} increased with temperature as expected. However, no significant amounts of CaCO{sub 3} were formed from CaSO{sub 4} at elevated pressure. It was also concluded that since the formation of CaO from CaSO{sub 4} was relatively slow it could not explain the sharp sulfur capture maximum at about 850 C. Therefore, it was assumed that the strongly reducing zones, where CaS thermodynamically is the stable compound, may play a more important role than the slightly reducing zones, concerning the sulfur capture in fluidized bed combustors.« less

Onboard Detection of Active Canadian Sulfur Springs: A Europa Analogue

NASA Technical Reports Server (NTRS)

Castano, Rebecca; Wagstaff, Kiri; Gleeson, Damhnait; Pappalardo, Robert; Chien, Steve; Tran, Daniel; Scharenbroich, Lucas; Moghaddam, Baback; Tang, Benyang; Bue, Brian;

Dry syngas purification process for coal gas produced in oxy-fuel type integrated gasification combined cycle power generation with carbon dioxide capturing feature.

PubMed

Kobayashi, Makoto; Akiho, Hiroyuki

2017-12-01

Electricity production from coal fuel with minimizing efficiency penalty for the carbon dioxide abatement will bring us sustainable and compatible energy utilization. One of the promising options is oxy-fuel type Integrated Gasification Combined Cycle (oxy-fuel IGCC) power generation that is estimated to achieve thermal efficiency of 44% at lower heating value (LHV) base and provide compressed carbon dioxide (CO 2 ) with concentration of 93 vol%. The proper operation of the plant is established by introducing dry syngas cleaning processes to control halide and sulfur compounds satisfying tolerate contaminants level of gas turbine. To realize the dry process, the bench scale test facility was planned to demonstrate the first-ever halide and sulfur removal with fixed bed reactor using actual syngas from O 2 -CO 2 blown gasifier for the oxy-fuel IGCC power generation. Design parameter for the test facility was required for the candidate sorbents for halide removal and sulfur removal. Breakthrough test was performed on two kinds of halide sorbents at accelerated condition and on honeycomb desulfurization sorbent at varied space velocity condition. The results for the both sorbents for halide and sulfur exhibited sufficient removal within the satisfactory short depth of sorbent bed, as well as superior bed conversion of the impurity removal reaction. These performance evaluation of the candidate sorbents of halide and sulfur removal provided rational and affordable design parameters for the bench scale test facility to demonstrate the dry syngas cleaning process for oxy-fuel IGCC system as the scaled up step of process development. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of an Integrated Multi-Contaminant Removal Process Applied to Warm Syngas Cleanup for Coal-Based Advanced Gasification Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Howard

2010-11-30

This project met the objective to further the development of an integrated multi-contaminant removal process in which H2S, NH3, HCl and heavy metals including Hg, As, Se and Cd present in the coal-derived syngas can be removed to specified levels in a single/integrated process step. The process supports the mission and goals of the Department of Energy's Gasification Technologies Program, namely to enhance the performance of gasification systems, thus enabling U.S. industry to improve the competitiveness of gasification-based processes. The gasification program will reduce equipment costs, improve process environmental performance, and increase process reliability and flexibility. Two sulfur conversion conceptsmore » were tested in the laboratory under this project, i.e., the solventbased, high-pressure University of California Sulfur Recovery Process High Pressure (UCSRP-HP) and the catalytic-based, direct oxidation (DO) section of the CrystaSulf-DO process. Each process required a polishing unit to meet the ultra-clean sulfur content goals of <50 ppbv (parts per billion by volume) as may be necessary for fuel cells or chemical production applications. UCSRP-HP was also tested for the removal of trace, non-sulfur contaminants, including ammonia, hydrogen chloride, and heavy metals. A bench-scale unit was commissioned and limited testing was performed with simulated syngas. Aspen-Plus®-based computer simulation models were prepared and the economics of the UCSRP-HP and CrystaSulf-DO processes were evaluated for a nominal 500 MWe, coal-based, IGCC power plant with carbon capture. This report covers the progress on the UCSRP-HP technology development and the CrystaSulf-DO technology.« less

Multi-functional sorbents for the simultaneous removal of sulfur and lead compounds from hot flue gases.

PubMed

Zhao, Yi; Lin, Wen-Chiang

2003-10-01

A multi-functional sorbent is developed for the simultaneous removal of PbCl(2) vapor and sulfur dioxide from the combustion gases. The sorbent is tested in a bench-scale reactor at the temperature of 700 degrees C, using simulated flue gas (SFG) containing controlled amounts of PbCl(2) and SO(2) compounds. The removal characteristics of PbCl(2) and SO(2), individually and in combination, are investigated. The results show that the mechanism of capture by the sorbent is not a simple physical adsorption process but seems to involve a chemical reaction between the Ca-based sorbent and the contaminants from the simulated flue gas. The porous product layer in the case of individual SO(2) sorption is in a molten state at the reaction temperature. In contrast, the combined sorption of lead and sulfur compounds generates a flower-shaped polycrystalline product layer.

Thermodynamics Calculation and Experimental Study on Separation of Bismuth from a Bismuth Glance Concentrate Through a Low-Temperature Molten Salt Smelting Process

NASA Astrophysics Data System (ADS)

Yang, Jian-Guang; He, De-Wen; Tang, Chao-Bo; Chen, Yong-Ming; Sun, Ya-Hui; Tang, Mo-Tang

2011-08-01

The main purpose of this study is to characterize and separate bismuth from a bismuth glance concentrate through a low-temperature, sulfur-fixing smelting process. This article reports on a study conducted on the optimization of process parameters, such as Na2CO3 and zinc oxide wt pct in charging, smelting temperature, smelting duration on the bismuth yield, resultant crude bismuth grade, and sulfur-fixing rate. A maximum bismuth recovery of 97.31 pct, crude bismuth grade of 96.93 pct, and 98.23 pct sulfur-fixing rate are obtained when a charge (containing 63.50 wt pct of Na2CO3 and 22.50 wt pct of bismuth glance, as well as 5 pct in excess of the stoichiometric requirement of zinc oxide dosage) is smelted at 1000 K (727 °C) for 150 minutes. This smelting operation is free from atmospheric pollution because zinc oxide is used as the sulfur-fixing agent, which can capture sulfur from bismuth sulfide and form the more thermodynamic-stable compound, zinc sulfide. The solid residue is subjected to a mineral dressing operation to obtain suspension, which is filtered to produce a cake, representing the solid particles of zinc sulfide. Based on the results of the chemical content analysis of the as-resultant zinc sulfide, more than 93 pct zinc sulfide can be recovered, and the recovered zinc sulfide grade can reach 60.20 pct. This material can be sold as zinc sulfide concentrate or roasted to be regenerated as zinc oxide.

Hydrogen sulfide capture by limestone and dolomite at elevated pressure. 1: Sorbent performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yrjas, K.P.; Zevenhoven, C.A.P.; Hupa, M.M.

1996-01-01

Sulfur emission control in fossil fuel gasification plants implies the removal of H{sub 2}S from the product gas either inside the furnace or in the gas clean-up system. In a fluidized-bed gasifier, in-bed sulfur capture can be accomplished by adding a calcium-based sorbent such as limestone or dolomite to the bend and removing the sulfur from the system with the bottom ash in the form of CaS. This work describes the H{sub 2}S uptake by a set of physically and chemically different limestones and dolomites under pressurized conditions, typically for those in a pressurized fluidized-bed gasifier (2 MPa, 950 C).more » The tests were done with a pressurized thermobalance at two p{sub CO{sub 2}} levels. Thus, the sulfidation of both calcined and uncalcined sorbents could be analyzed. The effect of p{sub H{sub 2}S} was also investigated for uncalcined limestones and half-calcined dolomites. The results are presented as conversion of CaCO{sub 3} or CaO to CaS vs time plots. The results are also compared with the sulfur capture performance of the same sorbents under pressurized combustion conditions.« less

Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

DOEpatents

Ramkumar, Shwetha; Fan, Liang-Shih

2013-07-30

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas.

PubMed

Lee, How Ming; Chang, Moo Been; Wu, Kuan Yu

2004-08-01

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.

Destruction of a high sulfur pitch in an industrial scale fluidized bed combustor

DOE Office of Scientific and Technical Information (OSTI.GOV)

North, B.; Eleftheriades, C.; Engelbrecht, A.

Sasol approached the CSIR's division of Materials Science and Technology (CSIR Mattek) for an environmentally acceptable solution to their steadily increasing stockpiles of a high sulfur pitch. Conventional incineration of the pitch would result in unacceptably high levels of sulfur dioxide emission to the atmosphere. In addition to the pitch, Sasol indicated a need to dispose of a waste water stream contaminated with organic compounds. After some initial development work CSIR Mattek, in conjunction with its licensee IMS Process Plant, presented a design for a multipurpose bubbling fluidized bed incineration plant that completely destroys the pitch and effluent water whilemore » capturing a minimum of 85% of the incoming sulfur in the pitch by limestone injection. The plant design caters for the variable consistency of both the pitch and the organic waste water, which can contain from 0 to 10% organics. The design also allows for potential future treatment of contaminated soils. In addition to the environment benefit of the reduction of sulfur dioxide emissions, the plant also makes use of the hot combustion gases to raise 20 t/hr of saturated steam at 20 bar via an external waste heat boiler. This represents a valuable commodity for the business unit responsible for the waste incineration and makes the Sasol plant a more energy efficient entity. It also represents a net reduction in CO{sub 2} emissions from Sasol. The high sulfur pitch incineration plant was commissioned in Sasolburg by a team of engineers from CSIR Mattek, IMS Process Plant and Sasol during December 1996 and January/February 1997. The plant has performed extremely well and it has complied with the environmental emission requirements as set out by the Department of Environmental Affairs and Tourism.« less

ENHANCEMENT OF REACTIVITY IN SURFACTANT-MODIFIED SORBENTS FOR SULFUR DIOXIDE CONTROL

EPA Science Inventory

Injection of calcium-based sorbents into the postflame zone of utility boilers is capable of achieving sulfur dioxide (SO2) captures of 50-60% at a stoichiometry of 2. Calcium hydroxide [Ca(OH)2] appears to be the most effective commercially available sorbent. Recent attempts to ...

Sodium and sulfur release and recapture during black liquor burning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frederick, W.J.; Iisa, K.; Wag, K.

1995-08-01

The objective of this study was to provide data on sulfur and sodium volatilization during black liquor burning, and on SO2 capture by solid sodium carbonate and sodium chloride. This data was interpreted and modeled into rate equations suitable for use in computational models for recovery boilers.

Determination of sulfur dioxide in wine using headspace gas chromatography and electron capture detection.

PubMed

Aberl, A; Coelhan, M

2013-01-01

Sulfites are routinely added as preservatives and antioxidants in wine production. By law, the total sulfur dioxide content in wine is restricted and therefore must be monitored. Currently, the method of choice for determining the total content of sulfur dioxide in wine is the optimised Monier-Williams method, which is time consuming and laborious. The headspace gas chromatographic method described in this study offers a fast and reliable alternative method for the detection and quantification of the sulfur dioxide content in wine. The analysis was performed using an automatic headspace injection sampler, coupled with a gas chromatograph and an electron capture detector. The method is based on the formation of gaseous sulfur dioxide subsequent to acidification and heating of the sample. In addition to free sulfur dioxide, reversibly bound sulfur dioxide in carbonyl compounds, such as acetaldehyde, was also measured with this method. A total of 20 wine samples produced using diverse grape varieties and vintages of varied provenance were analysed using the new method. For reference and comparison purposes, 10 of the results obtained by the proposed method were compared with those acquired by the optimised Monier-Williams method. Overall, the results from the headspace analysis showed good correlation (R = 0.9985) when compared with the conventional method. This new method requires minimal sample preparation and is simple to perform, and the analysis can also be completed within a short period of time.

Measurement of cardiac output using improved chromatographic analysis of sulfur hexafluoride (SF6).

PubMed

Klocke, F J; Roberts, D L; Farhi, E R; Naughton, B J; Sekovski, B; Klocke, R A

1977-06-01

A constant current variable frequency pulsed electron capture detector has been incorporated into the gas chromatographic analysis of trace amounts of sulfur hexafluoride (SF6) in water and blood. The resulting system offers a broader effective operating range than more conventional electron capture units and has been utilized for measurements of cardiac output employing constant-rate infusion of dissolved SF6. The SF6 technique has been validated against direct volumetric measurements of cardiac output in a canine right-heart bypass preparation and used subsequently for rapidly repeated measurements in conscious animals and man.

Recovery of ammonia from poultry litter using flat gas permeable membranes.

PubMed

Rothrock, M J; Szögi, A A; Vanotti, M B

2013-06-01

The use of flat gas-permeable membranes was investigated as components of a new process to capture and recover ammonia (NH3) in poultry houses. This process includes the passage of gaseous NH3 through a microporous hydrophobic membrane, capture with a circulating dilute acid on the other side of the membrane, and production of a concentrated ammonium (NH4) salt. Bench- and pilot-scale prototype systems using flat expanded polytetrafluoroethylene (ePTFE) membranes and a sulfuric acid solution consistently reduced headspace NH3 concentrations from 70% to 97% and recovered 88% to 100% of the NH3 volatilized from poultry litter. The potential benefits of this technology include cleaner air inside poultry houses, reduced ventilation costs, and a concentrated liquid ammonium salt that can be used as a plant nutrient solution. Published by Elsevier Ltd.

EERC pilot-scale CFBC evaluation facility Project CFB test results. Topical report, Task 7.30

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mann, M.D.; Hajicek, D.R.; Henderson, A.K.

Project CFB was initiated at the University of North Dakota Energy and Environmental Research Center (EERC) in May 1988. Specific goals of the project were to (1) construct a circulating fluidized-bed combustor (CFBC) facility representative of the major boiler vendors` designs with the capability of producing scalable data, (2) develop a database for use in making future evaluations of CFBC technology, and (3) provide a facility for evaluating fuels, free of vendor bias for use in the - energy industry. Five coals were test-burned in the 1-MWth unit: North Dakota and Asian lignites, a Wyoming subbituminous, and Colorado and Pennsylvaniamore » bituminous coats. A total of 54 steady-state test periods were conducted, with the key test parameters being the average combustor temperature, excess air, superficial gas velocity, calcium-to-sulfur molar ratio, and the primary air-to-secondary air split. The capture for a coal fired in a CFBC is primarily dependent upon the total alkali-to-sulfur ratio. The required alkali-to ratio for 90% sulfur retention ranged from 1.4 to 4.9, depending upon coal type. While an alkali-to-ratio of 4.9 was required to meet 90% sulfur retention for the Salt Creek coal versus 1.4 for the Asian lignite, the total amount of sorbent addition required is much less for the Salt Creek coal, 4.2 pound sorbent per million Btu coal input, versus 62 pound/million Btu for the Asian lignite. The bituminous coals tested show optimal capture at combustor temperatures of approximately 1550{degree}F, with low-rank coals having optimal sulfur capture approximately 100{degree}F lower.« less

EERC pilot-scale CFBC evaluation facility Project CFB test results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mann, M.D.; Hajicek, D.R.; Henderson, A.K.

Project CFB was initiated at the University of North Dakota Energy and Environmental Research Center (EERC) in May 1988. Specific goals of the project were to (1) construct a circulating fluidized-bed combustor (CFBC) facility representative of the major boiler vendors' designs with the capability of producing scalable data, (2) develop a database for use in making future evaluations of CFBC technology, and (3) provide a facility for evaluating fuels, free of vendor bias for use in the - energy industry. Five coals were test-burned in the 1-MWth unit: North Dakota and Asian lignites, a Wyoming subbituminous, and Colorado and Pennsylvaniamore » bituminous coats. A total of 54 steady-state test periods were conducted, with the key test parameters being the average combustor temperature, excess air, superficial gas velocity, calcium-to-sulfur molar ratio, and the primary air-to-secondary air split. The capture for a coal fired in a CFBC is primarily dependent upon the total alkali-to-sulfur ratio. The required alkali-to ratio for 90% sulfur retention ranged from 1.4 to 4.9, depending upon coal type. While an alkali-to-ratio of 4.9 was required to meet 90% sulfur retention for the Salt Creek coal versus 1.4 for the Asian lignite, the total amount of sorbent addition required is much less for the Salt Creek coal, 4.2 pound sorbent per million Btu coal input, versus 62 pound/million Btu for the Asian lignite. The bituminous coals tested show optimal capture at combustor temperatures of approximately 1550[degree]F, with low-rank coals having optimal sulfur capture approximately 100[degree]F lower.« less

Strategies for Carbon and Sulfur Tolerant Solid Oxide Fuel Cell Materials, Incorporating Lessons from Heterogeneous Catalysis.

PubMed

Boldrin, Paul; Ruiz-Trejo, Enrique; Mermelstein, Joshua; Bermúdez Menéndez, José Miguel; Ramı Rez Reina, Tomás; Brandon, Nigel P

2016-11-23

Solid oxide fuel cells (SOFCs) are a rapidly emerging energy technology for a low carbon world, providing high efficiency, potential to use carbonaceous fuels, and compatibility with carbon capture and storage. However, current state-of-the-art materials have low tolerance to sulfur, a common contaminant of many fuels, and are vulnerable to deactivation due to carbon deposition when using carbon-containing compounds. In this review, we first study the theoretical basis behind carbon and sulfur poisoning, before examining the strategies toward carbon and sulfur tolerance used so far in the SOFC literature. We then study the more extensive relevant heterogeneous catalysis literature for strategies and materials which could be incorporated into carbon and sulfur tolerant fuel cells.

Highly efficient SO2 capture through tuning the interaction between anion-functionalized ionic liquids and SO2.

PubMed

Wang, Congmin; Zheng, Junjie; Cui, Guokai; Luo, Xiaoyan; Guo, Yan; Li, Haoran

2013-02-11

A strategy to improve SO(2) capture through tuning the electronegativity of the interaction site in ILs has been presented. Two types of imidazolium ionic liquids that include less electronegative sulfur or carbon sites were used for the capture of SO(2), which exhibit extremely highly available capacity, rapid absorption rate and excellent reversibility.

Simultaneous removal of SO2 and trace SeO2 from flue gas: effect of SO2 on selenium capture and kinetics study.

PubMed

Li, Yuzhong; Tong, Huiling; Zhuo, Yuqun; Wang, Shujuan; Xu, Xuchang

2006-12-15

Sulfur dioxide (SO2) and trace elements are all pollutants derived from coal combustion. This study relates to the simultaneous removal of SO2 and trace selenium dioxide (SeO2) from flue gas by calcium oxide (CaO) adsorption in the moderate temperature range, especially the effect of SO2 presence on selenium capture. Experiments performed on a thermogravimetric analyzer (TGA) can reach the following conclusions. When the CaO conversion is relatively low and the reaction rate is controlled by chemical kinetics, the SO2 presence does not affect the selenium capture. When the CaO conversion is very high and the reaction rate is controlled by product layer diffusion, the SO2 presence and the product layer diffusion resistance jointly reduce the selenium capture. On the basis of the kinetics study, a method to estimate the trace selenium removal efficiency using kinetic parameters and the sulfur removal efficiency is developed.

Producing fired bricks using coal slag from a gasification plant in indiana

USGS Publications Warehouse

Chen, L.-M.; Chou, I.-Ming; Chou, S.-F.J.; Stucki, J.W.

2009-01-01

Integrated gasification combined cycle (IGCC) is a promising power generation technology which increases the efficiency of coal-to-power conversion and enhances carbon dioxide concentration in exhaust emissions for better greenhouse gas capture. Two major byproducts from IGCC plants are bottom slag and sulfur. The sulfur can be processed into commercially viable products, but high value applications need to be developed for the slag material in order to improve economics of the process. The purpose of this study was to evaluate the technical feasibility of incorporating coal slag generated by the Wabash River IGCC plant in Indiana as a raw material for the production of fired bricks. Full-size bricks containing up to 20 wt% of the coal slag were successfully produced at a bench-scale facility. These bricks have color and texture similar to those of regular fired bricks and their water absorption properties met the ASTM specifications for a severe weathering grade. Other engineering properties tests, including compressive strength tests, are in progress.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marrocco, M.

The Ohio Power Company`s Tidd Pressurized Fluidized Bed Combined Cycle (PFBC) program continues to be the only operating PFBC demonstration program in the nation. The 70 MWe Tidd Demonstration Plant is a Round 1 Clean Coal Technology Project constructed to demonstrate the viability of PFBC combined cycle technology. The plant is now in Rs fourth year of operation. The technology has clearly demonstrated Rs ability to achieve sulfur capture of greater than 95%. The calcium to sulfur molar ratios have been demonstrated to exceed original projections. Unit availability has steadily increased and has been demonstrated to be competitive with othermore » technologies. The operating experience of the first forty-four months of testing has moved the PFBC process from a {open_quotes}promising technology{close_quotes} to available, proven option for efficient, environmentally acceptable base load generation. Funding for the $210 million program is provided by Ohio Power Company, The U.S. Department of Energy, The Ohio Coal Development Office, and the PFBC process vendors - Asea Brown Boveri Carbon (ABBC) and Babcock and Wilcox (B&W).« less

Designing and Validating Ternary Pd Alloys for Optimum Sulfur/Carbon Resistance in Hydrogen Separation and Carbon Capture Membrane Systems Using High-Throughput Combinatorial Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewis, Amanda; Zhao, Hongbin; Hopkins, Scott

2014-12-01

This report summarizes the work completed under the U.S. Department of Energy Project Award No.: DE-FE0001181 titled “Designing and Validating Ternary Pd Alloys for Optimum Sulfur/Carbon Resistance in Hydrogen Separation and Carbon Capture Membrane Systems Using High-Throughput Combinatorial Methods.” The project started in October 1, 2009 and was finished September 30, 2014. Pall Corporation worked with Cornell University to sputter and test palladium-based ternary alloys onto silicon wafers to examine many alloys at once. With the specialized equipment at Georgia Institute of Technology that analyzed the wafers for adsorbed carbon and sulfur species six compositions were identified to have resistancemore » to carbon and sulfur species. These compositions were deposited on Pall AccuSep® supports by Colorado School of Mines and then tested in simulated synthetic coal gas at the Pall Corporation. Two of the six alloys were chosen for further investigations based on their performance. Alloy reproducibility and long-term testing of PdAuAg and PdZrAu provided insight to the ability to manufacture these compositions for testing. PdAuAg is the most promising alloy found in this work based on the fabrication reproducibility and resistance to carbon and sulfur. Although PdZrAu had great initial resistance to carbon and sulfur species, the alloy composition has a very narrow range that hindered testing reproducibility.« less

The study of the burning possibilities of solid combustibles in the determined conditions for complete usage of caloric [energy] and ashes resulted

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voina, N.I.; Barca, F.; Mogos, D.

1995-12-31

In modern combustors, 95--98% of the organic mass of a solid combustible is converted into caloric energy; 2--4% remain in the fly ash captured in electrofilters and hydraulically removed in most cases. The 2--4% unburned materials in fly ash, together with the water from being hydraulically transported, make it difficult for the use of the fly ash for metal extraction or as a binder in the materials industry. This work presents the research results of a study in which the burning process was modified to result in fly ash without carbon content and fly ash removal by dry capture. Laboratorymore » fluidized-bed combustion of lignite with and without addition of limestone for sulfur capture was used to generate ashes for further study. The ashes were studied for their use as binders and as a cement substitute.« less

Reducing mode circulating fluid bed combustion

DOEpatents

Lin, Yung-Yi; Sadhukhan, Pasupati; Fraley, Lowell D.; Hsiao, Keh-Hsien

1986-01-01

A method for combustion of sulfur-containing fuel in a circulating fluid bed combustion system wherein the fuel is burned in a primary combustion zone under reducing conditions and sulfur captured as alkaline sulfide. The reducing gas formed is oxidized to combustion gas which is then separated from solids containing alkaline sulfide. The separated solids are then oxidized and recycled to the primary combustion zone.

Evaluation of an 18-year CMAQ simulation: Seasonal variations and long-term temporal changes in sulfate and nitrate

NASA Astrophysics Data System (ADS)

Civerolo, Kevin; Hogrefe, Christian; Zalewsky, Eric; Hao, Winston; Sistla, Gopal; Lynn, Barry; Rosenzweig, Cynthia; Kinney, Patrick L.

2010-10-01

This paper compares spatial and seasonal variations and temporal trends in modeled and measured concentrations of sulfur and nitrogen compounds in wet and dry deposition over an 18-year period (1988-2005) over a portion of the northeastern United States. Substantial emissions reduction programs occurred over this time period, including Title IV of the Clean Air Act Amendments of 1990 which primarily resulted in large decreases in sulfur dioxide (SO 2) emissions by 1995, and nitrogen oxide (NO x) trading programs which resulted in large decreases in warm season NO x emissions by 2004. Additionally, NO x emissions from mobile sources declined more gradually over this period. The results presented here illustrate the use of both operational and dynamic model evaluation and suggest that the modeling system largely captures the seasonal and long-term changes in sulfur compounds. The modeling system generally captures the long-term trends in nitrogen compounds, but does not reproduce the average seasonal variation or spatial patterns in nitrate.

An Integrated, Low Temperature Process to Capture and Sequester Carbon Dioxide from Industrial Emissions

NASA Astrophysics Data System (ADS)

Wendlandt, R. F.; Foremski, J. J.

2013-12-01

Laboratory experiments show that it is possible to integrate (1) the chemistry of serpentine dissolution, (2) capture of CO2 gas from the combustion of natural gas and coal-fired power plants using aqueous amine-based solvents, (3) long-term CO2 sequestration via solid phase carbonate precipitation, and (4) capture solvent regeneration with acid recycling in a single, continuous process. In our process, magnesium is released from serpentine at 300°C via heat treatment with ammonium sulfate salts or at temperatures as low as 50°C via reaction with sulfuric acid. We have also demonstrated that various solid carbonate phases can be precipitated directly from aqueous amine-based (NH3, MEA, DMEA) CO2 capture solvent solutions at room temperature. Direct precipitation from the capture solvent enables regenerating CO2 capture solvent without the need for heat and without the need to compress the CO2 off gas. We propose that known low-temperature electrochemical methods can be integrated with this process to regenerate the aqueous amine capture solvent and recycle acid for dissolution of magnesium-bearing mineral feedstocks and magnesium release. Although the direct precipitation of magnesite at ambient conditions remains elusive, experimental results demonstrate that at temperatures ranging from 20°C to 60°C, either nesquehonite Mg(HCO3)(OH)●2H2O or a double salt with the formula [NH4]2Mg(CO3)2●4H2O or an amorphous magnesium carbonate precipitate directly from the capture solvent. These phases are less desirable for CO2 sequestration than magnesite because they potentially remove constituents (water, ammonia) from the reaction system, reducing the overall efficiency of the sequestration process. Accordingly, the integrated process can be accomplished with minimal energy consumption and loss of CO2 capture and acid solvents, and a net generation of 1 to 4 moles of H2O/6 moles of CO2 sequestered (depending on the solid carbonate precipitate and amount of produced H2 and O2 gas reacted to produce heat and water). Features of the integrated process include the following: 1) the four separate processes have compatible chemistry, enabling design of an integrated, continuous process scheme for CO2 capture and sequestration; 2) all 4 stages of the process can be conducted at ambient or slightly elevated temperatures; 3) precipitating carbonate directly from the capture solvent eliminates the need for costly CO2 gas compression; and 4) recycling the acid used for serpentine dissolution and the solvent used for CO2 capture reduces feed stock costs.

Particles of spilled oil-absorbing carbon in contact with water

DOEpatents

Muradov, Nazim [Melbourne, FL

2011-03-29

Hydrogen generator coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. Carbon particles with surface filaments having a hydrophobic property of oil film absorption, compositions of matter containing those particles, and a system for using the carbon particles for cleaning oil spills.

Filamentous carbon particles for cleaning oil spills and method of production

DOEpatents

Muradov, Nazim

2010-04-06

A compact hydrogen generator is coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. The hydrogen generator can be conveniently integrated with high temperature fuel cells to produce an efficient and self-contained source of electrical power.

Low Cost High-H 2 Syngas Production for Power and Liquid Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, S. James

2015-07-31

This report summarizes the technical progress made of the research project entitled “Low Cost High-H2 Syngas Production for Power and Liquid Fuels,” under DOE Contract No. DE-FE-0011958. The period of performance was October 1, 2013 through July 30, 2015. The overall objectives of this project was to determine the technical and economic feasibility of a systems approach for producing high hydrogen syngas from coal with the potential to reduce significantly the cost of producing power, chemical-grade hydrogen or liquid fuels, with carbon capture to reduce the environmental impact of gasification. The project encompasses several areas of study and the resultsmore » are summarized here. (1) Experimental work to determine the technical feasibility of a novel hybrid polymer/metal H2-membrane to recover pure H2 from a coal-derived syngas was done. This task was not successful. Membranes were synthesized and show impermeability of any gases at required conditions. The cause of this impermeability was most likely due to the densification of the porous polymer membrane support made from polybenzimidazole (PBI) at test temperatures above 250 °C. (2) Bench-scale experimental work was performed to extend GTI's current database on the University of California Sulfur Recovery Process-High Pressure (UCSRP-HP) and recently renamed Sulfur Removal and Recovery (SR2) process for syngas cleanup including removal of sulfur and other trace contaminants, such as, chlorides and ammonia. The SR2 process tests show >90% H2S conversion with outlet H2S concentrations less than 4 ppmv, and 80-90% ammonia and chloride removal with high mass transfer rates. (3) Techno-economic analyses (TEA) were done for the production of electric power, chemical-grade hydrogen and diesel fuels, from a mixture of coal- plus natural gas-derived syngas using the Aerojet Rocketdyne (AR) Advanced Compact coal gasifier and a natural gas partial oxidation reactor (POX) with SR2 technology. Due to the unsuccessful experimental results with the hybrid polymer/metal H2 membrane, a conventional CO2 capture (single-stage Selexol) and hydrogen purification (PSA) technologies were used in the appropriate cases. In all cases, the integrated system of Advanced Compact coal gasifier, non-catalytic natural gas partial oxidation, and SR2 multicontaminant removal with state-of-the-art auxiliary system provided a 5-25% cost advantage over the base line plants using GEE coal gasifier with conventional Selexol/Claus sulfur removal and recovery. These plants also produce 18-30% less CO2 than with the conventional coal gasification plants.« less

Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

PubMed Central

Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

2017-01-01

The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

Efficient removal of sulfur hexafluoride (SF6) through reacting with recycled electroplating sludge.

PubMed

Zhang, Jia; Zhou, Ji Zhi; Liu, Qiang; Qian, Guangren; Xu, Zhi Ping

2013-06-18

This paper reports that recycled electroplating sludge is able to efficiently remove greenhouse gas sulfur hexafluoride (SF6). The removal process involves various reactions of SF6 with the recycled sludge. Remarkably, the sludge completely removed SF6 at a capacity of 1.10 mmol/g (SF6/sludge) at 600 °C. More importantly, the evolved gases were SO2, SiF4, and a limited amount of HF, with no toxic SOF4, SO2F2, or SF4 being detected. These generated gases can be readily captured and removed by NaOH solution. The reacted solids were further found to be various metal fluorides, thus revealing that SF6 removal takes place by reacting with various metal oxides and silicate in the sludge. Moreover, the kinetic investigation revealed that the SF6 reaction with the sludge is a first-order chemically controlled process. This research thus demonstrates that the waste electroplating sludge can be potentially used as an effective removal agent for one of the notorious greenhouse gases, SF6.

Iodide-Photocatalyzed Reduction of Carbon Dioxide to Formic Acid with Thiols and Hydrogen Sulfide.

PubMed

Berton, Mateo; Mello, Rossella; González-Núñez, María Elena

2016-12-20

The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO 2 capture coupled with H 2 S removal may have been relevant as a prebiotic carbon dioxide fixation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation of fluidized bed coal combustors

NASA Technical Reports Server (NTRS)

Rajan, R.

1979-01-01

The many deficiencies of previous work on simulation of fluidized bed combustion (FBC) processes are presented. An attempt is made to reduce these deficiencies, and to formulate a comprehensive FBC model taking into account the following elements: (1) devolatilization of coal and the subsequent combustion of volatiles and residual char; (2) sulfur dioxide capture by limestone; (3) NOx release and reduction of NOx by char; (4) attrition and elutriation of char and limestone; (5) bubble hydrodynamics; (6) solids mixing; (7) heat transfer between gas and solid, and solid and heat exchange surfaces; and (8) freeboard reactions.

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hao; Sa, Niya; He, Meinan

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE PAGES

Wang, Hao; Sa, Niya; He, Meinan; ...

2017-03-03

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

Characterization of the enhancement effect of Na2CO3 on the sulfur capture capacity of limestones.

PubMed

Laursen, Karin; Kern, Arnt A; Grace, John R; Lim, C Jim

2003-08-15

It has been known for a long time that certain additives (e.g., NaCl, CaCl2, Na2CO3, Fe2O3) can increase the sulfur dioxide capture-capacity of limestones. In a recent study we demonstrated that very small amounts of Na2CO3 can be very beneficial for producing sorbents of very high sorption capacities. This paper explores what contributes to these significant increases. Mercury porosimetry measurements of calcined limestone samples reveal a change in the pore-size from 0.04-0.2 microm in untreated samples to 2-10 microm in samples treated with Na2CO3--a pore-size more favorable for penetration of sulfur into the particles. The change in pore-size facilitates reaction with lime grains throughout the whole particle without rapid plugging of pores, avoiding premature change from a fast chemical reaction to a slow solid-state diffusion controlled process, as seen for untreated samples. Calcination in a thermogravimetric reactor showed that Na2CO3 increased the rate of calcination of CaCO3 to CaO, an effect which was slightly larger at 825 degrees C than at 900 degrees C. Peak broadening analysis of powder X-ray diffraction data of the raw, calcined, and sulfated samples revealed an unaffected calcite size (approximately 125-170 nm) but a significant increase in the crystallite size for lime (approximately 60-90 nm to approximately 250-300 nm) and less for anhydrite (approximately 125-150 nm to approximately 225-250 nm). The increase in the crystallite and pore-size of the treated limestones is attributed to an increase in ionic mobility in the crystal lattice due to formation of vacancies in the crystals when Ca is partly replaced by Na.

Influence of Sulfur Fertilization on the Antioxidant Activities of Onion Juices Prepared by Thermal Treatment

PubMed Central

Koh, Eunmi; Surh, Jeonghee

2016-01-01

Two onions (Sulfur-1 and Sulfur-4) cultivated with different sulfur applications were thermally processed to elucidate the effects of heat treatment on browning index and antioxidant activity. Sulfur-4 onion had higher sulfur content compared with the Sulfur-1 onion. After thermal processing, browning intensity was different between the two onions juices, with lower values observed for Sulfur-4 onion juice. This suggests that sulfur inhibits the Maillard browning reaction. The total reducing capacity of the juices increased at higher thermal processing temperatures; however, it was also lower in the Sulfur-4 onion juice. This suggests that the heat treatment of onions enhanced their antioxidant activity, but the effect was offset in the Sulfur-4 onion juice presumably due to higher sulfur content. This study indicates that sulfur, a core element for the functionality of onions, can decrease the antioxidant activity of thermally processed onions because of its potential as a Maillard reaction inhibitor. PMID:27390734

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S. H. D.; Kumar, R.; Krumpelt, M.

Methanol is considered to be a potential on-board fuel for fuel cell-powered vehicles. In current distribution systems for liquid fuels used in the transportation sector, commodity methanol can occasionally become contaminated with the sulfur in diesel fuel or gasoline. This sulfur would poison the catalytic materials used in fuel reformers for fuel cells. We tested the removal of this sulfur by means of ten activated carbons (AC) that are commercially available. Tests were conducted with methanol doped with 1 vol.% grade D-2 diesel fuel containing 0.29% sulfur, which was present essentially as 33-35 wt.% benzothiophenes (BTs) and 65-67 wt.% dibenzothiophenesmore » (DBT). In general, coconut shell-based carbons activated by high-temperature steam were more effective at sulfur removal than coal-based carbons. Equilibrium sorption data showed linear increase in sulfur capture with the increase of sulfur concentration in methanol. Both types of carbons had similar breakthrough characteristics, with the dynamic sorption capacity of each being about one-third of its equilibrium sorption capacity. Results of this study suggest that a fixed-bed sorber of granular AC can be used, such as in refueling stations, for the removal of sulfur in diesel fuel-contaminated methanol.« less

Coal-Derived Warm Syngas Purification and CO 2 Capture-Assisted Methane Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dagle, Robert A.; King, David L.; Li, Xiaohong S.

2014-10-01

Gasifier-derived syngas from coal has many applications in the area of catalytic transformation to fuels and chemicals. Raw syngas must be treated to remove a number of impurities that would otherwise poison the synthesis catalysts. Inorganic impurities include alkali salts, chloride, sulfur compounds, heavy metals, ammonia, and various P, As, Sb, and Se- containing compounds. Systems comprising multiple sorbent and catalytic beds have been developed for the removal of impurities from gasified coal using a warm cleanup approach. This approach has the potential to be more economic than the currently available acid gas removal (AGR) approaches and improves upon currentlymore » available processes that do not provide the level of impurity removal that is required for catalytic synthesis application. Gasification also lends itself much more readily to the capture of CO 2, important in the regulation and control of greenhouse gas emissions. CO 2 capture material was developed and in this study was demonstrated to assist in methane production from the purified syngas. Simultaneous CO 2 sorption enhances the CO methanation reaction through relaxation of thermodynamic constraint, thus providing economic benefit rather than simply consisting of an add-on cost for carbon capture and release. Molten and pre-molten LiNaKCO 3 can promote MgO and MgO-based double salts to capture CO 2 with high cycling capacity. A stable cycling CO 2 capacity up to 13 mmol/g was demonstrated. This capture material was specifically developed in this study to operate in the same temperature range and therefore integrate effectively with warm gas cleanup and methane synthesis. By combining syngas methanation, water-gas-shift, and CO 2 sorption in a single reactor, single pass yield to methane of 99% was demonstrated at 10 bar and 330°C when using a 20 wt% Ni/MgAl 2O 4 catalyst and a molten-phase promoted MgO-based sorbent. Under model feed conditions both the sorbent and catalyst exhibited favorable stability after multiple test cycles. The cleanup for warm gas cleanup of inorganics was broken down into three major steps: chloride removal, sulfur removal, and the removal for a multitude of trace metal contaminants. Na 2CO 3 was found to optimally remove chlorides at an operating temperature of 450ºC. For sulfur removal two regenerable ZnO beds are used for bulk H 2S removal at 450ºC (<5 ppm S) and a non-regenerable ZnO bed for H 2S polishing at 300ºC (<40 ppb S). It was also found that sulfur from COS could be adsorbed (to levels below our detection limit of 40 ppb) in the presence of water that leads to no detectable slip of H 2S. Finally, a sorbent material comprising of Cu and Ni was found to be effective in removing trace metal impurities such as AsH 3 and PH 3 when operating at 300ºC. Proof-of-concept of the integrated cleanup process was demonstrated with gasifier-generated syngas produced at the Western Research Institute using Wyoming Decker Coal. When operating with a ~1 SLPM feed, multiple inorganic contaminant removal sorbents and a tar-reforming bed was able to remove the vast majority of contaminants from the raw syngas. A tar-reforming catalyst was employed due to the production of tars generated from the gasifier used in this particular study. It is envisioned that in a real application a commercial scale gasifier operating at a higher temperature would produce lesser amount of tar. Continuous operation of a poison-sensitive copper-based WGS catalyst located downstream from the cleanup steps resulted in successful demonstration.« less

Modeling Macro- and Micro-Scale Turbulent Mixing and Chemistry in Engine Exhaust Plumes

NASA Technical Reports Server (NTRS)

Menon, Suresh

1998-01-01

Simulation of turbulent mixing and chemical processes in the near-field plume and plume-vortex regimes has been successfully carried out recently using a reduced gas phase kinetics mechanism which substantially decreased the computational cost. A detailed mechanism including gas phase HOx, NOx, and SOx chemistry between the aircraft exhaust and the ambient air in near-field aircraft plumes is compiled. A reduced mechanism capturing the major chemical pathways is developed. Predictions by the reduced mechanism are found to be in good agreement with those by the detailed mechanism. With the reduced chemistry, the computer CPU time is saved by a factor of more than 3.5 for the near-field plume modeling. Distributions of major chemical species are obtained and analyzed. The computed sensitivities of major species with respect to reaction step are deduced for identification of the dominant gas phase kinetic reaction pathways in the jet plume. Both the near field plume and the plume-vortex regimes were investigated using advanced mixing models. In the near field, a stand-alone mixing model was used to investigate the impact of turbulent mixing on the micro- and macro-scale mixing processes using a reduced reaction kinetics model. The plume-vortex regime was simulated using a large-eddy simulation model. Vortex plume behind Boeing 737 and 747 aircraft was simulated along with relevant kinetics. Many features of the computed flow field show reasonable agreement with data. The entrainment of the engine plumes into the wing tip vortices and also the partial detrainment of the plume were numerically captured. The impact of fluid mechanics on the chemical processes was also studied. Results show that there are significant differences between spatial and temporal simulations especially in the predicted SO3 concentrations. This has important implications for the prediction of sulfuric acid aerosols in the wake and may partly explain the discrepancy between past numerical studies (that employed parabolic or temporal approximations) and the measured data. Finally to address the major uncertainty in the near-field plume modeling related to the plume processing of sulfur compounds and advanced model was developed to evaluate its impact on the chemical processes in the near wake. A comprehensive aerosol model is developed and it is coupled with chemical kinetics and the axisymmetric turbulent jet flow models. The integrated model is used to simulate microphysical processes in the near-field jet plume, including sulfuric acid and water binary homogeneous nucleation, coagulation, non-equilibrium heteromolecular condensation, and sulfur-induced soot activation. The formation and evolution of aerosols are computed and analyzed. The computed results show that a large number of ultra-fine (0.3--0.6 nm in radius) volatile HSO4 - HO embryos are generated in the near-field plume. These embryos further grow in size by self coagulation and condensation. Soot particles can be activated by both heterogeneous nucleation and scavenging of H2SO4-H2O aerosols. These activated soot particles can serve as water condensation nuclei for contrail formation. Conditions under which ice contrails can form behind aircrafts are studied. The sensitivities of the threshold temperature for contrail formation with respect to aircraft propulsion efficiency, relative humidity, and ambient pressure are evaluated. The computed aerosol properties for different extent of fuel sulfur conversion to S(VI) (SO3 and H2SO4) in engine are examined and the results are found to be sensitive to this conversion fraction.

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

NASA Astrophysics Data System (ADS)

Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

Coal Gasification - section in Kirk-Othmer Concise Encyclopedia of Chemical Technology, 5th Edition, 2-vol. set, July 2007, ISBN 978-0-470-04748-4, pp. 580-587

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shadle, L.J.; Berry, D.A.; Syamlal, Madhava

2007-07-01

Coal gasification is the process of reacting coal with oxygen, steam, and carbon dioxide to form a product gas containing hydrogen and carbon monoxide. Gasification is essentially incomplete combustion. The chemical and physical processes are quite similar, the main difference being the nature of the final products. From a processing point of view the main operating difference is that gasification consumes heat evolved during combustion. Under the reducing environment of gasification the sulfur in the coal is released as hydrogen sulfide rather than sulfur dioxide and the coal's nitrogen is converted mostly to ammonia rather than nitrogen oxides. These reducedmore » forms of sulfur and nitrogen are easily isolated, captured, and utilized, and thus gasification is a clean coal technology with better environmental performance than coal combustion. Depending on the type of gasifier and the operating conditions, gasification can be used to produce a fuel gas suitable for any number of applications. A low heating value fuel gas is produced from an air blown gasifier for use as an industrial fuel and for power production. A medium heating value fuel gas is produced from enriched oxygen blown gasification for use as a synthesis gas in the production of chemicals such as ammonia, methanol, and transportation fuels. A high heating value gas can be produced from shifting the medium heating value product gas over catalysts to produce a substitute or synthetic natural gas (SNG).« less

Process for removing sulfur from sulfur-containing gases

DOEpatents

Rochelle, Gary T.; Jozewicz, Wojciech

1989-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accorda The government may own certain rights in the present invention pursuant to EPA Cooperative Agreement CR 81-1531.

ADVANCED SULFUR CONTROL CONCEPTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce themore » number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).« less

Elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, M.; Zhicheng Hu.

1993-09-07

An improved catalytic reduction process for the direct recovery of elemental sulfur from various SO[sub 2]-containing industrial gas streams. The catalytic process provides combined high activity and selectivity for the reduction of SO[sub 2] to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over certain catalyst formulations based on cerium oxide. The process is a single-stage, catalytic sulfur recovery process in conjunction with regenerators, such as those used in dry, regenerative flue gas desulfurization or other processes, involving direct reduction of the SO[sub 2] in the regenerator off gas stream to elemental sulfur in the presence of a catalyst. 4 figures.

Elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, Maria; Hu, Zhicheng

1993-01-01

An improved catalytic reduction process for the direct recovery of elemental sulfur from various SO.sub.2 -containing industrial gas streams. The catalytic process provides combined high activity and selectivity for the reduction of SO.sub.2 to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over certain catalyst formulations based on cerium oxide. The process is a single-stage, catalytic sulfur recovery process in conjunction with regenerators, such as those used in dry, regenerative flue gas desulfurization or other processes, involving direct reduction of the SO.sub.2 in the regenerator off gas stream to elemental sulfur in the presence of a catalyst.

Synergistic Effect of Molecular-Type Electrocatalysts with Ultrahigh Pore Volume Carbon Microspheres for Lithium-Sulfur Batteries.

PubMed

Lim, Won-Gwang; Mun, Yeongdong; Cho, Ara; Jo, Changshin; Lee, Seonggyu; Han, Jeong Woo; Lee, Jinwoo

2018-05-14

Lithium-sulfur (Li-S) batteries are regarded as potential high-energy storage devices due to their outstanding energy density. However, the low electrical conductivity of sulfur, dissolution of the active material, and sluggish reaction kinetics cause poor cycle stability and rate performance. A variety of approaches have been attempted to resolve the above issues and achieve enhanced electrochemical performance. However, inexpensive multifunctional host materials which can accommodate large quantities of sulfur and exhibit high electrode density are not widely available, which hinders the commercialization of Li-S batteries. Herein, mesoporous carbon microspheres with ultrahigh pore volume are synthesized, followed by the incorporation of Fe-N-C molecular catalysts into the mesopores, which can act as sulfur hosts. The ultrahigh pore volume of the prepared host material can accommodate up to ∼87 wt % sulfur, while the uniformly controlled spherical morphology and particle size of the carbon microspheres enable high areal/volumetric capacity with high electrode density. Furthermore, the uniform distribution of Fe-N-C (only 0.33 wt %) enhances the redox kinetics of the conversion reaction of sulfur and efficiently captures the soluble intermediates. The resulting electrode with 5.2 mg sulfur per cm 2 shows excellent cycle stability and 84% retention of the initial capacity even after 500 cycles at a 3 C rate.

Sulfone-stabilized carbanions for the reversible covalent capture of a posttranslationally-generated cysteine oxoform found in protein tyrosine phosphatase 1B (PTP1B).

PubMed

Parsons, Zachary D; Ruddraraju, Kasi Viswanatharaju; Santo, Nicholas; Gates, Kent S

2016-06-15

Redox regulation of protein tyrosine phosphatase 1B (PTP1B) involves oxidative conversion of the active site cysteine thiolate into an electrophilic sulfenyl amide residue. Reduction of the sulfenyl amide by biological thiols regenerates the native cysteine residue. Here we explored fundamental chemical reactions that may enable covalent capture of the sulfenyl amide residue in oxidized PTP1B. Various sulfone-containing carbon acids were found to react readily with a model peptide sulfenyl amide via attack of the sulfonyl carbanion on the electrophilic sulfur center in the sulfenyl amide. Both the products and the rates of these reactions were characterized. The results suggest that capture of a peptide sulfenyl amide residue by sulfone-stabilized carbanions can slow, but not completely prevent, thiol-mediated generation of the corresponding cysteine-containing peptide. Sulfone-containing carbon acids may be useful components in the construction of agents that knock down PTP1B activity in cells via transient covalent capture of the sulfenyl amide oxoform generated during insulin signaling processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

On a new ironmaking process to produce hydrogen and reduce energy consumption

NASA Astrophysics Data System (ADS)

Corbari, Rodrigo

The primary purpose of the present work is to compute the volume and composition of the products of a theoretical charring unit for high volatile coals. In particular, the compositions of volatile gas and char and the hydrogen yield of the process. The volume of oxygen necessary to supply the energy for the process was also calculated. The model consists of materials and energy balance equations and local thermodynamic equilibrium. The model was combined with experimental results relating the effect of temperature on the extent of devolatilization and chemistry evolution of coal. Results of the model indicated that temperature plays a major role defining the quantities and composition of charring products. The H2 concentration of the volatile gas increased from about 16vol% at 700°C to 47vol% at 900°C, leveling off at approximately 52vol% at 1100°C. The hydrogen yield of the process increased from 7 to 60 percent at 700°C and 1100°C respectively. For a typical high volatile coal considered, the volume of gas generated varied from about 210 to 780 liters/kg-coal(STP) according to temperature and fraction of solids combusted. The char becomes enriched in carbon and depleted in hydrogen as temperature is increased. As much as 97 percent of the hydrogen in coal is removed at 1100°C. In the second part of this study, the kinetics of reduction of iron oxide fines with simulated smelter gas was experimentally studied by thermogravimetry. An equimolar CO/CO2 mixture was selected to simulate the off-gas of a smelter operating with char at 50 percent post combustion. Reduction temperatures ranged from 590°C to 1000°C. Under these conditions, reduction was limited to wustite. Results indicated that the reduction kinetics and dominating reaction mechanism varied with temperature, extent of reduction and type of iron oxide employed. Reduction from hematite to wustite proceeded in two consecutive reaction steps with magnetite as an intermediate oxide. The first reduction step, hematite to magnetite, was fast and controlled by external gas mass transfer independently of type of iron oxide and temperature employed in this work. The second reduction step, magnetite to wustite, was the overall reaction controlling step. The reduction mechanism varied with temperature and type of iron oxide. For moderately porous oxide fines (VALE and Taconite ores), the magnetite to wustite reduction followed a uniform internal reaction regime, where the chemical reaction at the gas-solid surface is the slowest step. For highly porous oxide (PAH), the magnetite to wustite reduction step was controlled by external gas mass transfer above 700°C. Below that, a mixed regime involving external gas mass transfer and limited mixed control, which comprises pore diffusion and chemical reaction, took place. The rate equations for this mixed control reaction mechanism were developed and the limited mixed control rate constant (klm) was computed. For denser oxides under uniform internal reaction, the product of the rate constant and pore surface area (k·S) was calculated. The final part of this research focused on the study of the mechanisms contributing for the distribution of sulfur in the smelter process. A methodology was developed for this purpose, which computes the sulfur concentration and distribution between the metal, slag and gas phases of the smelter for selected case scenarios. The model assumed the smelter as an ideal continuous stirred reactor under steady state conditions. Sulfur in the gas phase resulted from slag desulfurization by reaction with gas and the direct transfer of sulfur from coal or char. In general, it was found that a large fraction of sulfur leaves the smelter with the gas when coal or char is the only sulfur input to the process. However, the predominant mechanism for transfer of sulfur into the gas depended on process operating conditions. The effect of recycling sulfur back into the smelter was also evaluated. This is important when sulfur leaving with the smelter gas is captured by pre-reduced iron oxide or by dust particles and re-introduced in the process. In general, the more sulfur is recycled into the smelter, the higher the metal and slag sulfur concentration. However, the increasing sulfur content of metal and slag when sulfur is recycled may be partially counter-balanced by the use of char in place of coal. (Abstract shortened by UMI.)

Effect of Dietary Processed Sulfur Supplementation on Water-holding Capacity, Color, and Lipid Profiles of Pork

PubMed Central

Yang, FengQi; Kim, Ji-Han; Yeon, Su Jung; Hong, Go-Eun; Park, Woojoon; Lee, Chi-Ho

2015-01-01

This study was performed to investigate the effect of dietary processed sulfur supplementation on water-holding capacity, color, and lipid profiles of pork according to the level of dietary processed sulfur (0%, CON; 0.3%, S). The pigs were slaughtered at an average final weight of 120 kg, and the longissimus dorsi muscles were collected from the carcasses. As results, pork processed with sulfur had significantly higher moisture and ash contents compared to those of CON but lower crude fat, pH, expressible drip, lower redness and yellowness, and greater lightness. Pork processed with sulfur showed significantly lower total lipid content, triglycerides, and atherosclerosis index but significantly higher high-density lipoprotein cholesterol. Feeding processed sulfur significantly lowered myristic acid, heptadecanoic acid, and stearic acid contents, whereas monounsaturated fatty acids and oleic acids were significantly higher compared to those in the CON. Higher amounts of polyunsaturated fatty acids and n-6 fatty acids were observed in the pork processed with sulfur than that of the CON. Therefore, supplementing pigs with dietary sulfur improved nutrient and meat quality. PMID:26877643

Hydrogen sulfide capture by limestone and dolomite at elevated pressure. 2: Sorbent particle conversion modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven, C.A.P.; Yrjas, K.P.; Hupa, M.M.

1996-03-01

The physical structure of a limestone or dolomite to be used in in-bed sulfur capture in fluidized bed gasifiers has a great impact on the efficiency of sulfur capture and sorbent use. In this study an unreacted shrinking core model with variable effective diffusivity is applied to sulfidation test data from a pressurized thermogravimetric apparatus (P-TGA) for a set of physically and chemically different limestone and dolomite samples. The particle size was 250--300 {micro}m for all sorbents, which were characterized by chemical composition analysis, particle density measurement, mercury porosimetry, and BET internal surface measurement. Tests were done under typical conditionsmore » for a pressurized fluidized-bed gasifier, i.e., 20% CO{sub 2}, 950 C, 20 bar. At these conditions the limestone remains uncalcined, while the dolomite is half-calcined. Additional tests were done at low CO{sub 2} partial pressures, yielding calcined limestone and fully calcined dolomite. The generalized model allows for determination of values for the initial reaction rate and product layer diffusivity.« less

Regenerative process for removal of mercury and other heavy metals from gases containing H.sub.2 and/or CO

DOEpatents

Jadhav, Raja A [Naperville, IL

2009-07-07

A method for removal of mercury from a gaseous stream containing the mercury, hydrogen and/or CO, and hydrogen sulfide and/or carbonyl sulfide in which a dispersed Cu-containing sorbent is contacted with the gaseous stream at a temperature in the range of about 25.degree. C. to about 300.degree. C. until the sorbent is spent. The spent sorbent is contacted with a desorbing gaseous stream at a temperature equal to or higher than the temperature at which the mercury adsorption is carried out, producing a regenerated sorbent and an exhaust gas comprising released mercury. The released mercury in the exhaust gas is captured using a high-capacity sorbent, such as sulfur-impregnated activated carbon, at a temperature less than about 100.degree. C. The regenerated sorbent may then be used to capture additional mercury from the mercury-containing gaseous stream.

Electron-induced chemistry in microhydrated sulfuric acid clusters

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Sulfur flows and biosolids processing: Using Material Flux Analysis (MFA) principles at wastewater treatment plants.

PubMed

Fisher, R M; Alvarez-Gaitan, J P; Stuetz, R M; Moore, S J

2017-08-01

High flows of sulfur through wastewater treatment plants (WWTPs) may cause noxious gaseous emissions, corrosion of infrastructure, inhibit wastewater microbial communities, or contribute to acid rain if the biosolids or biogas is combusted. Yet, sulfur is an important agricultural nutrient and the direct application of biosolids to soils enables its beneficial re-use. Flows of sulfur throughout the biosolids processing of six WWTPs were investigated to identify how they were affected by biosolids processing configurations. The process of tracking sulfur flows through the sites also identified limitations in data availability and quality, highlighting future requirements for tracking substance flows. One site was investigated in more detail showing sulfur speciation throughout the plant and tracking sulfur flows in odour control systems in order to quantify outflows to air, land and ocean sinks. While the majority of sulfur from WWTPs is removed as sulfate in the secondary effluent, the sulfur content of biosolids is valuable as it can be directly returned to soils to combat the potential sulfur deficiencies. Biosolids processing configurations, which focus on maximising solids recovery, through high efficiency separation techniques in primary sedimentation tanks, thickeners and dewatering centrifuges retain more sulfur in the biosolids. However, variations in sulfur loads and concentrations entering the WWTPs affect sulfur recovery in the biosolids, suggesting industrial emitters, and chemical dosing of iron salts are responsible for differences in recovery between sites. Copyright © 2017 Elsevier Ltd. All rights reserved.

The use of elemental sulfur as an alternative feedstock for polymeric materials

NASA Astrophysics Data System (ADS)

Chung, Woo Jin; Griebel, Jared J.; Kim, Eui Tae; Yoon, Hyunsik; Simmonds, Adam G.; Ji, Hyun Jun; Dirlam, Philip T.; Glass, Richard S.; Wie, Jeong Jae; Nguyen, Ngoc A.; Guralnick, Brett W.; Park, Jungjin; Somogyi, Árpád; Theato, Patrick; Mackay, Michael E.; Sung, Yung-Eun; Char, Kookheon; Pyun, Jeffrey

2013-06-01

An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li-S batteries, exhibiting high specific capacity (823 mA h g-1 at 100 cycles) and enhanced capacity retention.

Capture of trace sulfur gases from binary mixtures by single-walled carbon nanotube arrays: a molecular simulation study.

PubMed

Wang, Wenjuan; Peng, Xuan; Cao, Dapeng

2011-06-01

Adsorption of H(2)S and SO(2) pure gases and their selective capture from the H(2)S-CH(4), H(2)S-CO(2), SO(2)-N(2), and SO(2)-CO(2) binary mixtures by the single-walled carbon nanotubes (SWNT) are investigated via using the grand canonical Monte Carlo (GCMC) method. It is found that the (20, 20) SWNT with larger diameter shows larger capacity for H(2)S and SO(2) pure gases at T = 303 K, in which the uptakes reach 16.31 and 16.03 mmol/g, respectively. However, the (6,6) SWNT with small diameter exhibits the largest selectivity for binary mixtures containing trace sulfur gases at T = 303 K and P = 100 kPa. By investigating the effect of pore size on the separation of gas mixtures, we found that the optimized pore size is 0.81 nm for separation of H(2)S-CH(4), H(2)S-CO(2), and SO(2)-N(2) binary mixtures, while it is 1.09 nm for the SO(2)-CO(2) mixture. The effects of concentration and temperature on the selectivity of sulfide are also studied at the optimal pore size. It is found that the concentration (ppm) of sulfur components has little effect on selectivity of SWNTs for these binary mixtures. However, the selectivity decreases obviously with the increase of temperature. To improve the adsorption capacities, we further modify the surface of SWNTs with the functional groups. The selectivities of H(2)S-CO(2) and SO(2)-CO(2) mixtures are basically uninfluenced by the site density, while the increase of site density can improve the selectivity of H(2)S-CH(4) mixture doubly. It is expected that this work could provide useful information for sulfur gas capture.

An Alternate View of Venus

NASA Astrophysics Data System (ADS)

Ackerman, J.

2002-05-01

Overwhelming physical evidence has been present since Pioneer Venus (PV), indicating that Venus is a hot new planet. I maintain that a fireball, with a mass some ten times that of Venus, rebounded from a high energy impact (1043 ergs) on Jupiter 6,000 years ago. Heating due to the gravitational contraction of the ejected material along with tidal and electromagnetic braking at subsequent perihelion passes produced temperatures >10,000 K. The rapid conversion of orbital energy to heat reduced proto-Venus' eccentricity and expelled the lighter atoms into space, resulting in a high average density terrestrial body. Differentiation of heavy elements and fractionation of naturally radioactive elements occurred quickly. Subsequent close planetary interactions resulted in its final orbit and uplifted the continents, by means of which the tidal force of the Earth induced Venus' spin orbit resonance. This process left much volatile material in interplanetary space, for later acquisition by the proto-planet as it cooled and by extant planets. I maintain that this is the genesis of all terrestrial bodies. Corroborating evidence exists in the form of upwelling radiation measurements from five independent PV probes, all indicating that Venus is radiating 20 w/m2. Due to its recent catastrophic origin, the interior is molten rock with a tenuous crust less than a kilometer thick. Venus' rapid cooling is manifested by two processes: (1) Via radiation from raw lava lying in many surface cracks, radiation which was so strong, that the PV LIR (sensitive infrared radiometer) data collected below the lower cloud layer was discarded; (2) The high velocity expulsion, from 200,000 small domes, of massive quantities of S8, which shoots to an altitude of 48 km. Evidence for (2) stems from the temperatures of three interfaces in the lower atmosphere. The surface temperature is maintained just above 444.5 C, the boiling point of S8, by the evaporation of raining sulfur. The altitude of the ubiquitous lower cloud layer corresponds to the exact temperatures at which the rising S8 gas freezes to form monoclinic (119.2 C) and rhombic (96. C) crystals. These comprise the lower cloud layer and catalyze reactions which capture sulfur, creating a sulfur 'cap.' The energy being released at this level was measured as a +20 C temperature offset. This hot rising S8 flux was so intense that it disabled the sensors on all the PV probes at 14 km (40,000 feet!) CS also apparently crystalizes (200. C) from the rising gases at 31 km causing the thin red haze which extends upward to the lower cloud layer. CS crystals catalyze reactions which capture carbon in that altitude range. This caused the `dropout' of CO2, CO and COS between 31 and 50 km, in the PV mass spec data, not a clogging of the input leak. Thus S8 dominates the lower atmosphere, and it is the great mass of sulfur suspended there which produces the high surface pressure, not CO2. S8 was not detected because it is beyond the mass range of the PV instruments. This paradigm reveals the driving force behind the 'four day' zonal winds, which encircle the planet at all latitudes. S8 jetting vertically from 200,000 small domes, is continuously transferring angular momentum from the slowly rotating planet to the atmosphere. Venus' atmosphere is composed of two altitude regimes. The sulfur dominated 'Hadesphere' extends from the surface to 50 km. The upper atmosphere, captured from interactions with Mars or reacquired from interplanetary space, exhibits earthlike temperatures and pressures. As Venus cools and the intensity of the jetting sulfur gases decreases, the Hadesphere will gradually collapse, bringing the normal atmosphere down to the surface.

Kinetics and mechanism of hydration of o-thioquinone methide in aqueous solution. Rate-determining protonation of sulfur.

PubMed

Chiang, Yvonne; Kresge, A Jerry; Sadovski, Oleg; Zhan, Hao-Qiang

2005-03-04

o-Thioquinone methide, 2, was generated in aqueous solution by flash photolysis of benzothiete, 1, and rates of hydration of this quinone methide to o-mercaptobenzyl alcohol, 3, were measured in perchloric acid solutions, using H2O and D2O as the solvent, and also in acetic acid and tris(hydroxymethyl)methylammonium ion buffers, using H2O as the solvent. The rate profiles constructed from these data show hydronium-ion-catalyzed and uncatalyzed hydration reaction regions, just like the rate profiles based on literature data for hydration of the oxygen analogue, o-quinone methide, of the presently examined substrate. Solvent isotope effects on hydronium-ion catalysis of hydration for the two substrates, however, are quite different: k(H)/k(D) = 0.42 for the oxygen quinone methide, whereas k(H)/k(D) = 1.66 for the sulfur substrate. The inverse nature (k(H)/k(D) < 1) of the isotope effect in the oxygen system indicates that this reaction occurs by a preequilibrium proton-transfer reaction mechanism, with protonation of the substrate on its oxygen atom being fast and reversible and capture of the benzyl-type carbocationic intermediate so formed being rate-determining. The normal direction (k(H)/k(D) > 1) of the isotope effect in the sulfur system, on the other hand, suggests that protonation of the substrate on its sulfur atom is in this case rate-determining, with carbocation capture a fast following step. A semiquantitative argument supporting this hypothesis is presented.

Mineral resource of the month: sulfur

USGS Publications Warehouse

,

2010-01-01

The article presents information on sulfur. Sulfur is said to be among the few solid elements found in elemental form in nature and has industrial uses. Changes in the sulfur production process over the years are discussed as well as the mining process developed by German engineer Herman Frasch that involves melting the sulfur underground and pumping it to the surface.

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, M.R.; Gal, E.

1993-04-13

A process and system are described for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous mixture.

Advanced Acid Gas Separation Technology for the Utilization of Low Rank Coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kloosterman, Jeff

2012-12-31

Air Products has developed a potentially ground-breaking technology – Sour Pressure Swing Adsorption (PSA) – to replace the solvent-based acid gas removal (AGR) systems currently employed to separate sulfur containing species, along with CO{sub 2} and other impurities, from gasifier syngas streams. The Sour PSA technology is based on adsorption processes that utilize pressure swing or temperature swing regeneration methods. Sour PSA technology has already been shown with higher rank coals to provide a significant reduction in the cost of CO{sub 2} capture for power generation, which should translate to a reduction in cost of electricity (COE), compared to baselinemore » CO{sub 2} capture plant design. The objective of this project is to test the performance and capability of the adsorbents in handling tar and other impurities using a gaseous mixture generated from the gasification of lower rank, lignite coal. The results of this testing are used to generate a high-level pilot process design, and to prepare a techno-economic assessment evaluating the applicability of the technology to plants utilizing these coals.« less

Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

NASA Astrophysics Data System (ADS)

Garces Trujillo, Hector Fabian

This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous manganese oxide (AMO) has been used in catalytic processes such as for the catalytic oxidation of benzyl alcohol, the preferential oxidation of CO, and for the capture of formate species. This chapter explores the possibility of using AMO in sorption processes for the removal of two contaminants; H 2S and COS in the temperature range 200 - 400 °C.

Method for removing sulfur oxide from waste gases and recovering elemental sulfur

DOEpatents

Moore, Raymond H.

1977-01-01

A continuous catalytic fused salt extraction process is described for removing sulfur oxides from gaseous streams. The gaseous stream is contacted with a molten potassium sulfate salt mixture having a dissolved catalyst to oxidize sulfur dioxide to sulfur trioxide and molten potassium normal sulfate to solvate the sulfur trioxide to remove the sulfur trioxide from the gaseous stream. A portion of the sulfur trioxide loaded salt mixture is then dissociated to produce sulfur trioxide gas and thereby regenerate potassium normal sulfate. The evolved sulfur trioxide is reacted with hydrogen sulfide as in a Claus reactor to produce elemental sulfur. The process may be advantageously used to clean waste stack gas from industrial plants, such as copper smelters, where a supply of hydrogen sulfide is readily available.

Multiple sulfur isotopes monitor fluid evolution of an Archean orogenic gold deposit

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Sugiono, Dennis; Thébaud, Nicolas; Caruso, Stefano; Fiorentini, Marco; Selvaraja, Vikraman; Jeon, Heejin; Voute, François; Martin, Laure

2018-02-01

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼-0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = -7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a homogeneous MIF-S-bearing fluid reservoir at depth, rather than being locally sourced at the site of Au precipitation. Finally, by constraining the MIF-S-bearing sulfur source to a fixed reservoir, we are able to display the thermochemical evolution of the ore fluid in δ34S space and capture the abrupt change in oxidation state that causes Au precipitation. Our results highlight the importance of constraining multiple sulfur isotopes in space and time in order to elucidate the source and evolution of any given Au-bearing fluid.

A New Use for High-Sulfur Coal

NASA Technical Reports Server (NTRS)

Lawson, D. D.; England, C.

1982-01-01

New process recovers some of economic value of high-sulfur coal. Although high-sulfur content is undesirable in most coal-utilization schemes (such as simple burning), proposed process prefers high-sulfur coal to produce electrical power or hydrogen. Potential exists for widespread application in energy industry.

Enhancement of the sulfur capture capacity of limestones by the addition of Na2CO3 and NaCl.

PubMed

Laursen, K; Grace, J R; Lim, C J

2001-11-01

The ability of Na2CO3 and NaCl to enhance the sulfur capture capacity of three limestones was evaluated via fixed-bed calcination and sulfation experiments. The tested limestones represent three different sulfation morphologies: unreacted-core, network, and uniformly sulfated. Treatment with aqueous or powdered Na2CO3 significantly increased the Ca-utilization for two stones which normally sulfate in an unreacted-core pattern (20% to 45%) and network pattern (33% to 49%). The increase was lower for the uniformly sulfated stone (44% to 48%). Na2CO3 treatment increased the number of macropores leading to uniform sulfation of all particles, nearly eliminating the normal strong dependence of utilization on limestone type and particle size. The effect of Na2CO3 is believed to be associated with formation of a eutectic melt which enhances ionic diffusion and accelerates molecular rearrangement of the CaO. Treatment with aqueous NaCl solution caused a decrease in utilization, probably due to formation of large grains and plugging of pores caused by formation of a large amount of eutectic melt. The effect of Na2CO3 is less sensitive than that of NaCl to the amount added and the combustion environment (temperature and gas composition). In addition, Na2CO3 neither promotes corrosion nor forms chlorinated byproducts, which are main concerns associated with NaCl. Thus, Na2CO3 appears to have significant advantages over NaCl for enhancement of limestone sulfur capture capacity in fluidized-bed combustors.

The Sulfur Dioxide Plume from the February 26, 2000 Eruption of Mt. Hekla, Iceland

NASA Technical Reports Server (NTRS)

Krueger, Arlin J.; Krotkov, N. A.; Einaudi, Franco (Technical Monitor)

2000-01-01

The February 2000 fissure eruption of Mt. Hekla, Iceland was captured in sulfur dioxide data from the Earth Probe TOMS. A special algorithm is used to discriminate sulfur dioxide from ozone. The eruption began at 18:19 GMT on February 26, 2000 and was first viewed by TOMS at 09:55 GMT on February 27. The volcanic cloud at that time appeared as a very long and narrow arc extending west from the volcano in southern Iceland, then north across Greenland, and finally east towards Norway. The cloud altitude was reported from aircraft sightings and data to be above 10 km. The circulation of a ridge located north of Iceland produced the large arc shaped cloud. As the eruption is non-explosive the high altitude cloud contains little ash. Almost all the ash from the eruption fell out locally across Iceland. By February 29, the sulfur dioxide cloud had drifted eastward in a band along the Barents Sea coast of Norway and Russia. The analysis includes an assessment of the initial sulfur dioxide content and its rate of conversion to sulfate.

Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report, July-September 1984

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, J.; Talbott, J.

1984-01-01

Task 1. Methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2. Methods development for the speciation of dithionite and polythionates. Work on Task 2 has been completed in June 1984 and has been reported accordingly in DOE/PC/40783-T15. Task 3. Total accounting of the sulfur balance in representative samples of synfuel process streams. A systematic and critical comparison of results, obtained in the analysis of sulfur moieties in representative samples of coal conversion process streams, revealed the following general trends. (a) In specimens of highmore » pH (9-10) and low redox potential (-0.3 to -0.4 volt versus NHE) sulfidic and polysulfidic sulfur moieties predominate. (b) In process streams of lower pH and more positive redox potential, higher oxidation states of sulfur (notably sulfate) account for most of the total sulfur present. (c) Oxidative wastewater treatment procedures by the PETC stripping process convert lower oxidation states of sulfur into thiosulfate and sulfate. In this context, remarkable similarities were observed between liquefaction and gasification process streams. However, the thiocyanate present in samples from the Grand Forks gasifier were impervious to the PETC stripping process. (d) Total sulfur contaminant levels in coal conversion process stream wastewater samples are primarily determined by the abundance of sulfur in the coal used as starting material than by the nature of the conversion process (liquefaction or gasification). 13 references.« less

Process for removing sulfur from sulfur-containing gases: high calcium fly-ash

DOEpatents

Rochelle, Gary T.; Chang, John C. S.

1991-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accordance with the present invention include preparing an aqueous slurry composed of a calcium alkali source and a source of reactive silica and/or alumina, heating the slurry to above-ambient temperatures for a period of time in order to facilitate the formation of sulfur-absorbing calcium silicates or aluminates, and treating the gas with the heat-treated slurry components. Examples disclosed herein demonstrate the utility of these processes in achieving improved sulfur-absorbing capabilities. Additionally, disclosure is provided which illustrates preferred configurations for employing the present processes both as a dry sorbent injection and for use in conjunction with a spray dryer and/or bagfilter. Retrofit application to existing systems is also addressed.

Process for combined control of mercury and nitric oxide.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Livengood, C. D.; Mendelsohn, M. H.

Continuing concern about the effects of mercury in the environment may lead to requirements for the control of mercury emissions from coal-fired power plants. If such controls are mandated, the use of existing flue-gas cleanup systems, such as wet scrubbers currently employed for flue-gas desulfurization, would be desirable, Such scrubbers have been shown to be effective for capturing oxidized forms of mercury, but cannot capture the very insoluble elemental mercury (Hg{sup 0}) that can form a significant fraction of the total emissions. At Argonne National Laboratory, we have proposed and tested a concept for enhancing removal of Hg{sup 0}, as well as nitric oxide, through introduction of an oxidizing agent into the flue gas upstream of a scrubber, which readily absorbs the soluble reaction products. Recently, we developed a new method for introducing the oxidizing agent into the flue-gas stream that dramatically improved reactant utilization. The oxidizing agent employed was NOXSORB{trademark}, which is a commercial product containing chloric acid and sodium chlorate. When a dilute solution of this agent was introduced into a gas stream containing Hg{sup 0} and other typical flue-gas species at 300 F, we found that about 100% of the mercury was removed from the gas phase and recovered in process liquids. At the same time, approximately 80% of the nitric oxide was removed. The effect of sulfur dioxide on this process was also investigated and the results showed that it slightly decreased the amount of Hg{sup 0} oxidized while appearing to increase the removal of nitric oxide from the gas phase. We are currently testing the effects of variations in NOXSORB{trademark} concentration, sulfur dioxide concentration, nitric oxide concentration, and reaction time (residence time). Preliminary economic projections based on the results to date indicate that the chemical cost for nitric oxide oxidation could be less thanmore » $$5,000/ton removed, while for Hg{sup 0} oxidation it would be about $$20,000/lb removed.« less

Chemical-Looping Combustion and Gasification of Coals and Oxygen Carrier Development: A Brief Review

DOE PAGES

Wang, Ping; Means, Nicholas; Shekhawat, Dushyant; ...

2015-09-24

Chemical-looping technology is one of the promising CO 2 capture technologies. It generates a CO 2 enriched flue gas, which will greatly benefit CO 2 capture, utilization or sequestration. Both chemical-looping combustion (CLC) and chemical-looping gasification (CLG) have the potential to be used to generate power, chemicals, and liquid fuels. Chemical-looping is an oxygen transporting process using oxygen carriers. Recently, attention has focused on solid fuels such as coal. Coal chemical-looping reactions are more complicated than gaseous fuels due to coal properties (like mineral matter) and the complex reaction pathways involving solid fuels. The mineral matter/ash and sulfur in coalmore » may affect the activity of oxygen carriers. Oxygen carriers are the key issue in chemical-looping processes. Thermogravimetric analysis (TGA) has been widely used for the development of oxygen carriers (e.g., oxide reactivity). Two proposed processes for the CLC of solid fuels are in-situ Gasification Chemical-Looping Combustion (iG-CLC) and Chemical-Looping with Oxygen Uncoupling (CLOU). The objectives of this review are to discuss various chemical-looping processes with coal, summarize TGA applications in oxygen carrier development, and outline the major challenges associated with coal chemical-looping in iG-CLC and CLOU.« less

The role of crystallization-driven exsolution on the sulfur mass balance in volcanic arc magmas

USGS Publications Warehouse

Su, Yanqing; Huber, Christian; Bachmann, Olivier; Zajacz, Zoltán; Wright, Heather M.; Vazquez, Jorge A.

2016-01-01

The release of large amounts of sulfur to the stratosphere during explosive eruptions affects the radiative balance in the atmosphere and consequentially impacts climate for up to several years after the event. Quantitative estimations of the processes that control the mass balance of sulfur between melt, crystals, and vapor bubbles is needed to better understand the potential sulfur yield of individual eruption events and the conditions that favor large sulfur outputs to the atmosphere. The processes that control sulfur partitioning in magmas are (1) exsolution of volatiles (dominantly H2O) during decompression (first boiling) and during isobaric crystallization (second boiling), (2) the crystallization and breakdown of sulfide or sulfate phases in the magma, and (3) the transport of sulfur-rich vapor (gas influx) from deeper unerupted regions of the magma reservoir. Vapor exsolution and the formation/breakdown of sulfur-rich phases can all be considered as closed-system processes where mass balance arguments are generally easier to constrain, whereas the contribution of sulfur by vapor transport (open system process) is more difficult to quantify. The ubiquitous “excess sulfur” problem, which refers to the much higher sulfur mass released during eruptions than what can be accounted for by amount of sulfur originally dissolved in erupted melt, as estimated from melt inclusion sulfur concentrations (the “petrologic estimate”), reflects the challenges in closing the sulfur mass balance between crystals, melt, and vapor before and during a volcanic eruption. In this work, we try to quantify the relative importance of closed- and open-system processes for silicic arc volcanoes using kinetic models of sulfur partitioning during exsolution. Our calculations show that crystallization-induced exsolution (second boiling) can generate a significant fraction of the excess sulfur observed in crystal-rich arc magmas. This result does not negate the important role of vapor migration in sulfur mass balance but rather points out that second boiling (in situ exsolution) can provide the necessary yield to drive the excess sulfur to the levels observed for crystal-rich systems. In contrast, in crystal-poor systems, magma recharge that releases sulfur-rich bubbles is necessary and most likely the primary contributor to sulfur mass balance. Finally, we apply our model to account for the effect of sulfur partitioning during second boiling and its impact on sulfur released during the Cerro Galan supereruption in Argentina (2.08 Ma) and show the potential importance of second boiling in releasing a large amount of sulfur to the atmosphere during the eruption of large crystal-rich ignimbrites.

Zero Liquid Discharge (ZLD) System for Flue-Gas Derived Water From Oxy-Combustion Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivaram Harendra; Danylo Oryshchyn; Thomas Ochs

2011-10-16

Researchers at the National Energy Technology Laboratory (NETL) located in Albany, Oregon, have patented a process - Integrated Pollutant Removal (IPR) that uses off-the-shelf technology to produce a sequestration ready CO{sub 2} stream from an oxy-combustion power plant. Capturing CO{sub 2} from fossil-fuel combustion generates a significant water product which can be tapped for use in the power plant and its peripherals. Water condensed in the IPR{reg_sign} process may contain fly ash particles, sodium (from pH control), and sulfur species, as well as heavy metals, cations and anions. NETL is developing a treatment approach for zero liquid discharge while maximizingmore » available heat from IPR. Current treatment-process steps being studied are flocculation/coagulation, for removal of cations and fine particles, and reverse osmosis, for anion removal as well as for scavenging the remaining cations. After reverse osmosis process steps, thermal evaporation and crystallization steps will be carried out in order to build the whole zero liquid discharge (ZLD) system for flue-gas condensed wastewater. Gypsum is the major product from crystallization process. Fast, in-line treatment of water for re-use in IPR seems to be one practical step for minimizing water treatment requirements for CO{sub 2} capture. The results obtained from above experiments are being used to build water treatment models.« less

Biologically removing sulfur from dilute gas flows

NASA Astrophysics Data System (ADS)

Ruitenberg, R.; Dijkman, H.; Buisman, C. J. N.

1999-05-01

A biological process has been developed to clean off-gases containing sulfur dioxide from industrial installations. The sulfur dioxide is converted into hydrogen sulfide, which can then be oxidized to elemental sulfur if not used on-site. The process produces no waste products that require disposal and has a low reagent consumption.

Sulfur Dioxide Capture by Heterogeneous Oxidation on Hydroxylated Manganese Dioxide.

PubMed

Wu, Haodong; Cai, Weimin; Long, Mingce; Wang, Hairui; Wang, Zhiping; Chen, Chen; Hu, Xiaofang; Yu, Xiaojuan

2016-06-07

Here we demonstrate that sulfur dioxide (SO2) is efficiently captured via heterogeneous oxidation into sulfate on the surface of hydroxylated manganese dioxide (MnO2). Lab-scale activity tests in a fluidized bed reactor showed that the removal efficiency for a simulated flue gas containing 5000 mg·Nm(-3) SO2 could reach nearly 100% with a GHSV (gas hourly space velocity) of 10000 h(-1). The mechanism was investigated using a combination of experimental characterizations and theoretical calculations. It was found that formation of surface bound sulfate proceeds via association of SO2 with terminal hydroxyls. Both H2O and O2 are essential for the generation of reactive terminal hydroxyls, and the indirect role of O2 in heterogeneous SO2 oxidation at low temperature was also revealed. We propose that the high reactivity of terminal hydroxyls is attributed to the proper surface configuration of MnO2 to adsorb water with degenerate energies for associative and dissociative states, and maintain rapid proton dynamics. Viability analyses suggest that the desulfurization method that is based on such a direct oxidation reaction at the gas/solid interface represents a promising approach for SO2 capture.

Sulfur emission from Victorian brown coal under pyrolysis, oxy-fuel combustion and gasification conditions.

PubMed

Chen, Luguang; Bhattacharya, Sankar

2013-02-05

Sulfur emission from a Victorian brown coal was quantitatively determined through controlled experiments in a continuously fed drop-tube furnace under three different atmospheres: pyrolysis, oxy-fuel combustion, and carbon dioxide gasification conditions. The species measured were H(2)S, SO(2), COS, CS(2), and more importantly SO(3). The temperature (873-1273 K) and gas environment effects on the sulfur species emission were investigated. The effect of residence time on the emission of those species was also assessed under oxy-fuel condition. The emission of the sulfur species depended on the reaction environment. H(2)S, SO(2), and CS(2) are the major species during pyrolysis, oxy-fuel, and gasification. Up to 10% of coal sulfur was found to be converted to SO(3) under oxy-fuel combustion, whereas SO(3) was undetectable during pyrolysis and gasification. The trend of the experimental results was qualitatively matched by thermodynamic predictions. The residence time had little effect on the release of those species. The release of sulfur oxides, in particular both SO(2) and SO(3), is considerably high during oxy-fuel combustion even though the sulfur content in Morwell coal is only 0.80%. Therefore, for Morwell coal utilization during oxy-fuel combustion, additional sulfur removal, or polishing systems will be required in order to avoid corrosion in the boiler and in the CO(2) separation units of the CO(2) capture systems.

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worthington, Max J. H.; Kucera, Renata L.; Albuquerque, Inês S.

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkalai plant operation, metallurgy, and areas of agriculture in which mercuryrich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils.more » A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry.« less

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils

DOE PAGES

Worthington, Max J. H.; Kucera, Renata L.; Albuquerque, Inês S.; ...

2017-08-30

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkalai plant operation, metallurgy, and areas of agriculture in which mercuryrich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils.more » A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry.« less

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils

PubMed Central

Worthington, Max J. H.; Kucera, Renata L.; Albuquerque, Inês S.; Gibson, Christopher T.; Sibley, Alexander; Slattery, Ashley D.; Campbell, Jonathan A.; Alboaiji, Salah F. K.; Muller, Katherine A.; Young, Jason; Adamson, Nick; Gascooke, Jason R.; Jampaiah, Deshetti; Sabri, Ylias M.; Bhargava, Suresh K.; Ippolito, Samuel J.; Lewis, David A.; Quinton, Jamie S.; Ellis, Amanda V.; Johs, Alexander; Bernardes, Gonçalo J. L.

2017-01-01

Abstract Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkali plant operation, metallurgy, and areas of agriculture in which mercury‐rich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low‐cost mercury sorbents made solely from sulfur and unsaturated cooking oils. A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by‐product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury‐capturing polymers can be synthesised entirely from waste and supplied on multi‐kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry. PMID:28763123

Chemical profiling in Moutan Cortex after sulfuring and desulfuring processes reveals further insights into the quality control of TCMs by nontargeted metabolomic analysis.

PubMed

Zhan, Zhi-Lai; Deng, Ai-Ping; Kang, Li-Ping; Tang, Jin-Fu; Nan, Tie-Gui; Chen, Tong; He, Ya-Li; Guo, Lan-Ping; Huang, Lu-Qi

2018-05-01

As a traditional processing method, sulfuring has been used in the processing of many traditional Chinese medicines (TCMs). Desulfuring, which has emerged in recent years, is a new method applied to sulfured herbs so they can comply with regulations regarding residual SO 2 . Due to the chemical transformations and the residual SO 2 in the herbs, both sulfuring and desulfuring have negative effects on the safety and therapeutic effects of TCMs, and Moutan Cortex is one of the TCMs most susceptible to these effects. Here, a new strategy was developed to differentiate normal, sulfured and desulfured Moutan Cortex, and the transformations of compounds in sulfuring and desulfuring processes were analyzed using ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF-MSE) method based on metabolomic analysis. Our findings were as follows: (1) a total of 119 compounds were identified or tentatively identified, including 9 compounds that are being reported for the first time as natural products; (2) 15 sulfocompounds were generated during the sulfuring process; (3) these sulfocompounds could not be converted back into their corresponding glycosides by the desulfuring process, and the desulfuring decreased the residual SO 2 ,while also removing some soluble compounds in the sulfured Moutan Cortex; and (4) 28 compounds were screened and tentatively identified as markers for distinguishing normal, sulfured and desulfured Moutan Cortex. Our findings provide a new practical strategy for evaluating how sulfuring and desulfuring affect the quality of TCMs. Copyright © 2018 Elsevier B.V. All rights reserved.

THE SPONTANEOUSLY HYPERTENSIVE RAT: AN EXPERIMENTAL MODEL OF SULFUR DIOXIDE-INDUCED AIRWAYS DISEASE

EPA Science Inventory

Chronic obstructive pulmonary disease (COPD) is characterized by airway obstruction, inflammation and mucus hypersecretion; features that capture bronchitis, emphysema and often asthma. However, current rodent models do not reflect this human disease. Because genetically predisp...

Process and technoeconomic analysis of leading pretreatment technologies for lignocellulosic ethanol production using switchgrass.

PubMed

Tao, Ling; Aden, Andy; Elander, Richard T; Pallapolu, Venkata Ramesh; Lee, Y Y; Garlock, Rebecca J; Balan, Venkatesh; Dale, Bruce E; Kim, Youngmi; Mosier, Nathan S; Ladisch, Michael R; Falls, Matthew; Holtzapple, Mark T; Sierra, Rocio; Shi, Jian; Ebrik, Mirvat A; Redmond, Tim; Yang, Bin; Wyman, Charles E; Hames, Bonnie; Thomas, Steve; Warner, Ryan E

2011-12-01

Six biomass pretreatment processes to convert switchgrass to fermentable sugars and ultimately to cellulosic ethanol are compared on a consistent basis in this technoeconomic analysis. The six pretreatment processes are ammonia fiber expansion (AFEX), dilute acid (DA), lime, liquid hot water (LHW), soaking in aqueous ammonia (SAA), and sulfur dioxide-impregnated steam explosion (SO(2)). Each pretreatment process is modeled in the framework of an existing biochemical design model so that systematic variations of process-related changes are consistently captured. The pretreatment area process design and simulation are based on the research data generated within the Biomass Refining Consortium for Applied Fundamentals and Innovation (CAFI) 3 project. Overall ethanol production, total capital investment, and minimum ethanol selling price (MESP) are reported along with selected sensitivity analysis. The results show limited differentiation between the projected economic performances of the pretreatment options, except for processes that exhibit significantly lower monomer sugar and resulting ethanol yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

Electrochemical Behavior of Sulfur in Aqueous Alkaline Solutions

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul; Mamitova, A. D.; Mamyrbekova, Aizhan

2018-03-01

The kinetics and mechanism of the electrode oxidation-reduction of sulfur on an electrically conductive sulfur-graphite electrode in an alkaline solution was studied by the potentiodynamic method. To examine the mechanism of electrode processes occurring during AC polarization on a sulfur-graphite electrode, the cyclic polarization in both directions and anodic polarization curves were recorded. The kinetic parameters: charge transfer coefficients (α), diffusion coefficients ( D), heterogeneous rate constants of electrode process ( k s), and effective activation energies of the process ( E a) were calculated from the results of polarization measurements. An analysis of the results and calculated kinetic parameters of electrode processes showed that discharge ionization of sulfur in alkaline solutions occurs as a sequence of two stages and is a quasireversible process.

Process for forming sulfuric acid

DOEpatents

Lu, Wen-Tong P.

1981-01-01

An improved electrode is disclosed for the anode in a sulfur cycle hydrogen generation process where sulfur dioxie is oxidized to form sulfuric acid at the anode. The active compound in the electrode is palladium, palladium oxide, an alloy of palladium, or a mixture thereof. The active compound may be deposited on a porous, stable, conductive substrate.

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

PubMed

Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

2018-05-17

Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

DEFE0023863 Final Report, Technology for GHG Emission Reduction and CostCompetitive MilSpec Jet Fuel Production using CTL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hartvigsen, Joseph J; Dimick, Paul; Laumb, Jason D

Ceramatec Inc, in collaboration with IntraMicron (IM), the Energy & Environmental Research Center (EERC) and Sustainable Energy Solutions, LLC (SES), have completed a three-year research project integrating their respective proprietary technologies in key areas to demonstrate production of a jet fuel from coal and biomass sources. The project goals and objectives were to demonstrate technology capable of producing a “commercially-viable quantity” of jet fuel and make significant progress toward compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements. The Ceramatec led team completed the demonstration of nominalmore » 2 bbl/day Fischer-Tropsch (FT) synthesis pilot plant design, capable of producing a nominal 1 bbl/day in the Jet-A/JP-8 fraction. This production rate would have a capacity of 1,000 gallons of jet fuel per month and provide the design basis of a 100 bbl/day module producing over 2,000 gallons of jet fuel per day. Co-gasification of coal-biomass blends enables a reduction of lifecycle greenhouse gas emissions from equivalent conventional petroleum derived fuel basis. Due to limits of biomass availability within an economic transportation range, implementation of a significant biomass feed fraction will require smaller plants than current world scale CTL and GTL FT plants. Hence a down-scaleable design is essential. The pilot plant design leverages Intramicron’s MicroFiber Entrapped Catalyst (MFEC) support which increases the catalyst bed thermal conductivity two orders of magnitude, allowing thermal management of the FT reaction exotherm in much larger reactor tubes. In this project, single tube reactors having 4.5 inch outer diameter and multi-tube reactors having 4 inch outer diameters were operated, with productivities as high as 1.5 gallons per day per linear foot of reactor tube. A significant reduction in tube count results from the use of large diameter reactor tubes, with an associated reduction in reactor cost. The pilot plant was designed with provisions for product collection capable of operating with conventional wax producing FT catalysts but was operated with a Chevron hybrid wax-free FT catalyst. Process simplification enabled by elimination of the wax hydrocracking process unit provides economic advantages in scaling to biomass capable plant sizes. Intramicron also provided a sulfur capture system based on their Oxidative Sulfur Removal (OSR) catalyst process. The integrated sulfur removal and FT systems were operated with syngas produced by the Transport Reactor Development Unit (TRDU) gasifier at the University of North Dakota EERC. SES performed modeling of their cryogenic carbon capture process on the energy, cost and CO2 emissions impact of the Coal-biomass synthetic fuel process.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

A rapid method for the measurement of sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), and Halon 1211 (CF2ClBr) in hydrologic tracer studies

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

2010-01-01

A rapid headspace method for the simultaneous laboratory determination of intentionally introduced hydrologic tracers, sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), Halon 1211 (CF2ClBr), and other halocarbons in water and gases is described. The high sensitivity of the procedure allows for introduction of minimal tracer mass (a few grams) into hydrologic systems with a large dynamic range of analytical detection (dilutions to 1:108). Analysis times by gas chromatography with electron capture detector are less than 1 min for SF6; about 2 min for SF6 and SF5CF3; and 4 min for SF6, SF5CF3, and Halon 1211. Many samples can be rapidly collected, preserved in stoppered septum bottles, and analyzed at a later time in the laboratory. Examples are provided showing the effectiveness of the gas tracer test studies in varied hydrogeological settings.

A rapid method for the measurement of sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), and Halon 1211 (CF2ClBr) in hydrologic tracer studies

NASA Astrophysics Data System (ADS)

Busenberg, Eurybiades; Plummer, L. Niel

2010-11-01

A rapid headspace method for the simultaneous laboratory determination of intentionally introduced hydrologic tracers, sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), Halon 1211 (CF2ClBr), and other halocarbons in water and gases is described. The high sensitivity of the procedure allows for introduction of minimal tracer mass (a few grams) into hydrologic systems with a large dynamic range of analytical detection (dilutions to 1:108). Analysis times by gas chromatography with electron capture detector are less than 1 min for SF6; about 2 min for SF6 and SF5CF3; and 4 min for SF6, SF5CF3, and Halon 1211. Many samples can be rapidly collected, preserved in stoppered septum bottles, and analyzed at a later time in the laboratory. Examples are provided showing the effectiveness of the gas tracer test studies in varied hydrogeological settings.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Study of variation grain size in desulfurization process of calcined petroleum coke

NASA Astrophysics Data System (ADS)

Pintowantoro, Sungging; Setiawan, Muhammad Arif; Abdul, Fakhreza

2018-04-01

Indonesia is a country with abundant natural resources, such as mineral mining and petroleum. In petroleum processing, crude oil can be processed into a source of fuel energy such as gasoline, diesel, oil, petroleum coke, and others. One of crude oil potentials in Indonesia is petroleum coke. Petroleum coke is a product from oil refining process. Sulfur reducing process in calcined petroleum cokes can be done by desulfurization process. The industries which have potential to become petroleum coke processing consumers are industries of aluminum smelting (anode, graphite block, carbon mortar), iron riser, calcined coke, foundry coke, etc. Sulfur reducing process in calcined petroleum coke can be done by thermal desulfurization process with alkaline substance NaOH. Desulfurization of petroleum coke process can be done in two ways, which are thermal desulfurization and hydrodesulphurization. This study aims to determine the effect of various grain size on sulfur, carbon, and chemical bond which contained by calcined petroleum coke. The raw material use calcined petroleum coke with 0.653% sulfur content. The grain size that used in this research is 50 mesh, then varied to 20 mesh and 100 mesh for each desulfurization process. Desulfurization are tested by ICP, UV-VIS, and FTIR to determine levels of sulfur, carbon, chemical bonding and sulfur dissolved water which contained in the residual washing of calcined petroleum coke. From various grain size that mentioned before, the optimal value is on 100 mesh grain size, where the sulfur content in petroleum coke is 0.24% and carbon content reaches the highest level of 97.8%. Meanwhile for grain size 100 mesh in the desulfurization process is enough to break the chemical bonds of organic sulfur in petroleum coke.

Multifunctional Interlayer Based on Molybdenum Diphosphide Catalyst and Carbon Nanotube Film for Lithium-Sulfur Batteries.

PubMed

Luo, Yufeng; Luo, Nannan; Kong, Weibang; Wu, Hengcai; Wang, Ke; Fan, Shoushan; Duan, Wenhui; Wang, Jiaping

2018-02-01

A multifunctional interlayer, composed of molybdenum diphosphide (MoP 2 ) nanoparticles and a carbon nanotube (CNT) film, is introduced into a lithium-sulfur (Li-S) battery system to suppress polysulfide migration. Molybdenum diphosphide acts as the catalyst and can capture polysulfides and improve the polysulfide conversion activity during the discharge/charge processes. The CNT film acts as a conductive skeleton to support the MoP 2 nanoparticles and to ensure their uniform distribution. The CNT film physically hinders polysulfide migration, acts as a current collector, and provides abundant electron pathways. The Li-S battery containing the multifunctional MoP 2 /CNT interlayer exhibits excellent electrochemical performance. It delivers a reversible specific capacity of 905 mA h g -1 over 100 cycles at 0.2 C, with a capacity decay of 0.152% per cycle. These results suggest the introduction of the multifunctional CNT/MoP 2 interlayer as an effective and practical method for producing high-performance Li-S batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Comparison of sulfur fumigation processing and direct hot air heating technology on puerarin contents and efficacy of Puerariae Thomsonii Radix].

PubMed

Yu, Hong-Li; Zhang, Qian; Jin, Yang-Ping; Wang, Kui-Long; Lu, Tu-Lin; Li, Lin

2016-07-01

In order to compare the effect of sulfur fumigation processing and direct hot air heating technology on puerarin contents and efficacy of Puerariae Thomsonii Radix, the fresh roots of Pueraria thomsonii were cut into small pieces and prepared into direct sunshine drying samples, direct hot air drying samples, and sulfur fumigation-hot air drying samples. Moisture contents of the samples were then determined. The puerarin contents of different samples were compared by HPLC method. Moreover, the models of drunkenness mice were established, and then with superoxide dismutase (SOD) content as the index, aqueous decoction extracts of Puerariae Thomsonii Radix samples with sulfur fumigation processing and non-sulfur fumigation processing methods were administrated by ig; the effects of sulfur fumigation on contents of SOD in mice liver and serum were determined, and the sulfur fumigation samples and non-sulfur fumigation samples were investigated for moth and mildew under different packaging and storage conditions. Results showed that the sulfur fumigation samples significantly changed the puerarin content from Puerariae Thomsonii Radix. The content of puerarin was decreased gradually when increasing the times of sulfur fumigation and amount of sulfur. SOD content in drunken mice liver and serum was significantly decreased when increasing the times of sulfur fumigation, showing significant difference with both direct sunshine drying group and direct hot air drying group. Moth and mildew were not found in the sulfur fumigation samples and direct hot air drying samples whose moisture contents were lower than the limit in Pharmacopoeia. Research showed that sulfur fumigation can significantly reduce the content of main active ingredients and reduce the efficacy of Puerariae Thomsonii Radix, indicating that the quality of Puerariae Thomsonii Radix was significantly decreased after sulfur fumigation. However, the contents of the main active ingredients, efficacy and storage results of the direct hot air drying samples were similar to those in direct sunshine drying samples, so the hot air drying process was a nice drying technology which could be promoted for use. Copyright© by the Chinese Pharmaceutical Association.

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur contentmore » is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)« less

A large column analog experiment of stable isotope variations during reactive transport: I. A comprehensive model of sulfur cycling and δ34S fractionation

NASA Astrophysics Data System (ADS)

Druhan, Jennifer L.; Steefel, Carl I.; Conrad, Mark E.; DePaolo, Donald J.

2014-01-01

This study demonstrates a mechanistic incorporation of the stable isotopes of sulfur within the CrunchFlow reactive transport code to model the range of microbially-mediated redox processes affecting kinetic isotope fractionation. Previous numerical models of microbially mediated sulfate reduction using Monod-type rate expressions have lacked rigorous coupling of individual sulfur isotopologue rates, with the result that they cannot accurately simulate sulfur isotope fractionation over a wide range of substrate concentrations using a constant fractionation factor. Here, we derive a modified version of the dual-Monod or Michaelis-Menten formulation (Maggi and Riley, 2009, 2010) that successfully captures the behavior of the 32S and 34S isotopes over a broad range from high sulfate and organic carbon availability to substrate limitation using a constant fractionation factor. The new model developments are used to simulate a large-scale column study designed to replicate field scale conditions of an organic carbon (acetate) amended biostimulation experiment at the Old Rifle site in western Colorado. Results demonstrate an initial period of iron reduction that transitions to sulfate reduction, in agreement with field-scale behavior observed at the Old Rifle site. At the height of sulfate reduction, effluent sulfate concentrations decreased to 0.5 mM from an influent value of 8.8 mM over the 100 cm flow path, and thus were enriched in sulfate δ34S from 6.3‰ to 39.5‰. The reactive transport model accurately reproduced the measured enrichment in δ34S of both the reactant (sulfate) and product (sulfide) species of the reduction reaction using a single fractionation factor of 0.987 obtained independently from field-scale measurements. The model also accurately simulated the accumulation and δ34S signature of solid phase elemental sulfur over the duration of the experiment, providing a new tool to predict the isotopic signatures associated with reduced mineral pools. To our knowledge, this is the first rigorous treatment of sulfur isotope fractionation subject to Monod kinetics in a mechanistic reactive transport model that considers the isotopic spatial distribution of both dissolved and solid phase sulfur species during microbially-mediated sulfate reduction. describe the design and results of the large-scale column experiment; demonstrate incorporation of the stable isotopes of sulfur in a dual-Monod kinetic expression such that fractionation is accurately modeled at both high and low substrate availability; verify accurate simulation of the chemical and isotopic gradients in reactant and product sulfur species using a kinetic fractionation factor obtained from field-scale analysis (Druhan et al., 2012); utilize the model to predict the final δ34S values of secondary sulfur minerals accumulated in the sediment over the course of the experiment. The development of rigorous isotope-specific Monod-type rate expressions are presented here in application to sulfur cycling during amended biostimulation, but are readily applicable to a variety of stable isotope systems associated with both steady state and transient biogenic redox environments. In other words, the association of this model with a uranium remediation experiment does not limit its applicability to more general redox systems. Furthermore, the ability of this model treatment to predict the isotopic composition of secondary minerals accumulated as a result of fractionating processes (item 4) offers an important means of interpreting solid phase isotopic compositions and tracking long-term stability of precipitates.

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, Mitchell R.; Gal, Eli

1993-01-01

A process and system for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous The government of the United States of America has rights in this invention pursuant to Contract No. DE-AC21-88MC 23174 awarded by the U.S. Department of Energy.

Sex and age differences in meat composition of Yeso sika deer (Cervus nippon yesoensis) reared for a short period after capture in the wild.

PubMed

Hayashida, Maki; Souma, Kousaku; Sugo, Kazuki; Araki, Shin-Ichi; Ishizaka, Fumiaki; Ueda, Masami; Kasai, Takamasa; Masuko, Takayoshi

2015-02-01

Yeso sika deer captured in winter around Lake Akan in Hokkaido were reared for 8-10 months at Tokyo University of Agriculture in Abashiri. Six 1-year-old females and males and six 2-year-old or older (adult) females and males were slaughtered and their carcasses were processed. The chemical composition, mineral contents and fatty acid composition of the loin were measured. No marked influence of gender or age was noted in the chemical composition of loin. In the mineral contents, significant differences were noted. The potassium and sulfur contents were lower and the sodium content was higher in adult deer meat (P < 0.05, respectively) and the potassium content was higher in male deer meat (P < 0.05). Arsenic, cadmium or lead were not detected. In the unsaturated fatty acid, a significant interaction was detected (P < 0.05), and it was high in 1-year-old female deer meat and low in 1-year-old male deer meat. Significant gender or age differences were noted only in the mineral contents in the loin of deer reared for a short period after capture. © 2014 Japanese Society of Animal Science.

Sulfur tolerant highly durable CO.sub.2 sorbents

DOEpatents

Smirniotis, Panagiotis G [Cincinnati, OH; Lu, Hong [Urbana, IL

2012-02-14

A sorbent for the capture of carbon dioxide from a gas stream is provided, the sorbent containing calcium oxide (CaO) and at least one refractory dopant having a Tammann temperature greater than about 530.degree. C., wherein the refractory dopant enhances resistance to sintering, thereby conserving performance of the sorbent at temperatures of at least about 530.degree. C. Also provided are doped CaO sorbents for the capture of carbon dioxide in the presence of SO.sub.2.

Insight into the molecular mechanism of the sulfur oxidation process by reverse sulfite reductase (rSiR) from sulfur oxidizer Allochromatium vinosum.

PubMed

Ghosh, Semanti; Bagchi, Angshuman

2018-04-26

Sulfur metabolism is one of the oldest known biochemical processes. Chemotrophic or phototrophic proteobacteria, through the dissimilatory pathway, use sulfate, sulfide, sulfite, thiosulfate or elementary sulfur by either reductive or oxidative mechanisms. During anoxygenic photosynthesis, anaerobic sulfur oxidizer Allochromatium vinosum forms sulfur globules that are further oxidized by dsr operon. One of the key redox enzymes in reductive or oxidative sulfur metabolic pathways is the DsrAB protein complex. However, there are practically no reports to elucidate the molecular mechanism of the sulfur oxidation process by the DsrAB protein complex from sulfur oxidizer Allochromatium vinosum. In the present context, we tried to analyze the structural details of the DsrAB protein complex from sulfur oxidizer Allochromatium vinosum by molecular dynamics simulations. The molecular dynamics simulation results revealed the various types of molecular interactions between DsrA and DsrB proteins during the formation of DsrAB protein complex. We, for the first time, predicted the mode of binding interactions between the co-factor and DsrAB protein complex from Allochromatium vinosum. We also compared the binding interfaces of DsrAB from sulfur oxidizer Allochromatium vinosum and sulfate reducer Desulfovibrio vulgaris. This study is the first to provide a comparative aspect of binding modes of sulfur oxidizer Allochromatium vinosum and sulfate reducer Desulfovibrio vulgaris.

A novel process for low-sulfur biodiesel production from scum waste.

PubMed

Ma, Huan; Addy, Min M; Anderson, Erik; Liu, Weiwei; Liu, Yuhuan; Nie, Yong; Chen, Paul; Cheng, Beijiu; Lei, Hanwu; Ruan, Roger

2016-08-01

Scum is an oil-rich waste from the wastewater treatment plants with a high-sulfur level. In this work, a novel process was developed to convert scum to high quality and low sulfur content biodiesel. A combination of solvent extraction and acid washing as pretreatment was developed to lower the sulfur content in the scum feedstock and hence improve biodiesel conversion yield and quality. Glycerin esterification was then employed to convert free fatty acids to glycerides. Moreover, a new distillation process integrating the traditional reflux distillation and adsorptive desulfurization was developed to further remove sulfur from the crude biodiesel. As a result, 70% of the filtered and dried scum was converted to biodiesel with sulfur content lower than 15ppm. The fatty acid methyl ester profiles showed that the refined biodiesel from the new process exhibited a higher quality and better properties than that from traditional process reported in previous studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reduction in environmental impact of sulfuric acid hydrolysis of bamboo for production of fuel ethanol.

PubMed

Sun, Zhao-Yong; Tang, Yue-Qin; Morimura, Shigeru; Kida, Kenji

2013-01-01

Fuel ethanol can be produced from bamboo by concentrated sulfuric acid hydrolysis followed by continuous ethanol fermentation. To reduce the environmental impact of this process, treatment of the stillage, reuse of the sulfuric acid and reduction of the process water used were studied. The total organic carbon (TOC) concentration of stillage decreased from 29,688 to 269 mg/l by thermophilic methane fermentation followed by aerobic treatment. Washing the solid residue from acid hydrolysis with effluent from the biological treatment increased the sugar recovery from 69.3% to 79.3%. Sulfuric acid recovered during the acid-sugar separation process was condensed and reused for hydrolysis, resulting in a sugar recovery efficiency of 76.8%, compared to 80.1% when fresh sulfuric acid was used. After acetate removal, the condensate could be reused as elution water in the acid-sugar separation process. As much as 86.3% of the process water and 77.6% of the sulfuric acid could be recycled. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sulfuric acid on Europa and the radiolytic sulfur cycle.

PubMed

Carlson, R W; Johnson, R E; Anderson, M S

1999-10-01

A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

Catalyst for elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, M.; Liu, W.

1995-01-24

A catalytic reduction process is described for the direct recovery of elemental sulfur from various SO[sub 2]-containing industrial gas streams. The catalytic process provides high activity and selectivity, as well as stability in the reaction atmosphere, for the reduction of SO[sub 2] to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over a metal oxide composite catalyst having one of the following empirical formulas: [(FO[sub 2])[sub 1[minus]n](RO)[sub n

Snapshots of C-S Cleavage in Egt2 Reveals Substrate Specificity and Reaction Mechanism.

PubMed

Irani, Seema; Naowarojna, Nathchar; Tang, Yang; Kathuria, Karan R; Wang, Shu; Dhembi, Anxhela; Lee, Norman; Yan, Wupeng; Lyu, Huijue; Costello, Catherine E; Liu, Pinghua; Zhang, Yan Jessie

2018-05-17

Sulfur incorporation in the biosynthesis of ergothioneine, a histidine thiol derivative, differs from other well-characterized transsulfurations. A combination of a mononuclear non-heme iron enzyme-catalyzed oxidative C-S bond formation and a subsequent pyridoxal 5'-phosphate (PLP)-mediated C-S lyase reaction leads to the net transfer of a sulfur atom from a cysteine to a histidine. In this study, we structurally and mechanistically characterized a PLP-dependent C-S lyase Egt2, which mediates the sulfoxide C-S bond cleavage in ergothioneine biosynthesis. A cation-π interaction between substrate and enzyme accounts for Egt2's preference of sulfoxide over thioether as a substrate. Using mutagenesis and structural biology, we captured three distinct states of the Egt2 C-S lyase reaction cycle, including a labile sulfenic intermediate captured in Egt2 crystals. Chemical trapping and high-resolution mass spectrometry were used to confirm the involvement of the sulfenic acid intermediate in Egt2 catalysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

A new process for converting SO2 to sulfur without generating secondary pollutants through reactions involving CaS and CaSO4.

PubMed

Sohn, H Y; Kim, Byung-Su

2002-07-01

Nonferrous smelters and coal gasification processes generate environmentally harmful sulfur dioxide streams, most of which are treated to produce sulfuric acid with the accompanying problems of market shortage and transportation difficulties. Some sulfur dioxide streams are scrubbed with an alkali solution or a solid substance such as limestone or dolomite, which in turn generates wastes that pose other pollution problems. While the conversion of sulfur dioxide to elemental sulfur has many environmental advantages, no processes exist that are environmentally acceptable and economically viable. A new method for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating solid wastes has been developed. In this process, calcium sulfate pellets as the starting raw material are reduced by a suitable reducing agent such as hydrogen to produce calcium sulfide pellets, which are used to reduce sulfur dioxide producing elemental sulfur vapor and calcium sulfate. The latter is then reduced to regenerate calcium sulfide. Thermodynamic analysis and experimental results indicated that the CaS-SO2 reaction produces mainly sulfur vapor and solid calcium sulfate and that the gaseous product from the CaSO4-H2 reaction is mainly water vapor. The rates of the two reactions are reasonably rapid in the temperature range 1000-1100 K, and, importantly, the physical strengths and reactivities of the pellets are maintained largely unchanged up to the tenth cycle, the last cycle tested in this work. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated gasification combined cycle desulfurization unit and new sulfide smelting plants, contain much higher partial pressures of SO2. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this paper.

Geochemical evidence for cryptic sulfur cycling in salt marsh sediments

NASA Astrophysics Data System (ADS)

Mills, Jennifer V.; Antler, Gilad; Turchyn, Alexandra V.

2016-11-01

Cryptic sulfur cycling is an enigmatic process in which sulfate is reduced to some lower-valence state sulfur species and subsequently quantitatively reoxidized; the rate and microbial energetics of this process and how prevalent it may be in the environment remain controversial. Here we investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through a reductive cycle replacing its oxygen atoms. This cryptic sulfur cycle was replicated in laboratory incubations using 18O-enriched water, demonstrating that the field results do not solely result from mixing processes in the natural environment. Numerical modeling of the laboratory incubations scaled to represent the salt marsh sediments suggests that the uptake rate of sulfate during this cryptic sulfur cycling is similar to the uptake rate of sulfate during the fastest microbial sulfate reduction that has been measured in the natural environment. The difference is that during cryptic sulfur cycling, all of the sulfur is subsequently reoxidized to sulfate. We discuss mechanisms for this pathway of sulfur cycling including the possible link to the subsurface iron cycle.

Comparison Analysis of Coal Biodesulfurization and Coal's Pyrite Bioleaching with Acidithiobacillus ferrooxidans

PubMed Central

Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

2013-01-01

Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process. PMID:24288464

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.

SORPTION OF ELEMENTAL MERCURY BY ACTIVATED CARBONS

EPA Science Inventory

The mechanisms and rate of elemental mercury (HgO) capture by activated carbons have been studied using a bench-scale apparatus. Three types of activated carbons, two of which are thermally activated (PC-100 and FGD) and one with elemental sulfur (S) impregnated in it (HGR), were...

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils.

PubMed

Worthington, Max J H; Kucera, Renata L; Albuquerque, Inês S; Gibson, Christopher T; Sibley, Alexander; Slattery, Ashley D; Campbell, Jonathan A; Alboaiji, Salah F K; Muller, Katherine A; Young, Jason; Adamson, Nick; Gascooke, Jason R; Jampaiah, Deshetti; Sabri, Ylias M; Bhargava, Suresh K; Ippolito, Samuel J; Lewis, David A; Quinton, Jamie S; Ellis, Amanda V; Johs, Alexander; Bernardes, Gonçalo J L; Chalker, Justin M

2017-11-16

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkali plant operation, metallurgy, and areas of agriculture in which mercury-rich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils. A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Computational screening of functional groups for capture of toxic industrial chemicals in porous materials.

PubMed

Kim, Ki Chul; Fairen-Jimenez, David; Snurr, Randall Q

2017-12-06

A thermodynamic analysis using quantum chemical methods was carried out to identify optimal functional group candidates that can be included in metal-organic frameworks and activated carbons for the selective capture of toxic industrial chemicals (TICs) in humid air. We calculated the binding energies of 14 critical TICs plus water with a series of 10 functional groups attached to a naphthalene ring model. Using vibrational calculations, the free energies of adsorption were calculated in addition to the binding energies. Our results show that, in these systems, the binding energies and free energies follow similar trends. We identified copper(i) carboxylate as the optimal functional group (among those studied) for the selective binding of the majority of the TICs in humid air, and this functional group exhibits especially strong binding for sulfuric acid. Further thermodynamic analysis shows that the presence of water weakens the binding strength of sulfuric acid with the copper carboxylate group. Our calculations predict that functionalization of aromatic rings would be detrimental to selective capture of COCl 2 , CO 2 , and Cl 2 under humid conditions. Finally, we found that forming an ionic complex, H 3 O + HSO 4 - , between H 2 SO 4 and H 2 O via proton transfer is not favorable on copper carboxylate.

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.

Woodchip-sulfur based heterotrophic and autotrophic denitrification (WSHAD) process for nitrate contaminated water remediation.

PubMed

Li, Rui; Feng, Chuanping; Hu, Weiwu; Xi, Beidou; Chen, Nan; Zhao, Baowei; Liu, Ying; Hao, Chunbo; Pu, Jiaoyang

2016-02-01

Nitrate contaminated water can be effectively treated by simultaneous heterotrophic and autotrophic denitrification (HAD). In the present study, woodchips and elemental sulfur were used as co-electron donors for HAD. It was found that ammonium salts could enhance the denitrifying activity of the Thiobacillus bacteria, which utilize the ammonium that is produced by the dissimilatory nitrate reduction to ammonium (DNRA) in the woodchip-sulfur based heterotrophic and autotrophic denitrification (WSHAD) process. The denitrification performance of the WSHAD process (reaction constants range from 0.05485 h(-1) to 0.06637 h(-1)) is better than that of sulfur-based autotrophic denitrification (reaction constants range from 0.01029 h(-1) to 0.01379 h(-1)), and the optimized ratio of woodchips to sulfur is 1:1 (w/w). No sulfate accumulation is observed in the WSHAD process and the alkalinity generated in the heterotrophic denitrification can compensate for alkalinity consumption by the sulfur-based autotrophic denitrification. The symbiotic relationship between the autotrophic and the heterotrophic denitrification processes play a vital role in the mixotrophic environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sulfur cycling, retention, and mobility in soils: A review

Treesearch

Pamela J. Edwards

1998-01-01

Sulfur inputs to forests originate from mineral weathering, atmospheric deposition, and organic matter decomposition. In the soil, sulfur occurs in organic and inorganic forms and is cycled within and between those forms via mobilization, immobilization, mineralization, oxidation, and reduction processes. Organic sulfur compounds are largely immobile. Inorganic sulfur...

40 CFR 436.190 - Applicability; description of the Frasch sulfur subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Frasch sulfur subcategory. 436.190 Section 436.190 Protection of Environment ENVIRONMENTAL PROTECTION... SOURCE CATEGORY Frasch Sulfur Subcategory § 436.190 Applicability; description of the Frasch sulfur subcategory. The provisions of this subpart are applicable to the processing of sulfur on shore and in marshes...

40 CFR 436.190 - Applicability; description of the Frasch sulfur subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Frasch sulfur subcategory. 436.190 Section 436.190 Protection of Environment ENVIRONMENTAL PROTECTION... Frasch Sulfur Subcategory § 436.190 Applicability; description of the Frasch sulfur subcategory. The provisions of this subpart are applicable to the processing of sulfur on shore and in marshes and estuaries...

40 CFR 436.190 - Applicability; description of the Frasch sulfur subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Frasch sulfur subcategory. 436.190 Section 436.190 Protection of Environment ENVIRONMENTAL PROTECTION... SOURCE CATEGORY Frasch Sulfur Subcategory § 436.190 Applicability; description of the Frasch sulfur subcategory. The provisions of this subpart are applicable to the processing of sulfur on shore and in marshes...

40 CFR 436.190 - Applicability; description of the Frasch sulfur subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Frasch sulfur subcategory. 436.190 Section 436.190 Protection of Environment ENVIRONMENTAL PROTECTION... Frasch Sulfur Subcategory § 436.190 Applicability; description of the Frasch sulfur subcategory. The provisions of this subpart are applicable to the processing of sulfur on shore and in marshes and estuaries...

40 CFR 436.190 - Applicability; description of the Frasch sulfur subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Frasch sulfur subcategory. 436.190 Section 436.190 Protection of Environment ENVIRONMENTAL PROTECTION... SOURCE CATEGORY Frasch Sulfur Subcategory § 436.190 Applicability; description of the Frasch sulfur subcategory. The provisions of this subpart are applicable to the processing of sulfur on shore and in marshes...

Liquid and Emulsified Sulfur in Submarine Solfatara Fields of two Northern Mariana Arc Volcanoes.

NASA Astrophysics Data System (ADS)

Nakamura, K.; Embley, R. W.; Chadwick, W. W.; Butterfield, D. A.; Takano, B.; Resing, J. A.; de Ronde, C. E.; Lilley, M. D.; Lupton, J. E.; Merle, S. G.; Inagaki, F.

2006-12-01

Because elemental sulfur melting point is ca 100 deg C (depend on allotropes and heating rate, S8 triple point temperature: 115 deg C), the evidence of liquid sulfur has been known for many subaerial crater lakes and small ponds in geothermal regions throughout the world. But the milky nature of water (sulfur-in- water emulsion in limited water mass) prohibited the direct observation of on-going processes at the bottom of these subaerial lakes. In the passive degassing environment at the summit craters of Daikoku and Nikko Seamounts of the northern Mariana Arc, the continuous flushing of sulfur emulsion by seawater allowed us to observe on- going submarine solfatara processes and associated chemistry through dives with ROVs during the NT05-18 cruise (JAMSTEC R/V Natsushima and ROV hyper-Dolphin) and the Submarine Ring of Fire 2006 cruise (R/V Melville and ROV JASON II). A higher viscosity for liquid elemental sulfur relative to that of seawater, as well as a limited stability of sulfur emulsion (aqueous sulfur sol) at high temperatures in electrolyte solution (seawater), ensures limited mobility of liquid sulfur in the conduits of hydrothermal vents. The subseafloor boiling depth of hydrothermal fluid limits the locus of any liquid sulfur reservoir. It was observed in an exposed liquid sulfur pond that the penetration of gas bubbles (mostly CO2) created sulfur emulsion while collapsing liquid sulfur film between seawater and gas bubbles. Liquid sulfur pits, encrusted sulfur, liquid sulfur fountain structure, sulfur stalactites and stalagmites, mini-pillow lava-like sulfur flows, accretionary sulfur lapilli and sulfur deltas were also observed at the summits of two volcanoes. Note: Solfatara: Italian. A type of fumarole, the gases of which are characteristically sulfurous. In 'Glossary of geology.'

A primer on sulfur for the planetary geologist

NASA Technical Reports Server (NTRS)

Theilig, E.

1982-01-01

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1985-01-01

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

PROCESS OF TREATING URANIUM HEXAFLUORIDE AND PLUTONIUM HEXAFLUORIDE MIXTURES WITH SULFUR TETRAFLUORIDE TO SEPARATE SAME

DOEpatents

Steindler, M.J.

1962-07-24

A process was developed for separating uranium hexafluoride from plutonium hexafluoride by the selective reduction of the plutonium hexafluoride to the tetrafluoride with sulfur tetrafluoride at 50 to 120 deg C, cooling the mixture to --60 to -100 deg C, and volatilizing nonreacted sulfur tetrafluoride and sulfur hexafluoride formed at that temperature. The uranium hexafluoride is volatilized at room temperature away from the solid plutonium tetrafluoride. (AEC)

Development of spent fuel reprocessing process based on selective sulfurization: Study on the Pu, Np and Am sulfurization

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Amano, Yuuki; Nihei, Toshifumi; Mitsugashira, Toshiaki; Sato, Nobuaki

2010-03-01

For the recovery of fissile materials from spent nuclear fuel, we have proposed a novel reprocessing process based on selective sulfurization of fission products (FPs). The key concept of this process is utilization of unique chemical property of carbon disulfide (CS2), i.e., it works as a reductant for U3O8 but works as a sulfurizing agent for minor actinides and lanthanides. Sulfurized FPs and minor actinides (MA) are highly soluble to dilute nitric acid while UO2 and PuO2 are hardly soluble, therefore, FPs and MA can be removed from Uranium and Plutonium matrix by selective dissolution. As a feasibility study of this new concept, the sulfurization behaviours of U, Pu, Np, Am and Eu are investigated in this paper by the thermodynamical calculation, phase analysis of chemical analogue elements and tracer experiments.

Formaldehyde instrument development and boundary layer sulfuric acid: Implications for photochemistry

NASA Astrophysics Data System (ADS)

Case Hanks, Anne Theresa

This work presents the development of a laser-induced fluorescence technique to measure atmospheric formaldehyde. In conjunction with the technique, the design of a compact, narrow linewidth, etalon-tuned titanium: sapphire laser cavity which is pumped by the second harmonic of a kilohertz Nd:YAG laser is also presented. The fundamental tunable range is from 690-1100 nm depending on mirror reflectivities and optics kit used. The conversion efficiency is at least 25% for the fundamental, and 2-3% for intracavity frequency doubling from 3.5-4W 532 nm pump power. The linewidth is <0.1 cm-1, and the pulsewidth is 18 nsec. Applications of this cavity include the measurement of trace gas species by laser-induced fluorescence, cavity ringdown spectroscopy, and micropulse lidar in the UV-visible region. Also presented are observations of gas-phase sulfuric acid from the NEAQS-ITCT 2K4 (New England Air Quality Study--- Intercontinental Transport and Chemical Transformation) field campaign in July and August 2004. Sulfuric acid values are reported for a polluted environment and possible nucleation events as well as particle growth within the boundary layer are explored. Sulfate production rates via gas phase oxidation of sulfur dioxide are also reported. This analysis allows an important test of our ability to predict sulfuric acid concentration and probe its use as a fast time response photochemical tracer for the hydroxyl radical, OH. In comparison, the NASA time-dependent photochemical box model is used to calculate OH concentration. Nighttime H2SO4 values are examined to test our understanding of nocturnal OH levels and oxidation processes. In comparison, sulfuric acid from a large ground based mission in Tecamac, Mexico (near the northern boundary of Mexico City) during MIRAGE-Mex field campaign (March 2006) is presented. This and other measurements are used to characterize atmospheric oxidation and predict sulfuric acid and OH concentrations at the site. The observations in conjunction with the NASA LARc Photochemical box model are used to explore ozone production, nitrate and sulfate formation, and radical levels and radical production rates during the day. The one minute observations of sulfuric acid, sulfur dioxide, and aerosol surface area were again used to calculate OH levels assuming steady state, and are in good agreement with observations of OH (R2 = 0.7). Photochemical activity is found to be a maximum during the morning hours, as seen in ozone and nitrate formation. Although the model predictions capture the observed diurnal profile, the model underpredicts RO2 concentrations in the morning hours and overpredicts in the afternoon (HO 2 + RO2 radical Model/observed (M/O) ˜ 1.15 and OH M/O ˜ 1.2).

PROCESS FOR COOLING A NUCLEAR REACTOR

DOEpatents

Borst, L.B.

1962-12-11

This patent relates to the operation of a reactor cooled by liquid sulfur dioxide. According to the invention the pressure on the sulfur dioxide in the reactor is maintained at least at the critical pressure of the sulfur dioxide. Heating the sulfur dioxide to its critical temperature results in vaporization of the sulfur dioxide without boiling. (AEC)

40 CFR 60.642 - Standards for sulfur dioxide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standards for sulfur dioxide. 60.642... Gas Processing: SO2 Emissions § 60.642 Standards for sulfur dioxide. (a) During the initial... reduction efficiency (Zi) to be determined from table 1 based on the sulfur feed rate (X) and the sulfur...

40 CFR 60.642 - Standards for sulfur dioxide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standards for sulfur dioxide. 60.642... Gas Processing: SO2 Emissions § 60.642 Standards for sulfur dioxide. (a) During the initial... reduction efficiency (Zi) to be determined from table 1 based on the sulfur feed rate (X) and the sulfur...

40 CFR 60.642 - Standards for sulfur dioxide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standards for sulfur dioxide. 60.642... Gas Processing: SO2 Emissions § 60.642 Standards for sulfur dioxide. (a) During the initial... reduction efficiency (Zi) to be determined from table 1 based on the sulfur feed rate (X) and the sulfur...

PILOT PLANT STUDY OF CONVERSION OF COAL TO LOW SULFUR FUEL

EPA Science Inventory

The report gives results of a program to develop, on bench and pilot scales, operating conditions for the key step in the IGT process to desulfurize coal by thermal and chemical treatment. This process, to date, uses the 'sulfur-getter' concept. (A sulfur-getter is a material tha...

Iron phthalocyanine modified mesoporous titania nanoparticles for photocatalytic activity and CO2 capture applications.

PubMed

Ramacharyulu, P V R K; Muhammad, Raeesh; Praveen Kumar, J; Prasad, G K; Mohanty, Paritosh

2015-10-21

An iron(II)phthalocyanine (Fepc) modified mesoporous titania (Fepc-TiO2) nanocatalyst with a specific surface area of 215 m(2) g(-1) has been synthesized by a hydrothermal method. Fepc-TiO2 degrades one of the highly toxic chemical warfare agents, sulfur mustard (SM), photocatalytically under sunlight with an exposure time of as low as 70 min. Furthermore, the mesoporous Fepc-TiO2 also captured 2.1 mmol g(-1) of CO2 at 273 K and 1 atm.

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes.

PubMed

Hua, Yujuan; Hawryluk, Myron; Gras, Ronda; Shearer, Randall; Luong, Jim

2018-01-01

A fast and reliable analytical technique for the determination of total sulfur levels in complex hydrocarbon matrices is introduced. The method employed flow injection technique using a gas chromatograph as a sample introduction device and a gas phase dual-plasma sulfur chemiluminescence detector for sulfur quantification. Using the technique described, total sulfur measurement in challenging hydrocarbon matrices can be achieved in less than 10 s with sample-to-sample time <2 min. The high degree of selectivity and sensitivity toward sulfur compounds of the detector offers the ability to measure low sulfur levels with a detection limit in the range of 20 ppb w/w S. The equimolar response characteristic of the detector allows the quantitation of unknown sulfur compounds and simplifies the calibration process. Response is linear over a concentration range of five orders of magnitude, with a high degree of repeatability. The detector's lack of response to hydrocarbons enables direct analysis without the need for time-consuming sample preparation and chromatographic separation processes. This flow injection-based sulfur chemiluminescence detection technique is ideal for fast analysis or trace sulfur analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Shared Sulfur Mobilization Routes for tRNA Thiolation and Molybdenum Cofactor Biosynthesis in Prokaryotes and Eukaryotes

PubMed Central

Leimkühler, Silke; Bühning, Martin; Beilschmidt, Lena

2017-01-01

Modifications of transfer RNA (tRNA) have been shown to play critical roles in the biogenesis, metabolism, structural stability and function of RNA molecules, and the specific modifications of nucleobases with sulfur atoms in tRNA are present in pro- and eukaryotes. Here, especially the thiomodifications xm5s2U at the wobble position 34 in tRNAs for Lys, Gln and Glu, were suggested to have an important role during the translation process by ensuring accurate deciphering of the genetic code and by stabilization of the tRNA structure. The trafficking and delivery of sulfur nucleosides is a complex process carried out by sulfur relay systems involving numerous proteins, which not only deliver sulfur to the specific tRNAs but also to other sulfur-containing molecules including iron–sulfur clusters, thiamin, biotin, lipoic acid and molybdopterin (MPT). Among the biosynthesis of these sulfur-containing molecules, the biosynthesis of the molybdenum cofactor (Moco) and the synthesis of thio-modified tRNAs in particular show a surprising link by sharing protein components for sulfur mobilization in pro- and eukaryotes. PMID:28098827

Tailoring Pore Size of Nitrogen-Doped Hollow Carbon Nanospheres for Confi ning Sulfur in Lithium–Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Weidong; Wang, Chong M.; Zhang, Quiglin

Three types of nitrogen-doped hollow carbon spheres with different pore sized porous shells are prepared to investigate the performance of sulfur confinement. The reason that why no sulfur is observed in previous research is determined and it is successfully demonstrated that the sulfur/polysulfide will overflow the porous carbon during the lithiation process.

HIGH TEMPERATURE SULFATION STUDIES IN AN ISOTHERMAL REACTOR: A COMPARISON OF THEORY AND EXPERIMENT

EPA Science Inventory

The paper gives high-temperature isothermal data on sulfur dioxide (SO2) capture, obtained as a function of temperature, SO2 partial pressure, and Ca/S molar ratio for a pulverized dolomite (34 micrometer mean size) and a high-purity calcite (11 micrometer mean size). The experim...

ENHANCEMENT OF REACTIVITY IN SURFACTANT-MODIFIED SORBENTS FOR SULFUR DIOXIDE CONTROL

EPA Science Inventory

The paper discusses the enhancement of reactivity in surfactant-modified sorbents for S02 control. Injecting calcium-based sorbents into the post-flame zone of utility boilers can achieve S02 captures of 50-60% at a stoichiometry of 2. Calcium hydroxide-- Ca(OH)2--appears to be t...

Recent approaches for the direct use of elemental sulfur in the synthesis and processing of advanced materials.

PubMed

Lim, Jeewoo; Pyun, Jeffrey; Char, Kookheon

2015-03-09

Elemental sulfur is an abundant and inexpensive material obtained as a by-product of natural-gas and petroleum refining operations. Recently, the need for the development of new energy-storage systems brought into light the potential of sulfur as a high-capacity cathode material in secondary batteries. Sulfur-containing materials were also shown to have useful IR optical properties. These developments coupled with growing environmental concerns related to the global production of excess elemental sulfur have led to a keen interest in its utilization as a feedstock in materials applications. This Minireview focuses on the recent developments on physical and chemical methods for directly processing elemental sulfur to produce functional composites and polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process and apparatus for generating elemental sulfur and re-usable metal oxide from spent metal sulfide sorbents

DOEpatents

Ayala, Raul E.; Gal, Eli

1995-01-01

A process and apparatus for generating elemental sulfur and re-usable metal oxide from spent metal-sulfur compound. Spent metal-sulfur compound is regenerated to re-usable metal oxide by moving a bed of spent metal-sulfur compound progressively through a single regeneration vessel having a first and second regeneration stage and a third cooling and purging stage. The regeneration is carried out and elemental sulfur is generated in the first stage by introducing a first gas of sulfur dioxide which contains oxygen at a concentration less than the stoichiometric amount required for complete oxidation of the spent metal-sulfur compound. A second gas containing sulfur dioxide and excess oxygen at a concentration sufficient for complete oxidation of the partially spent metal-sulfur compound, is introduced into the second regeneration stage. Gaseous sulfur formed in the first regeneration stage is removed prior to introducing the second gas into the second regeneration stage. An oxygen-containing gas is introduced into the third cooling and purging stage. Except for the gaseous sulfur removed from the first stage, the combined gases derived from the regeneration stages which are generally rich in sulfur dioxide and lean in oxygen, are removed from the regenerator as an off-gas and recycled as the first and second gas into the regenerator. Oxygen concentration is controlled by adding air, oxygen-enriched air or pure oxygen to the recycled off-gas.

Organismal and spatial partitioning of energy and macronutrient transformations within a hypersaline mat

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mobberley, Jennifer M.; Lindemann, Stephen R.; Bernstein, Hans C.

2017-03-21

Phototrophic mat communities are model ecosystems for studying energy cycling and elemental transformations because complete biogeochemical cycles occur over millimeter-to-centimeter scales. Characterization of energy and nutrient capture within hypersaline phototrophic mats has focused on specific processes and organisms, however little is known about community-wide distribution of and linkages between these processes. To investigate energy and macronutrient capture and flow through a structured community, the spatial and organismal distribution of metabolic functions within a compact hypersaline mat community from Hot Lake have been broadly elucidated through species-resolved metagenomics and geochemical, microbial diversity, and metabolic gradient measurements. Draft reconstructed genomes of abundantmore » organisms revealed three dominant cyanobacterial populations differentially distributed across the top layers of the mat suggesting niche separation along light and oxygen gradients. Many organisms contained diverse functional profiles, allowing for metabolic response to changing conditions within the mat. Organisms with partial nitrogen and sulfur metabolisms were widespread indicating dependence upon metabolite exchange. In addition, changes in community spatial structure were observed over the diel. These results indicate that organisms within the mat community have adapted to the temporally dynamic environmental gradients in this hypersaline mat through metabolic flexibility and fluid syntrophic interactions, including shifts in spatial arrangements.« less

Sulfur-oxidizing autotrophic and mixotrophic denitrification processes for drinking water treatment: elimination of excess sulfate production and alkalinity requirement.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin

2012-09-01

This study evaluated the elimination of alkalinity need and excess sulfate generation of sulfur-based autotrophic denitrification process by stimulating simultaneous autotrophic and heterotrophic (mixotrophic) denitrification process in a column bioreactor by methanol supplementation. Also, denitrification performances of sulfur-based autotrophic and mixotrophic processes were compared. In autotrophic process, acidity produced by denitrifying sulfur-oxidizing bacteria was neutralized by the external NaHCO(3) supplementation. After stimulating mixotrophic denitrification process, the alkalinity need of the autotrophic process was satisfied by the alkalinity produced by heterotrophic denitrifiers. Decreasing and lastly eliminating the external alkalinity supplementation did not adversely affect the process performance. Complete denitrification of 75 mg L(-1) NO(3)-N under mixotrophic conditions at 4 h hydraulic retention time was achieved without external alkalinity supplementation and with effluent sulfate concentration lower than the drinking water guideline value of 250 mg L(-1). The denitrification rate of mixotrophic process (0.45 g NO(3)-N L(-1) d(-1)) was higher than that of autotrophic one (0.3 g NO(3)-N L(-1) d(-1)). Batch studies showed that the sulfur-based autotrophic nitrate reduction rate increased with increasing initial nitrate concentration and transient accumulation of nitrite was observed. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sulfur compounds in coal

NASA Technical Reports Server (NTRS)

Attar, A.; Corcoran, W. H.

1977-01-01

The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

Desulfurization of gasoline.

PubMed Central

Berger, J E

1975-01-01

Although gasoline blending streams exhibit widely varying sulfur concentrations, significant quantities of low-sulfur motor gasoline cannot be manufactured by reallocation of existing components without substantial sacrifices in the useful properties of the remaining fuels having normal sulfur levels. To meet the anticipated demand for low-sulfur unleaded gasoline which may be required for catalyst-equipped automobiles it will be necessary to install process equipment based on known hydrotreating technology. The effects which this construction program would exert on the activities, abilities and needs of one petroleum refiner are sketched for two degrees of sulfur removal. The impacts of installing the process facilities which would be necessary are discussed in terms of time requirements, capital needs, and added energy expenditures. PMID:1157782

Sulfidation behavior of ZnFe2O4 roasted with pyrite: Sulfur inducing and sulfur-oxygen interface exchange mechanism

NASA Astrophysics Data System (ADS)

Min, Xiaobo; Zhou, Bosheng; Ke, Yong; Chai, Liyuan; Xue, Ke; Zhang, Chun; Zhao, Zongwen; Shen, Chen

2016-05-01

The sulfidation roasting behavior was analyzed in detail to reveal the reaction mechanism. Information about the sulfidation reaction, including phase transformation, ionic migration behavior and morphological change, were obtained by XRD, 57Fe Mossbauer spectroscopy, XPS and SEM analysis. The results showed that the sulfidation of zinc ferrite is a process of sulfur inducing and sulfur-oxygen interface exchange. This process can be divided into six stages: decomposition of FeS2, formation of the oxygen-deficient environment, migration of O2- induced by S2(g), formation of ZnFe2O4-δ, migration of Fe2+ accompanied by the precipitation of ZnO, and the sulfur-oxygen interface exchange reaction. The sulfidation products were zinc blende, wurtzite, magnetite and a fraction of zinc-bearing magnetite. These findings can provide theoretical support for controlling the process during which the recovery of Zn and Fe is achieved through the combined flotation-magnetic separation process.

Process for removing pyritic sulfur from bituminous coals

DOEpatents

Pawlak, Wanda; Janiak, Jerzy S.; Turak, Ali A.; Ignasiak, Boleslaw L.

1990-01-01

A process is provided for removing pyritic sulfur and lowering ash content of bituminous coals by grinding the feed coal, subjecting it to micro-agglomeration with a bridging liquid containing heavy oil, separating the microagglomerates and separating them to a water wash to remove suspended pyritic sulfur. In one embodiment the coal is subjected to a second micro-agglomeration step.

Process for removing sulfur from coal

DOEpatents

Aida, Tetsuo; Squires, Thomas G.; Venier, Clifford G.

1985-02-05

A process for the removal of divalent organic and inorganic sulfur compounds from coal and other carbonaceous material. A slurry of pulverized carbonaceous material is contacted with an electrophilic oxidant which selectively oxidizes the divalent organic and inorganic compounds to trivalent and tetravalent compounds. The carbonaceous material is then contacted with a molten caustic which dissolves the oxidized sulfur compounds away from the hydrocarbon matrix.

The in situ synthesis of PbS nanocrystals from lead(II) n-octylxanthate within a 1,3-diisopropenylbenzene–bisphenol A dimethacrylate sulfur copolymer

PubMed Central

Bear, J. C.; Mayes, A. G.; Parkin, I. P.; O'Brien, P.

2017-01-01

The synthesis of lead sulfide nanocrystals within a solution processable sulfur ‘inverse vulcanization’ polymer thin film matrix was achieved from the in situ thermal decomposition of lead(II) n-octylxanthate, [Pb(S2COOct)2]. The growth of nanocrystals within polymer thin films from single-source precursors offers a faster route to networks of nanocrystals within polymers when compared with ex situ routes. The ‘inverse vulcanization’ sulfur polymer described herein contains a hybrid linker system which demonstrates high solubility in organic solvents, allowing solution processing of the sulfur-based polymer, ideal for the formation of thin films. The process of nanocrystal synthesis within sulfur films was optimized by observing nanocrystal formation by X-ray photoelectron spectroscopy and X-ray diffraction. Examination of the film morphology by scanning electron microscopy showed that beyond a certain precursor concentration the nanocrystals formed were not only within the film but also on the surface suggesting a loading limit within the polymer. We envisage this material could be used as the basis of a new generation of materials where solution processed sulfur polymers act as an alternative to traditional polymers. PMID:28878986

Capturing a DNA duplex under near-physiological conditions

NASA Astrophysics Data System (ADS)

Zhang, Huijuan; Xu, Wei; Liu, Xiaogang; Stellacci, Francesco; Thong, John T. L.

2010-10-01

We report in situ trapping of a thiolated DNA duplex with eight base pairs into a polymer-protected gold nanogap device under near-physiological conditions. The double-stranded DNA was captured by electrophoresis and covalently attached to the nanogap electrodes through sulfur-gold bonding interaction. The immobilization of the DNA duplex was confirmed by direct electrical measurements under near-physiological conditions. The conductance of the DNA duplex was estimated to be 0.09 μS. We also demonstrate the control of DNA dehybridization by heating the device to temperatures above the melting point of the DNA.

Technology could deliver 90% Hg reduction from coal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maize, K.

2009-07-15

Reducing mercury emissions at coal-fired power plants by 90% has been considered the holy grail of mercury control. A new technology promises to get used there, but at a price. This is a mixture of chemical approaches, including activated carbon injection into the gases coming off the combustor along with injection of trona or calcium carbonate to reduce sulfur trioxide in the exhaust gases. The trick according to Babcock and Wilcox's manager Sam Kumar, to 'capture the mercury as a particulate on the carbon and then capture the particulate' in an electrostatic precipitator or a fabric filter baghouse. 2 figs.

Greening coal: breakthroughs and challenges in carbon capture and storage.

PubMed

Stauffer, Philip H; Keating, Gordon N; Middleton, Richard S; Viswanathan, Hari S; Berchtold, Kathryn A; Singh, Rajinder P; Pawar, Rajesh J; Mancino, Anthony

2011-10-15

Like it or not, coal is here to stay, for the next few decades at least. Continued use of coal in this age of growing greenhouse gas controls will require removing carbon dioxide from the coal waste stream. We already remove toxicants such as sulfur dioxide and mercury, and the removal of CO₂ is the next step in reducing the environmental impacts of using coal as an energy source (i.e., greening coal). This paper outlines some of the complexities encountered in capturing CO₂ from coal, transporting it large distances through pipelines, and storing it safely underground.

SOXAL combined SO{sub x}/NO{sub x} flue gas control demonstration. Quarterly report, October--December 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

AQUATECH Systems a business unit of Allied-Signal Inc., proposes to demonstrate the technical viability and cost effectiveness of the SOXAL process a combined SO{sub x}/NO{sub x} control process on a 2--3 MW equivalent flue gas slip stream from Niagara Mohawk Power Corporation, Dunkirk Steam Station Boiler {number_sign}4, a coal fired boiler. The SOXAL process combines 90+% sulfur dioxide removal from the flue gas using a sodium based scrubbing solution and regeneration of the spent scrubbing liquor using AQUATECH Systems` proprietary bipolar membrane technology. This regeneration step recovers a stream of sulfur dioxide suitable for subsequent processing to salable sulfur ormore » sulfuric acid. Additionally 90+% control of NO{sub x} gases can be achieved in combination with conventional urea/methanol injection of NO{sub 2} gas into the duct. The SOXAL process is applicable to both utility and industrial scale boilers using either high or low sulfur coal. The SOXAL Demonstration Program began September 10, 1991 and is approximately 22 months in duration.« less

Transition metal-catalyzed oxidation of sulfur(IV) oxides. Atmospheric-relevant processes and mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brandt, C.; Eldik, R. van

1995-01-01

The transition metal-catalyzed oxidation of sulfur(IV) oxides has been known for more than 100 years. There is a significant lack of information on the actual role of the transition metal-catalyzed reactions, and much of the earlier work was performed without a detailed knowledge of the chemical system. For this reason attention is focused on the role of transition metal ions in the oxidation of sulfur(IV) oxides in terms of the coordination chemistry involved, as well as the stability and chemical behavior of the various participating species. The oxidation process of sulfur(IV) oxides plays an important role in atmospheric chemistry (e.g.more » acid rain formation) as well as industrial processes (e.g. desulfurization of plume gases and ore). The present report deals with the mechanism of the transition metal-catalyzed oxidation of sulfur(IV) oxides with the aim to discuss this in terms of atmospheric and chemical processes. In addition, the authors would like to emphasize the key role of oxygen in these processes. 1,076 refs.« less

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.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments

PubMed Central

Wasmund, Kenneth; Mußmann, Marc

2017-01-01

Summary Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular‐ and ecosystem‐level processes. Sulfur‐transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate‐rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep‐subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. PMID:28419734

Zeolites Remove Sulfur From Fuels

NASA Technical Reports Server (NTRS)

Voecks, Gerald E.; Sharma, Pramod K.

1991-01-01

Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

PubMed

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

2017-08-01

Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Analysis of Operational Parameters Affecting the Sulfur Content in Hot Metal of the COREX Process

NASA Astrophysics Data System (ADS)

Wu, Shengli; Wang, Laixin; Kou, Mingyin; Wang, Yujue; Zhang, Jiacong

2017-02-01

The COREX process, which has obvious advantages in environment protection, still has some disadvantages. It has a higher sulfur content in hot metal (HM) than the blast furnace has. In the present work, the distribution and transfer of sulfur in the COREX have been analyzed and several operational parameters related to the sulfur content in HM ([pct S]) have been obtained. Based on this, the effects of the coal rate, slag ratio, temperature of HM, melting rate, binary basicity ( R 2), the ratio of MgO/Al2O3, utilization of reducing gas, top gas consumption per ton burden solid, metallization rate, oxidation degree of reducing gas, and coal and DRI distribution index on the sulfur content in HM are investigated. What's more, a linear model has been developed and subsequently used for predicting and controlling the S content in HM of the COREX process.

Mössbauer study of the inorganic sulfur removal from coals

NASA Astrophysics Data System (ADS)

Reyes Caballero, F.; Martínez Ovalle, S. A.

2014-01-01

Mössbauer Spectroscopy (MS) was applied to study the occurrence and behavior of the iron-sulfur-containing minerals in coal and coal fractions obtained by different separation methods: hydrocyclonic, flotation and chemical removal process. Samples of one high sulfur coal from Guachinte mine (Valle, Colombia) and three low sulfur coals from the El Salitre zone (Paipa-Boyacá, Colombia) were analyzed. MS evidenced only the presence of pyrite in Esmeralda and Las Casitas coals, while it identified pyrite and siderite on Cerezo coal. MS and SEM- EDX confirm the inorganic sulfur removal on Guachinte coal submitted to hydrocyclonic removal process. MS of the precipitated coal fraction from Las Casitas mine obtained by flotation in water showed the presence of ferrous sulfate because of coal-weathering process. Treatment with hot diluted HNO3 equal to 27 acid on raw coal sample from Las Casitas mine showed that almost all of the pyrite in raw coal was removed.

Enhanced electrochemical performance of sulfur/polyacrylonitrile composite by carbon coating for lithium/sulfur batteries

NASA Astrophysics Data System (ADS)

Peng, Huifen; Wang, Xiaoran; Zhao, Yan; Tan, Taizhe; Mentbayeva, Almagul; Bakenov, Zhumabay; Zhang, Yongguang

2017-10-01

A carbon-coated sulfur/polyacrylonitrile (C@S/PAN) core-shell structured composite is successfully prepared via a novel solution processing method. The sulfur/polyacrylonitrile (S/PAN) core particle has a diameter of 100 nm, whereas the carbon shell is about 2 nm thick. The as-prepared C@S/PAN composite shows outstanding electrochemical performance in lithium/sulfur (Li/S) batteries delivering a high initial discharge capacity of 1416 mAh g-1. Furthermore, it exhibits 89% retention of the initial reversible capacity over 200 cycles at a constant current rate of 0.1 C. The improved performance contributed by the unique composition and the core-shell structure, wherein carbon matrix can also withstand the volume change of sulfur during the process of charging and discharging as well as provide channels for electron transport. In addition, polyacrylonitrile (PAN) matrix suppresses the shuttle effect by the covalent bonding between sulfur (S) and carbon (C) in the PAN matrix. [Figure not available: see fulltext.

Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

NASA Astrophysics Data System (ADS)

Adam, P.; Schneckenburger, P.; Schaeffer, P.; Albrecht, P.

2000-10-01

Macromolecular fractions, isolated from the solvent extract of sulfur-rich Recent (Siders Pond, USA; Lake Cadagno, Switzerland; Walvis Bay, Namibia) and immature sediments (Gibellina, Messinian of Sicily; Vena del Gesso, Messinian of Italy), were investigated by chemical degradation using sodium ethanethiolate/methyliodide. This mild reagent which cleaves polysulfide bonds to yield methylsulfides has the advantage over other methods of leaving intact other functionalities (like double bonds) and preserving sulfur atoms at their incorporation site. The method is, therefore, well-suited to the molecular level investigation of sulfur-rich macromolecules from Recent sediments containing highly functionalized polysulfide-bound subunits. In Recent anoxic sulfur-rich sediments, the release of various methylthioethers clearly demonstrates that intermolecular sulfurization of organic matter does occur at the earliest stages of diagenesis. Steroids and phytane derivatives are the major sulfurized lipids, a feature also observed in more mature sulfur-rich sediments. Several phytene derivatives, such as cis and trans 1-methylthiophyt-2-enes, as well as methylthiosteroids, including 5α- and 5β-3-(methylthio)-cholest-2-enes, were identified by comparison with synthesized standards. Steroid methylthioenolethers are released from polysulfide-bound steroid enethiols present in the macromolecular fractions. The latter, which correspond to thioketones, can be considered as intermediates in the reductive sulfurization pathway leading from steroid ketones to polysulfide-bound saturated steroid skeletons and are characterized for the first time in the present study. Thus, it could be shown that the major part of the polysulfide-bound lipids occurring in Recent sediments is apparently the result of sulfurization processes affecting carbonyls (aldehydes and ketones). The unsaturated methylthioethers obtained from Recent sediments were not present in more mature evaporitic samples, which suggests that polysulfide-bound unsaturated thiols are intermediates formed during the first sulfurization steps occurring soon after deposition and that they are rapidly transformed by various processes taking place during early diagenesis, notably to yield their saturated counterparts.

Recovery of Water from Boiler Flue Gas Using Condensing Heat Exchangers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levy, Edward; Bilirgen, Harun; DuPont, John

2011-03-31

Most of the water used in a thermoelectric power plant is used for cooling, and DOE has been focusing on possible techniques to reduce the amount of fresh water needed for cooling. DOE has also been placing emphasis on recovery of usable water from sources not generally considered, such as mine water, water produced from oil and gas extraction, and water contained in boiler flue gas. This report deals with development of condensing heat exchanger technology for recovering moisture from flue gas from coal-fired power plants. The report describes: • An expanded data base on water and acid condensation characteristicsmore » of condensing heat exchangers in coal-fired units. This data base was generated by performing slip stream tests at a power plant with high sulfur bituminous coal and a wet FGD scrubber and at a power plant firing highmoisture, low rank coals. • Data on typical concentrations of HCl, HNO{sub 3} and H{sub 2}SO{sub 4} in low temperature condensed flue gas moisture, and mercury capture efficiencies as functions of process conditions in power plant field tests. • Theoretical predictions for sulfuric acid concentrations on tube surfaces at temperatures above the water vapor dewpoint temperature and below the sulfuric acid dew point temperature. • Data on corrosion rates of candidate heat exchanger tube materials for the different regions of the heat exchanger system as functions of acid concentration and temperature. • Data on effectiveness of acid traps in reducing sulfuric acid concentrations in a heat exchanger tube bundle. • Condensed flue gas water treatment needs and costs. • Condensing heat exchanger designs and installed capital costs for full-scale applications, both for installation immediately downstream of an ESP or baghouse and for installation downstream of a wet SO{sub 2} scrubber. • Results of cost-benefit studies of condensing heat exchangers.« less

Recovery of Water from Boiler Flue Gas Using Condensing Heat Exchangers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edward Levy; Harun Bilirgen; John DuPoint

2011-03-31

Most of the water used in a thermoelectric power plant is used for cooling, and DOE has been focusing on possible techniques to reduce the amount of fresh water needed for cooling. DOE has also been placing emphasis on recovery of usable water from sources not generally considered, such as mine water, water produced from oil and gas extraction, and water contained in boiler flue gas. This report deals with development of condensing heat exchanger technology for recovering moisture from flue gas from coal-fired power plants. The report describes: (1) An expanded data base on water and acid condensation characteristicsmore » of condensing heat exchangers in coal-fired units. This data base was generated by performing slip stream tests at a power plant with high sulfur bituminous coal and a wet FGD scrubber and at a power plant firing high-moisture, low rank coals. (2) Data on typical concentrations of HCl, HNO{sub 3} and H{sub 2}SO{sub 4} in low temperature condensed flue gas moisture, and mercury capture efficiencies as functions of process conditions in power plant field tests. (3) Theoretical predictions for sulfuric acid concentrations on tube surfaces at temperatures above the water vapor dewpoint temperature and below the sulfuric acid dew point temperature. (4) Data on corrosion rates of candidate heat exchanger tube materials for the different regions of the heat exchanger system as functions of acid concentration and temperature. (5) Data on effectiveness of acid traps in reducing sulfuric acid concentrations in a heat exchanger tube bundle. (6) Condensed flue gas water treatment needs and costs. (7) Condensing heat exchanger designs and installed capital costs for full-scale applications, both for installation immediately downstream of an ESP or baghouse and for installation downstream of a wet SO{sub 2} scrubber. (8) Results of cost-benefit studies of condensing heat exchangers.« less

Characterization and differential expression of microRNAs elicited by sulfur deprivation in Chlamydomonas reinhardtii

PubMed Central

2012-01-01

Background microRNAs (miRNAs) have been found to play an essential role in the modulation of numerous biological processes in eukaryotes. Chlamydomonas reinhardtii is an ideal model organism for the study of many metabolic processes including responses to sulfur-deprivation. We used a deep sequencing platform to extensively profile and identify changes in the miRNAs expression that occurred under sulfur-replete and sulfur-deprived conditions. The aim of our research was to characterize the differential expression of Chlamydomonas miRNAs under sulfur-deprived conditions, and subsequently, the target genes of miRNA involved in sulfur-deprivation were further predicted and analyzed. Results By using high-throughput sequencing, we characterized the microRNA transcriptomes under sulphur-replete and sulfur-deprived conditions in Chlamydomonas reinhardtii. We predicted a total of 310 miRNAs which included 85 known miRNAs and 225 novel miRNAs. 13 miRNAs were the specific to the sulfur-deprived conditions. 47 miRNAs showed significantly differential expressions responding to sulfur-deprivation, and most were up-regulated in the small RNA libraries with sulfur-deprivation. Using a web-based integrated system (Web MicroRNAs Designer 3) and combing the former information from a transcriptome of Chlamydomonas reinhardtii, 22 miRNAs and their targets involved in metabolism regulation with sulfur-deprivation were verified. Conclusions Our results indicate that sulfur-deprivation may have a significant influence on small RNA expression patterns, and the differential expressions of miRNAs and interactions between miRNA and its targets might further reveal the molecular mechanism responding to sulfur-deprivation in Chlamydomonas reinhardtii. PMID:22439676

Process for removing sulfur from coal

DOEpatents

Aida, T.; Squires, T.G.; Venier, C.G.

1983-08-11

A process is disclosed for the removal of divalent organic and inorganic sulfur compounds from coal and other carbonaceous material. A slurry of pulverized carbonaceous material is contacted with an electrophilic oxidant which selectively oxidizes the divalent organic and inorganic compounds to trivalent and tetravalent compounds. The carbonaceous material is then contacted with a molten caustic which dissolves the oxidized sulfur compounds away from the hydrocarbon matrix.

Multi-component removal in flue gas by aqua ammonia

DOEpatents

Yeh, James T [Bethel Park, PA; Pennline, Henry W [Bethel Park, PA

2007-08-14

A new method for the removal of environmental compounds from gaseous streams, in particular, flue gas streams. The new method involves first oxidizing some or all of the acid anhydrides contained in the gas stream such as sulfur dioxide (SO.sub.2) and nitric oxide (NO) and nitrous oxide (N.sub.2O) to sulfur trioxide (SO.sub.3) and nitrogen dioxide (NO.sub.2). The gas stream is subsequently treated with aqua ammonia or ammonium hydroxide which captures the compounds via chemical absorption through acid-base or neutralization reactions. The products of the reactions can be collected as slurries, dewatered, and dried for use as fertilizers, or once the slurries have been dewatered, used directly as fertilizers. The ammonium hydroxide can be regenerated and recycled for use via thermal decomposition of ammonium bicarbonate, one of the products formed. There are alternative embodiments which entail stoichiometric scrubbing of nitrogen oxides and sulfur oxides with subsequent separate scrubbing of carbon dioxide.

The Reactive Sulfur Species Concept: 15 Years On.

PubMed

Giles, Gregory I; Nasim, Muhammad Jawad; Ali, Wesam; Jacob, Claus

2017-05-23

Fifteen years ago, in 2001, the concept of "Reactive Sulfur Species" or RSS was advocated as a working hypothesis. Since then various organic as well as inorganic RSS have attracted considerable interest and stimulated many new and often unexpected avenues in research and product development. During this time, it has become apparent that molecules with sulfur-containing functional groups are not just the passive "victims" of oxidative stress or simple conveyors of signals in cells, but can also be stressors in their own right, with pivotal roles in cellular function and homeostasis. Many "exotic" sulfur-based compounds, often of natural origin, have entered the fray in the context of nutrition, ageing, chemoprevention and therapy. In parallel, the field of inorganic RSS has come to the forefront of research, with short-lived yet metabolically important intermediates, such as various sulfur-nitrogen species and polysulfides (S x 2- ), playing important roles. Between 2003 and 2005 several breath-taking discoveries emerged characterising unusual sulfur redox states in biology, and since then the truly unique role of sulfur-dependent redox systems has become apparent. Following these discoveries, over the last decade a "hunt" and, more recently, mining for such modifications has begun-and still continues-often in conjunction with new, innovative and complex labelling and analytical methods to capture the (entire) sulfur "redoxome". A key distinction for RSS is that, unlike oxygen or nitrogen, sulfur not only forms a plethora of specific reactive species, but sulfur also targets itself, as sulfur containing molecules, i.e., peptides, proteins and enzymes, preferentially react with RSS. Not surprisingly, today this sulfur-centred redox signalling and control inside the living cell is a burning issue, which has moved on from the predominantly thiol/disulfide biochemistry of the past to a complex labyrinth of interacting signalling and control pathways which involve various sulfur oxidation states, sulfur species and reactions. RSS are omnipresent and, in some instances, are even considered as the true bearers of redox control, perhaps being more important than the Reactive Oxygen Species (ROS) or Reactive Nitrogen Species (RNS) which for decades have dominated the redox field. In other(s) words, in 2017, sulfur redox is "on the rise", and the idea of RSS resonates throughout the Life Sciences. Still, the RSS story isn't over yet. Many RSS are at the heart of "mistaken identities" which urgently require clarification and may even provide the foundations for further scientific revolutions in the years to come. In light of these developments, it is therefore the perfect time to revisit the original hypotheses, to select highlights in the field and to question and eventually update our concept of "Reactive Sulfur Species".

The Reactive Sulfur Species Concept: 15 Years On

PubMed Central

Giles, Gregory I.; Nasim, Muhammad Jawad; Ali, Wesam; Jacob, Claus

2017-01-01

Fifteen years ago, in 2001, the concept of “Reactive Sulfur Species” or RSS was advocated as a working hypothesis. Since then various organic as well as inorganic RSS have attracted considerable interest and stimulated many new and often unexpected avenues in research and product development. During this time, it has become apparent that molecules with sulfur-containing functional groups are not just the passive “victims” of oxidative stress or simple conveyors of signals in cells, but can also be stressors in their own right, with pivotal roles in cellular function and homeostasis. Many “exotic” sulfur-based compounds, often of natural origin, have entered the fray in the context of nutrition, ageing, chemoprevention and therapy. In parallel, the field of inorganic RSS has come to the forefront of research, with short-lived yet metabolically important intermediates, such as various sulfur-nitrogen species and polysulfides (Sx2−), playing important roles. Between 2003 and 2005 several breath-taking discoveries emerged characterising unusual sulfur redox states in biology, and since then the truly unique role of sulfur-dependent redox systems has become apparent. Following these discoveries, over the last decade a “hunt” and, more recently, mining for such modifications has begun—and still continues—often in conjunction with new, innovative and complex labelling and analytical methods to capture the (entire) sulfur “redoxome”. A key distinction for RSS is that, unlike oxygen or nitrogen, sulfur not only forms a plethora of specific reactive species, but sulfur also targets itself, as sulfur containing molecules, i.e., peptides, proteins and enzymes, preferentially react with RSS. Not surprisingly, today this sulfur-centred redox signalling and control inside the living cell is a burning issue, which has moved on from the predominantly thiol/disulfide biochemistry of the past to a complex labyrinth of interacting signalling and control pathways which involve various sulfur oxidation states, sulfur species and reactions. RSS are omnipresent and, in some instances, are even considered as the true bearers of redox control, perhaps being more important than the Reactive Oxygen Species (ROS) or Reactive Nitrogen Species (RNS) which for decades have dominated the redox field. In other(s) words, in 2017, sulfur redox is “on the rise”, and the idea of RSS resonates throughout the Life Sciences. Still, the RSS story isn’t over yet. Many RSS are at the heart of “mistaken identities” which urgently require clarification and may even provide the foundations for further scientific revolutions in the years to come. In light of these developments, it is therefore the perfect time to revisit the original hypotheses, to select highlights in the field and to question and eventually update our concept of “Reactive Sulfur Species”. PMID:28545257

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

DOEpatents

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Mixing of sulfur between pyritic and organic phases during coal conversion processes: Annual final report, March 1, 1986-February 28, 1987

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunkerton, L.V.; Nigam, A.; Mitra, S.

1987-05-01

In preparation for using /sup 33/S NMR for characterization of organic sulfur types in coal, previously prepared substituted dibenzothiophene model compounds were converted to their corresponding sulfones and their sulfur-33 nmr recorded. The sulfur-33 NMR spectra of dibenzothiophene-5,5-dioxide (2), 2-(p-methylphenylsulfonyl) dibenzothiophene-5,5-dioxide (4), and 2-(methylsulfonyl) dibenzothiophene-5,5-dioxide (6) are reported. The chemical shifts were in the +2 to -21 ppM range. The line widths ranged 70 to 200 Hz. The changes in /sup 13/C chemical shift experienced by aromatic carbons upon oxidizing the sulfide to its sulfone were also studied and the data used to identify which sulfone was formed in multiplemore » thioether-containing aromatics after partial oxidation. Continuing results on the use of the substituted dibenzothiophenes to monitor mixing of sulfur between pyritic and organic phases are also reported. Non-isothermal hydrodesulfurization of model organic sulfur compounds was carried out in a cola-like environment. The model sulfur compounds represented different types of carbon-sulfur bonds commonly encountered in coal. Similar experiments were carried out in the presence of troilite (iron sulfide) to investigate the possibility of sulfur migration from the organic compound to the iron sulfide. Next, iron pyrite was hydrodesulfurized in the presence of some organic molecules to see if sulfur could be incorporated into the organic molecules during the process. Results show that sulfur from organic compounds can be absorbed by troilite, and, similarly, sulfur from pyrite can form new carbon-sulfur bonds during hydrodesulfurization. Based on these observations, it is suggested that during coal conversion reactions it is possible to have intermigration of sulfur between the organic and the inorganic phases.« less

Transcriptional and Proteomic Profiling of Aspergillus flavipes in Response to Sulfur Starvation.

PubMed

El-Sayed, Ashraf S A; Yassin, Marwa A; Ali, Gul Shad

2015-01-01

Aspergillus flavipes has received considerable interest due to its potential to produce therapeutic enzymes involved in sulfur amino acid metabolism. In natural habitats, A. flavipes survives under sulfur limitations by mobilizing endogenous and exogenous sulfur to operate diverse cellular processes. Sulfur limitation affects virulence and pathogenicity, and modulates proteome of sulfur assimilating enzymes of several fungi. However, there are no previous reports aimed at exploring effects of sulfur limitation on the regulation of A. flavipes sulfur metabolism enzymes at the transcriptional, post-transcriptional and proteomic levels. In this report, we show that sulfur limitation affects morphological and physiological responses of A. flavipes. Transcription and enzymatic activities of several key sulfur metabolism genes, ATP-sulfurylase, sulfite reductase, methionine permease, cysteine synthase, cystathionine β- and γ-lyase, glutathione reductase and glutathione peroxidase were increased under sulfur starvation conditions. A 50 kDa protein band was strongly induced by sulfur starvation, and the proteomic analyses of this protein band using LC-MS/MS revealed similarity to many proteins involved in the sulfur metabolism pathway.

Vapor phase elemental sulfur amendment for sequestering mercury in contaminated soil

DOEpatents

Looney, Brian B.; Denham, Miles E.; Jackson, Dennis G.

2014-07-08

The process of treating elemental mercury within the soil is provided by introducing into the soil a heated vapor phase of elemental sulfur. As the vapor phase of elemental sulfur cools, sulfur is precipitated within the soil and then reacts with any elemental mercury thereby producing a reaction product that is less hazardous than elemental mercury.

The Plant Target of Rapamycin Kinase: A connecTOR between Sulfur and Growth.

PubMed

Forzani, Céline; Turqueto Duarte, Gustavo; Meyer, Christian

2018-06-01

Sulfur is an essential macronutrient for plants that is incorporated into sulfur-containing amino acids or metabolites crucial for plant growth and stress adaptation. A recent publication shows a connection between sulfur sensing, growth processes, and the conserved eukaryotic target of rapamycin (TOR) kinase signaling pathway. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

PubMed

Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

2009-08-01

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions.

PubMed

Baroni, Mélanie; Thiemens, Mark H; Delmas, Robert J; Savarino, Joël

2007-01-05

The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.

Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents.

PubMed

Bobbitt, N Scott; Mendonca, Matthew L; Howarth, Ashlee J; Islamoglu, Timur; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

2017-06-06

Owing to the vast diversity of linkers, nodes, and topologies, metal-organic frameworks can be tailored for specific tasks, such as chemical separations or catalysis. Accordingly, these materials have attracted significant interest for capture and/or detoxification of toxic industrial chemicals and chemical warfare agents. In this paper, we review recent experimental and computational work pertaining to the capture of several industrially-relevant toxic chemicals, including NH 3 , SO 2 , NO 2 , H 2 S, and some volatile organic compounds, with particular emphasis on the challenging issue of designing materials that selectively adsorb these chemicals in the presence of water. We also examine recent research on the capture and catalytic degradation of chemical warfare agents such as sarin and sulfur mustard using metal-organic frameworks.

Reduction of produced elementary sulfur in denitrifying sulfide removal process.

PubMed

Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

2011-05-01

Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

Environmental Electrophiles: Protein Adducts, Modulation of Redox Signaling, and Interaction with Persulfides/Polysulfides.

PubMed

Kumagai, Yoshito; Abiko, Yumi

2017-01-17

Included among the many environmental electrophiles are aromatic hydrocarbon quinones formed during combustion of gasoline, crotonaldehyde in tobacco smoke, methylmercury accumulated in fish, cadmium contaminated in rice, and acrylamide in baked foods. These electrophiles can modify nucleophilic functions such as cysteine residues in proteins forming adducts and in the process activate cellular redox signal transduction pathways such as kinases and transcription factors. However, higher concentrations of electrophiles disrupt such signaling by nonselective covalent modification of cellular proteins. Persulfide/polysulfides produced by various enzymes appear to capture environmental electrophiles because of the formation of their sulfur adducts without electrophilicity. We therefore speculate that persulfide/polysulfides are candidates for the regulation of redox signal transduction pathways (e.g., cell survival, cell proliferation, and adaptive response) and toxicity during exposure to environmental electrophiles.

Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

NASA Astrophysics Data System (ADS)

Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

2014-12-01

Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

Sulfate- and Sulfur-Reducing Bacteria as Terrestrial Analogs for Microbial Life on Jupiter's Satellite Io

NASA Technical Reports Server (NTRS)

Pikuta, Elena V.; Hoover, Richard B.; Six, N. Frank (Technical Monitor)

2001-01-01

Observations from the Voyager and Galileo spacecraft have revealed Jupiter's moon Io to be the most volcanically active body of our Solar System. The Galileo Near Infrared Imaging Spectrometer (NIMS) detected extensive deposits of sulfur compounds, elemental sulfur and SO2 frost on the surface of Io. There are extreme temperature variations on Io's surface, ranging from -130 C to over 2000 C at the Pillan Patera volcanic vent. The active volcanoes, fumaroles, calderas, and lava lakes and vast sulfur deposits on this frozen moon indicate that analogs of sulfur- and sulfate-reducing bacteria might inhabit Io. Hence Io may have great significance to Astrobiology. Earth's life forms that depend on sulfur respiration are members of two domains: Bacteria and Archaea. Two basic links of the biogeochemical sulfur cycle of Earth have been studied: 1) the sulfur oxidizing process (occurring at aerobic conditions) and 2) the process of sulfur-reduction to hydrogen sulfide (anaerobic conditions). Sulfate-reducing bacteria (StRB) and sulfur-reducing bacteria (SrRB) are responsible for anaerobic reducing processes. At the present time the systematics of StRB include over 112 species distributed into 35 genera of Bacteria and Archaea. Moderately thermophilic and mesophilic SrRB belong to the Bacteria. The hyperthermophilic SrRB predominately belong to the domain Archaea and are included in the genera: Pyrodictium, Thermoproteus, Pyrobaculum, Thermophilum, Desulfurococcus, and Thermodiscus. The StRB and SrRB use a wide spectrum of substrates as electron donors for lithotrophic and heterotrophic type nutrition. The electron acceptors for the StRB include: sulfate, thiosulfate, sulfite, sulfur, arsenate, dithionite, tetrathionate, sulfur monoxide, iron, nitrite, selenite, fumarate, oxygen, carbon dioxide, and chlorine-containing phenol compounds. The Sulfate- and Sulfur-reducing bacteria are widely distributed in anaerobic ecosystems, including extreme environments like hot springs, deepsea hydrothermal vents, soda and high salinity lakes, and cryo-environments. Furthermore, the StRB and SrRB have Astrobiological significance as these anaerobic extremophiles may represent the dominant relic life forms that inhabited our planet during the extensive volcanic activity in the Earth's early evolutionary period.

Relationship between microbial community dynamics and process performance during thermophilic sludge bioleaching.

PubMed

Chen, Shen-Yi; Chou, Li-Chieh

2016-08-01

Heavy metals can be removed from the sludge using bioleaching technologies at thermophilic condition, thereby providing an option for biotreatment of wasted sludge generated from wastewater treatment. The purposes of this study were to establish a molecular biology technique, real-time PCR, for the detection and enumeration of the sulfur-oxidizing bacteria during the thermophilic sludge bioleaching. The 16S rRNA gene for real-time PCR quantification targeted the bioleaching bacteria: Sulfobacillus thermosulfidooxidans, Sulfobacillus acidophilus, and Acidithiobacillus caldus. The specificity and stringency for thermophilic sulfur-oxidizing bacteria were tested before the experiments of monitoring the bacterial community, bacterial number during the thermophilic sludge bioleaching and the future application on testing various environmental samples. The results showed that S. acidophilus was identified as the dominant sulfur-oxidizing bacteria, while A. caldus and S. thermosulfidooxidans occurred in relatively low numbers. The total number of the sulfur-oxidizing bacteria increased during the thermophilic bioleaching process. Meanwhile, the decrease of pH, production of sulfate, degradation of SS/VSS, and solubilization of heavy metal were found to correlate well with the population of thermophilic sulfur-oxidizing bacteria during the bioleaching process. The real-time PCR used in this study is a suitable method to monitor numbers of thermophilic sulfur-oxidizing bacteria during the bioleaching process.

Process development for production of coal/sorbent agglomerates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rapp, D.M.

1991-01-01

The goal of this work was to develop a process flow diagram to economically produce a clean-burning fuel from fine Illinois coal. To accomplish this, the process of pelletizing fine coal with calcium hydroxide, a sulfur capturing sorbent, was investigated. Carbonation, which is the reaction of calcium hydroxide with carbon dioxide (in the presence of moisture) to produce a bonding matrix of calcium carbonate, was investigated as a method for improving pellet quality and reducing binder costs. Proper moisture level is critical to allow the reaction to occur. If too much moisture is present in a pellet, the pore spacesmore » are filled and carbon dioxide must diffuse through the water to reach the calcium hydroxide and react. This severely slows or stops the reaction. The ideal situation is when there is just enough moisture to coat the calcium hydroxide allowing for the reaction to proceed. The process has been successfully demonstrated on a pilot-scale as a method of hardening iron ore pellets (Imperato, 1966). Two potential combustion options are being considered for the coal/calcium hydroxide pellets: fluidized bed combustors and industrial stoker boilers.« less

Towards Next Generation Lithium-Sulfur Batteries: Non-Conventional Carbon Compartments/Sulfur Electrodes and Multi-Scale Analysis

DOE PAGES

Dysart, Arthur D.; Burgos, Juan C.; Mistry, Aashutosh; ...

2016-02-09

In this work, a novel heterofunctional, bimodal-porous carbon morphology, termed the carbon compartment (CC), is utilized as a sulfur host as a lithium-sulfur battery cathode. A multi-scale model explores the physics and chemistry of the lithium-sulfur battery cathode. The CCs are synthesized by a rapid, low cost process to improve electrode-electrolyte interfacial contact and accommodate volumetric expansion associated with sulfide formation. The CCs demonstrate high sulfur loading (47 %-wt. S) and ca. 700 mAh g -1 reversible capacity with high coulombic efficiency due to their unique structures. Density functional theory and ab initio Molecular Dynamics characterize the interface between themore » C/S composite and electrolyte during the sulfur reduction mechanism. Stochastic realizations of 3D electrode microstructures are reconstructed based on representative SEM images to study the influence of solid sulfur loading and lithium sulfide precipitation on microstructural and electrochemical properties. A macroscale electrochemical performance model is developed to analyze the performance of lithium-sulfur batteries. The combined multi-scale simulation studies explain key fundamentals of sulfur reduction and its relation to the polysulfide shuttle mechanism: how the process is affected due to the presence of carbon substrate, thermodynamics of lithium sulfide formation and deposition on carbon, and microstructural effects on the overall cell performance.« less

The analysis of thermoplastic characteristics of special polymer sulfur composite

NASA Astrophysics Data System (ADS)

Książek, Mariusz

2017-01-01

Specific chemical environments step out in the industry objects. Portland cement composites (concrete and mortar) were impregnated by using the special polymerized sulfur and technical soot as a filler (polymer sulfur composite). Sulfur and technical soot was applied as the industrial waste. Portland cement composites were made of the same aggregate, cement and water. The process of special polymer sulfur composite applied as the industrial waste is a thermal treatment process in the temperature of about 150-155°C. The result of such treatment is special polymer sulfur composite in a liquid state. This paper presents the plastic constants and coefficients of thermal expansion of special polymer sulfur composites, with isotropic porous matrix, reinforced by disoriented ellipsoidal inclusions with orthotropic symmetry of the thermoplastic properties. The investigations are based on the stochastic differential equations of solid mechanics. A model and algorithm for calculating the effective characteristics of special polymer sulfur composites are suggested. The effective thermoplastic characteristics of special polymer sulfur composites, with disoriented ellipsoidal inclusions, are calculated in two stages: First, the properties of materials with oriented inclusions are determined, and then effective constants of a composite with disoriented inclusions are determined on the basis of the Voigt or Rice scheme. A brief summary of new products related to special polymer sulfur composites is given as follows: Impregnation, repair, overlays and precast polymer concrete will be presented. Special polymer sulfur as polymer coating impregnation, which has received little attention in recent years, currently has some very interesting applications.

Quadruple sulfur isotope constraints on the origin and cycling of volatile organic sulfur compounds in a stratified sulfidic lake

NASA Astrophysics Data System (ADS)

Oduro, Harry; Kamyshny, Alexey; Zerkle, Aubrey L.; Li, Yue; Farquhar, James

2013-11-01

We have quantified the major forms of volatile organic sulfur compounds (VOSCs) distributed in the water column of stratified freshwater Fayetteville Green Lake (FGL), to evaluate the biogeochemical pathways involved in their production. The lake's anoxic deep waters contain high concentrations of sulfate (12-16 mmol L-1) and sulfide (0.12 μmol L-1 to 1.5 mmol L-1) with relatively low VOSC concentrations, ranging from 0.1 nmol L-1 to 2.8 μmol L-1. Sulfur isotope measurements of combined volatile organic sulfur compounds demonstrate that VOSC species are formed primarily from reduced sulfur (H2S/HS-) and zero-valent sulfur (ZVS), with little input from sulfate. Thedata support a role of a combination of biological and abiotic processes in formation of carbon-sulfur bonds between reactive sulfur species and methyl groups of lignin components. These processes are responsible for very fast turnover of VOSC species, maintaining their low levels in FGL. No dimethylsulfoniopropionate (DMSP) was detected by Electrospray Ionization Mass Spectrometry (ESI-MS) in the lake water column or in planktonic extracts. These observations indicate a pathway distinct from oceanic and coastal marine environments, where dimethylsulfide (DMS) and other VOSC species are principally produced via the breakdown of DMSP by plankton species.

Sulfuric acid-sulfur heat storage cycle

DOEpatents

Norman, John H.

1983-12-20

A method of storing heat is provided utilizing a chemical cycle which interconverts sulfuric acid and sulfur. The method can be used to levelize the energy obtained from intermittent heat sources, such as solar collectors. Dilute sulfuric acid is concentrated by evaporation of water, and the concentrated sulfuric acid is boiled and decomposed using intense heat from the heat source, forming sulfur dioxide and oxygen. The sulfur dioxide is reacted with water in a disproportionation reaction yielding dilute sulfuric acid, which is recycled, and elemental sulfur. The sulfur has substantial potential chemical energy and represents the storage of a significant portion of the energy obtained from the heat source. The sulfur is burned whenever required to release the stored energy. A particularly advantageous use of the heat storage method is in conjunction with a solar-powered facility which uses the Bunsen reaction in a water-splitting process. The energy storage method is used to levelize the availability of solar energy while some of the sulfur dioxide produced in the heat storage reactions is converted to sulfuric acid in the Bunsen reaction.

Sulfur-based autotrophic denitrification with eggshell for nitrate-contaminated synthetic groundwater treatment.

PubMed

Xu, Yaxian; Chen, Nan; Feng, Chuanping; Hao, Chunbo; Peng, Tong

2016-12-01

Eggshell is considered to be a waste and a significant quantity of eggshell waste is generated from food processing, baking and hatching industries. In this study, the effect of different sulfur/eggshell (w/w) ratios and temperatures was investigated to evaluate the feasibility of the sulfur-based autotrophic denitrification with eggshell (SADE) process for nitrate removal. The results showed eggshell can maintain a neutral condition in a range of pH 7.05-7.74 in the SADE process, and remove 97% of nitrate in synthetic groundwater. Compared with oyster shell and limestone, eggshell was found to be a desirable alkaline material for sulfur-based autotrophic denitrification (SAD) with no nitrite accumulation and insignificant sulfate production. Denitrification reaction was found to follow the first-order kinetic models (R(2) > .9) having nitrate removal rate constants of 0.85 and 0.93 d(-1) for raw eggshell and boiled eggshell, respectively. Sulfur/eggshell ratio of 2:3 provided the best efficiency on nitrate removal. Nitrate was removed completely by the SADE process at a low temperature of 15°C. Eggshell could be used for the SAD process due to its good effect for nitrate removal from groundwater.

Biogeochemical zonation of sulfur during the discharge of groundwater to lake in desert plateau (Dakebo Lake, NW China).

PubMed

Su, Xiaosi; Cui, Geng; Wang, Huang; Dai, Zhenxue; Woo, Nam-Chil; Yuan, Wenzhen

2018-06-01

As one of the important elements of controlling the redox system within the hyporheic and hypolentic zone, sulfur is involved in a series of complex biogeochemical processes such as carbon cycle, water acidification, formation of iron and manganese minerals, redox processes of trace metal elements and a series of important ecological processes. Previous studies on biogeochemistry of the hyporheic and hypolentic zones mostly concentrated on nutrients of nitrogen and phosphorus, heavy metals and other pollutants. Systematic study of biogeochemical behavior of sulfur and its main controlling factors within the lake hypolentic zone is very urgent and important. In this paper, a typical desert plateau lake, Dakebo Lake in northwestern China, was taken for example within which redox zonation and biogeochemical characteristics of sulfur affected by hydrodynamic conditions were studied based on not only traditional hydrochemical analysis, but also environmental isotope evidence. In the lake hypolentic zone of the study area, due to the different hydrodynamic conditions, vertical profile of sulfur species and environmental parameters differ at the two sites of the lake (western side and center). Reduction of sulfate, deposition and oxidation of sulfide, dissolution and precipitation of sulfur-bearing minerals occurred are responded well to Eh, dissolved oxygen, pH, organic carbon and microorganism according to which the lake hypolentic zone can be divided into reduced zone containing H 2 S, reduced zone containing no H 2 S, transition zone and oxidized zone. The results of this study provide valuable insights for understanding sulfur conversion processes and sulfur biogeochemical zonation within a lake hypolentic zone in an extreme plateau arid environment and for protecting the lake-wetland ecosystem in arid and semiarid regions.

[Sulfur dioxide limit standard and residues in Chinese medicinal materials].

PubMed

Kang, Chuan-Zhi; Yang, Wan-Zhen; Mo, Ge; Zhou, Li; Jiang, Jing-Yi; Lv, Chao-Geng; Wang, Sheng; Zhou, Tao; Yang, Ye; Guo, Lan-Ping

2018-01-01

The traditional sulfur fumigation processing method has been widely used in the initial processing and storage of traditional Chinese medicinal materials due to its economy, efficiency, convenience, high operability and effect on mold and insect prevention. However, excessive sulfur fumigation of traditional Chinese medicinal materials would lead to the changes in chemical compositions, and even endanger human health. This study showed that traditional Chinese medicinal materials were sulfur fumigated directly after being harvested for quick drying, or fumigated after being weted in the storage process for preventing mold and insects. We found that the sulfur dioxide limits for traditional Chinese medicinal materials were stricter than those for foods. Based on the existing limit standards, we obtained the data of sulfur dioxide residues for 35 types of traditional Chinese medicinal materials in a total of 862 batches. According to the limit standard in the Chinese Pharmacopoeia (150， 400 mg·kg⁻¹), the average over-standard rate of sulfur dioxide was as high as 52.43%, but it was reduced to 29.47% if calculated based on the limit for vegetable additive standard (500 mg·kg⁻¹). Sulfur fumigation issue shall be considered correctly: sulfur dioxide is a type of low toxic substance and less dangerous than aflatoxin and other highly toxic substances, and a small amount of residue would not increase the toxicity of traditional Chinese medicinal materials. However, sulfur fumigation might change the content of chemical substances and affect the quality of traditional Chinese medicinal materials. Furthermore, the exposure hazards of toxic substances are comprehensively correlated with exposure cycle, exposure frequency, and application method. In conclusion, it is suggested to strengthen the studies on the limit standard of traditional Chinese medicinal materials, formulate practical and feasible limit standard for sulfur dioxide residues in traditional Chinese medicinal materials that are consistent with the medication characteristics of traditional Chinese medicinal materials and can guarantee people's demand for safe medication. Copyright© by the Chinese Pharmaceutical Association.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deepmore » cycles at 0.1 C.« less

Installation Assessment of Frankford Arsenal.

DTIC Science & Technology

1977-10-01

sulfate , sulfuric acid , ac ’solution 40 Hot water bath 41 Nickel plate Nickel sulfate and chloride sulfuric acid , acid ...solution 42 Chromium Copper plate Copper sulfate and sulfuric acid , acid solution 11-14 TABLE 11-2 (continued) Tank No. Plating Process Use Contents...46 Water rinse Water 47 Water rinse Water 48 Water rinse Water 49 Acid Chromic acid , acetic acid , nickel sulfate and sulfuric

Optimization of Microporous Carbon Structures for Lithium-Sulfur Battery Applications in Carbonate-Based Electrolyte.

PubMed

Hu, Lei; Lu, Yue; Li, Xiaona; Liang, Jianwen; Huang, Tao; Zhu, Yongchun; Qian, Yitai

2017-03-01

Developing appropriate sulfur cathode materials in carbonate-based electrolyte is an important research subject for lithium-sulfur batteries. Although several microporous carbon materials as host for sulfur reveal the effect, methods for producing microporous carbon are neither easy nor well controllable. Moreover, due to the complexity and limitation of microporous carbon in their fabrication process, there has been rare investigation of influence on electrochemical behavior in the carbonate-based electrolyte for lithium-sulfur batteries by tuning different micropore size(0-2 nm) of carbon host. Here, we demonstrate an immediate carbonization process, self-activation strategy, which can produce microporous carbon for a sulfur host from alkali-complexes. Besides, by changing different alkali-ion in the previous complex, the obtained microporous carbon exhibits a major portion of ultramicropore (<0.7 nm, from 54.9% to 25.8%) and it is demonstrated that the micropore structure of the host material plays a vital role in confining sulfur molecule. When evaluated as cathode materials in a carbonate-based electrolyte for Li-S batteries, such microporous carbon/sulfur composite can provide high reversible capacity, cycling stability and good rate capability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Critical Look at the Combined Use of Sulfur and Oxygen Isotopes to Study Microbial Metabolisms in Methane-Rich Environments

PubMed Central

Antler, Gilad; Pellerin, André

2018-01-01

Separating the contributions of anaerobic oxidation of methane and organoclastic sulfate reduction in the overall sedimentary sulfur cycle of marine sediments has benefited from advances in isotope biogeochemistry. Particularly, the coupling of sulfur and oxygen isotopes measured in the residual sulfate pool (δ18OSO4 vs. δ34SSO4). Yet, some important questions remain. Recent works have observed patterns that are inconsistent with previous interpretations. We differentiate the contributions of oxygen and sulfur isotopes to separating the anaerobic oxidation of methane and organoclastic sulfate reduction into three phases; first evidence from conventional high methane vs. low methane sites suggests a clear relationship between oxygen and sulfur isotopes in porewater and the metabolic process taking place. Second, evidence from pure cultures and organic matter rich sites with low levels of methane suggest the signatures of both processes overlap and cannot be differentiated. Third, we take a critical look at the use of oxygen and sulfur isotopes to differentiate metabolic processes (anaerobic oxidation of methane vs. organoclastic sulfate reduction). We identify that it is essential to develop a better understanding of the oxygen kinetic isotope effect, the degree of isotope exchange with sulfur intermediates as well as establishing their relationships with the cell-specific metabolic rates if we are to develop this proxy into a reliable tool to study the sulfur cycle in marine sediments and the geological record. PMID:29681890

Organic Matter Polymerization by Disulfide Bonding Near the Chemocline in Cariaco Basin

NASA Astrophysics Data System (ADS)

Raven, M. R.; Adkins, J. F.; Sessions, A. L.

2013-12-01

The preservation of organic carbon in sediments as kerogen is an essential pathway in the global carbon cycle, but the chemical reactions involved in kerogen formation remain poorly understood. Previous researchers have found that many sediments deposited under euxinic conditions contain sulfur-bearing non-polar lipids as well as disulfide bonds among lipid and carbohydrate monomers. It remains unclear, however, when during organic matter decomposition and diagenesis these different sulfur-bearing structures form, and how different environmental conditions affect the extent of organic matter sulfurization. We investigate organic sulfurization processes armed with a technique for measuring the sulfur-isotopic compositions of individual organosulfur compounds by coupled gas chromatography - inductively coupled plasma mass spectrometry. Organic compounds were extracted from sediments and water column sediment traps from Cariaco Basin, a euxinic basin in the Caribbean Sea. We measured the sulfur-isotopic compositions of both non-polar lipids and of derivatized disulfide-bound compounds from eight sediment trap profiles and a six-meter-long sediment core. In Cariaco Basin, lipid sulfurization processes appear to begin near the chemocline and continue in sediments on timescales of thousands of years. Slow diagenetic sulfurization in sediments produces lipid monomers with sulfur atoms in ring structures that are 34S-depleted relative to coexisting dissolved sulfide. Lipid monomers become progressively enriched in 34S over time, indicating ongoing formation coinciding with an increase in the amount of total sulfur in bulk kerogen. One of the most abundant monomers observed in Cariaco sediments, a phytol-related thiophene, is also produced intermittently near the chemocline. Phytol thiophene δ34S values in sediment traps are similar to those observed in shallow Cariaco sediments except during occasional ';enrichment events,' when phytol thiophene δ34S values increase to as high as -2‰. In contrast, disulfide bonding appears to affect both lipids and carbohydrates and occur exclusively at the chemocline on very short timescales of days to weeks. In both the water column and the sediments, the sulfur isotope ratios of disulfide-bound monosaccharides are dramatically 34S-enriched relative to dissolved sulfide at the chemocline (~-30‰), ranging from -11‰ to +9‰. Disulfide-bound phytenes, which likely derive from the same precursor compounds as phytol thiophenes, were observed in only a few of the sediment trap extracts and have sulfur-isotopic compositions near +4.5‰. These 34S-enriched compositions indicate that the source of sulfur for rapid disulfide bonding may be an intermediate sulfur species that is not in isotopic equilibrium with dissolved sulfide. Significantly, δ34S values for disulfide-bound compounds in Cariaco Basin appear to be set at the chemocline and stable during subsequent diagenesis, opening the possibility that organic sulfur isotopes may archive information about environmental conditions at the chemocline in low-maturity sediments. Disulfide bonding does not, however, appear to be the major process driving slower diagenetic sulfur incorporation into kerogen. Compound-specific organic sulfur isotope analysis makes it possible to distinguish the products of different lipid and carbohydrate sulfurization processes for the first time.

Desulfurization of Coal in Fluidized Beds

NASA Technical Reports Server (NTRS)

Maddury, R.; Kalvinskas, J.

1985-01-01

Experimental dry chemical process for removing sulfur from coal-and thereby reducing harmful sulfur emissions from coal-fired electric powerplants-promises more economical and effective than older wet chemical processes. New process faster, requires smaller amounts of chemical reagents, and produces no liquid effluents, which poses disposal problem.

Sulfur barrier for use with in situ processes for treating formations

DOEpatents

Vinegar, Harold J [Bellaire, TX; Christensen, Del Scot [Friendswood, TX

2009-12-15

Methods for forming a barrier around at least a portion of a treatment area in a subsurface formation are described herein. Sulfur may be introduced into one or more wellbores located inside a perimeter of a treatment area in the formation having a permeability of at least 0.1 darcy. At least some of the sulfur is allowed to move towards portions of the formation cooler than the melting point of sulfur to solidify the sulfur in the formation to form the barrier.

Process for reducing sulfur in coal char

DOEpatents

Gasior, Stanley J.; Forney, Albert J.; Haynes, William P.; Kenny, Richard F.

1976-07-20

Coal is gasified in the presence of a small but effective amount of alkaline earth oxide, hydroxide or carbonate to yield a char fraction depleted in sulfur. Gases produced during the reaction are enriched in sulfur compounds and the alkaline earth compound remains in the char fraction as an alkaline earth oxide. The char is suitable for fuel use, as in a power plant, and during combustion of the char the alkaline earth oxide reacts with at least a portion of the sulfur oxides produced from the residual sulfur contained in the char to further lower the sulfur content of the combustion gases.

Coal desulfurization process

NASA Technical Reports Server (NTRS)

Hsu, G. C.; Gavalas, G. R.; Ganguli, P. S.; Kalfayan, S. H.

1978-01-01

A method for chlorinolysis of coal is an organic solvent at a moderate temperautre and atmospheric pressure has been proven to be effective in removing sulfur, particularly the organic sulfur, from coal. Chlorine gas is bubbled through a slurry of moist coal in chlorinated solvent. The chlorinated coal is separated, hydrolyzed and the dechlorinated. Preliminary results of treating a high sulfutr (4.77%S) bituminous coal show that up to 70% organic sulfur, 90% hyritic sulfur and 76% total sulfur can be removed. The treated coal is dechlorinated by heating at 500 C. The presence of moisture helps to remove organic sulfur.

High temperature desulfurization of synthesis gas

DOEpatents

Najjar, Mitri S.; Robin, Allen M.

1989-01-01

The hot process gas stream from the partial oxidation of sulfur-containing heavy liquid hydrocarbonaceous fuel and/or sulfur-containing solid carbonaceous fuel comprising gaseous mixtures of H.sub.2 +CO, sulfur-containing gases, entrained particulate carbon, and molten slag is passed through the unobstructed central passage of a radiant cooler where the temperature is reduced to a temperature in the range of about 1800.degree. F. to 1200.degree. F. From about 0 to 95 wt. % of the molten slag and/or entrained material may be removed from the hot process gas stream prior to the radiant cooler with substantially no reduction in temperature of the process gas stream. In the radiant cooler, after substantially all of the molten slag has solidified, the sulfur-containing gases are contacted with a calcium-containing material to produce calcium sulfide. A partially cooled stream of synthesis gas, reducing gas, or fuel gas containing entrained calcium sulfide particulate matter, particulate carbon, and solidified slag leaves the radiant cooler containing a greatly reduced amount of sulfur-containing gases.

The removal of sulfur dioxide from flue gases

PubMed Central

Kettner, Helmut

1965-01-01

The growth of industrialization makes it imperative to reduce the amounts of sulfur dioxide emitted into the atmosphere. This article describes various processes for cleaning flue gases, and gives details of new methods being investigated. Wet scrubbing with water, though widely practised, has many disadvantages. Scrubbing with zinc oxide, feasible in zinc works, is more satisfactory. Dry methods use a solid absorbent; they have the advantage of a high emission temperature. Other methods are based on the addition to the fuel or the flue gases of substances such as activated metal oxides, which react with the sulfur to form compounds less harmful than sulfur dioxide. Also being investigated are a two-stage combustion system, in which the sulfur dioxide is removed in the first stage, and the injection of activated powdered dolomite into burning fuel; the resulting sulfates being removed by electrostatic precipitation. A wet catalysis process has recently been developed. Most of the cleaning processes are not yet technically mature, but first results show good efficiency and relatively low cost. PMID:14315714

Phosphonium-based ionic liquids and their use in the capture of polluting gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Wang, Congmin; Luo, Huimin

2017-06-06

An ionic liquid composition having the following chemical structural formula: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from hydrocarbon groups containing at least 1 and up to 20 carbon atoms, and X.sup.- is a cyclic anion that possesses a negatively-charged group reactive with a gaseous electrophilic species, particularly carbon dioxide or sulfur dioxide. Methods for capturing a gaseous electrophilic species, such as CO.sub.2 or SO.sub.2, by contacting the gaseous electrophilic species with an ionic liquid according to Formula (1) are also described.

Transcriptional and Proteomic Profiling of Aspergillus flavipes in Response to Sulfur Starvation

PubMed Central

El-Sayed, Ashraf S. A.; Yassin, Marwa A.; Ali, Gul Shad

2015-01-01

Aspergillus flavipes has received considerable interest due to its potential to produce therapeutic enzymes involved in sulfur amino acid metabolism. In natural habitats, A. flavipes survives under sulfur limitations by mobilizing endogenous and exogenous sulfur to operate diverse cellular processes. Sulfur limitation affects virulence and pathogenicity, and modulates proteome of sulfur assimilating enzymes of several fungi. However, there are no previous reports aimed at exploring effects of sulfur limitation on the regulation of A. flavipes sulfur metabolism enzymes at the transcriptional, post-transcriptional and proteomic levels. In this report, we show that sulfur limitation affects morphological and physiological responses of A. flavipes. Transcription and enzymatic activities of several key sulfur metabolism genes, ATP-sulfurylase, sulfite reductase, methionine permease, cysteine synthase, cystathionine β- and γ-lyase, glutathione reductase and glutathione peroxidase were increased under sulfur starvation conditions. A 50 kDa protein band was strongly induced by sulfur starvation, and the proteomic analyses of this protein band using LC-MS/MS revealed similarity to many proteins involved in the sulfur metabolism pathway. PMID:26633307

Solid oxide fuel cell process and apparatus

DOEpatents

Cooper, Matthew Ellis [Morgantown, WV; Bayless, David J [Athens, OH; Trembly, Jason P [Durham, NC

2011-11-15

Conveying gas containing sulfur through a sulfur tolerant planar solid oxide fuel cell (PSOFC) stack for sulfur scrubbing, followed by conveying the gas through a non-sulfur tolerant PSOFC stack. The sulfur tolerant PSOFC stack utilizes anode materials, such as LSV, that selectively convert H.sub.2S present in the fuel stream to other non-poisoning sulfur compounds. The remaining balance of gases remaining in the completely or near H.sub.2S-free exhaust fuel stream is then used as the fuel for the conventional PSOFC stack that is downstream of the sulfur-tolerant PSOFC. A broad range of fuels such as gasified coal, natural gas and reformed hydrocarbons are used to produce electricity.

Diagenetic gypsum related to sulfur deposits in evaporites (Libros Gypsum, Miocene, NE Spain)

NASA Astrophysics Data System (ADS)

Ortí, Federico; Rosell, Laura; Anadón, Pere

2010-07-01

The Libros Gypsum is the thickest evaporite unit of the Miocene infill of the Teruel Basin in NE Spain. During the deposition of this unit, intense bacterial sulfate-reducing (BSR) activity in the lake depocenter generated a native sulfur deposit. Diagenetic gypsum resulted from subsequent sulfur oxidation. The different processes involved in these transformations were first investigated by Anadón et al. (1992). The present paper is concerned with this diagenetic gypsum from the stratigraphic, petrographic, isotopic and genetic points of view. Diagenetic gypsum occurs mainly as continuous or discontinuous layers, individual levels or lenses, irregular masses, nodules and micronodules, and veins. Its main textures are coarse-crystalline anhedral and fine-grained (alabastrine), both of which can replace any former lithology (carbonate, gypsum, and sulfur). The following sequence of processes and mineral/textural transformations is deduced: primary gypsum deposition — BSR and biodiagenetic carbonate/H 2S production — growth of native sulfur — growth of diagenetic gypsum — partial recrystallization of the diagenetic gypsum textures. The gypsification of the native sulfur generated two types of banded structures in the diagenetic gypsum: (1) concentric structures of centripetal growth, and (2) expansive, roughly concentric structures. In the first type, the gypsification operated from the outer boundaries towards the inner parts. In the second type, part of the carbonate hosting the sulfur was also gypsified (replaced/cemented). In the diagenetic gypsum, the δ34S values are in agreement with a native sulfur and H 2S provenance. The δ18O sulfate values, however, enable us to differentiate two main groups of values: one with positive values and the other with negative values. In the group of positive values, interstitial (evaporated) solutions participated in the sulfur oxidation; this process presumably occurred in a first oxidation stage during shallow-to-deeper burial of the Libros Gypsum unit. In the group of negative values, however, only meteoric waters participated in the oxidation, which presumably occurred in a second oxidation stage during the final exhumation of the unit. A third group of values is characterized by very high sulfur and oxygen values, suggesting that BSR residual solutions also participated in the oxidation processes locally. During the two oxidation stages, both the textural characteristics and the isotopic composition of the diagenetic gypsum indicate that gypsification operated as a multistadic process.

Geochemical and Mineralogical Analyses of Cold Spring Deposits at Borup Fiord Pass, a Sulfur-Dominated Arctic Analog for Planetary Environments on Mars and Europa

NASA Astrophysics Data System (ADS)

Lau, Graham Elliot

Sulfur is one of the most ubiquitous elements in the universe and one of those that is crucial for life, as we know it. This graduate dissertation presents the culmination of work conducted to better understand biological and geochemical processes related to sulfur cycling at a sulfur-dominated field site in the Canadian High Arctic. This site, situated in a valley called Borup Fiord Pass, provides a unique environment where sulfide-rich fluids emerge from a glacier and form large deposits of ice that become covered in elemental sulfur. The role of biology is compelling and yet challenging to define in each step of sulfur cycling at Borup Fiord pass, whether one considers the origin of the sulfide (presumed biological sulfate reduction in the subsurface) or one focuses on the processes driving sulfur oxidation and stabilization at the glacier's surface. This dissertation presents results from a field expedition in 2014 as well as detailed mineralogical and spectroscopic analyses of sulfur-rich materials returned from the field. The importance of sulfur and carbonate minerals at this site is considered. Also, analyses of materials within pyrite alteration features in the valley are explored. These features appear to represent emplaced subsurface sulfide ores, which have been subsequently leached near the surface, forming gossanous structures. The geochemistry and mineralogy of these features is explored, as well as is their potential to serve as analogs for the exploration of Mars. The dissertation then concludes with some consideration of potential future work to be considered as well as a recapitulation of the current state of knowledge of processes at Borup Fiord Pass.

Design rules of heteroatom-doped graphene to achieve high performance lithium-sulfur batteries: Both strong anchoring and catalysing based on first principles calculation.

PubMed

Zhang, Lin; Liang, Pei; Shu, Hai B; Man, Xiao L; Du, Xiao Q; Chao, Dong L; Liu, Zu G; Sun, Yu P; Wan, Hou Z; Wang, Hao

2018-06-18

A number of observations have been reported on chemical capture and catalysis of anchoring materials for lithium-sulfur batteries. Here, we propose the design principles for the chemical functioned graphene as an anchor material to realize both strong chemical trapping and catalysis. Through the first principle, the periodic law is calculated from the theory. Seven different co-doping series were investigated, e.g. MN 4 @graphene (M = V, Cr, Mn, Fe, Co, Ni, and Cu). From binding energy, partial density of state, and charge density difference analysis, the FeN 4 and CrN 4 co-doped graphene show good performance for the lithium-sulfur battery from both strong anchoring and catalytic effects. For the most kinds of Li 2 S x (x = 1, 2, 4, 6, 8) absorption, two combinations can be achieved, including S-bonding and Li-bonding. The competition between the MS and the NLi shows the main difference of the co-doped configurations. Moreover, the S-bonding systems have better performance for both moderate chemical trapping and strong catalysis. The binding energies of Li 2 S x and Li decomposed properties considered as the key descriptors for the rational design of lithium-sulfur battery. Lastly, we offer design rules for high performance lithium-sulfur batteries based on the chemical functional graphene materials. Copyright © 2018 Elsevier Inc. All rights reserved.

Microscale sulfur cycling in the phototrophic pink berry consortia of the Sippewissett Salt Marsh

PubMed Central

Wilbanks, Elizabeth G; Jaekel, Ulrike; Salman, Verena; Humphrey, Parris T; Eisen, Jonathan A; Facciotti, Marc T; Buckley, Daniel H; Zinder, Stephen H; Druschel, Gregory K; Fike, David A; Orphan, Victoria J

2014-01-01

Microbial metabolism is the engine that drives global biogeochemical cycles, yet many key transformations are carried out by microbial consortia over short spatiotemporal scales that elude detection by traditional analytical approaches. We investigate syntrophic sulfur cycling in the ‘pink berry’ consortia of the Sippewissett Salt Marsh through an integrative study at the microbial scale. The pink berries are macroscopic, photosynthetic microbial aggregates composed primarily of two closely associated species: sulfide-oxidizing purple sulfur bacteria (PB-PSB1) and sulfate-reducing bacteria (PB-SRB1). Using metagenomic sequencing and 34S-enriched sulfate stable isotope probing coupled with nanoSIMS, we demonstrate interspecies transfer of reduced sulfur metabolites from PB-SRB1 to PB-PSB1. The pink berries catalyse net sulfide oxidation and maintain internal sulfide concentrations of 0–500 μm. Sulfide within the berries, captured on silver wires and analysed using secondary ion mass spectrometer, increased in abundance towards the berry interior, while δ34S-sulfide decreased from 6‰ to −31‰ from the exterior to interior of the berry. These values correspond to sulfate–sulfide isotopic fractionations (15–53‰) consistent with either sulfate reduction or a mixture of reductive and oxidative metabolisms. Together this combined metagenomic and high-resolution isotopic analysis demonstrates active sulfur cycling at the microscale within well-structured macroscopic consortia consisting of sulfide-oxidizing anoxygenic phototrophs and sulfate-reducing bacteria. PMID:24428801

Fluorine-Induced Chemiluminescence Detection of Biologically Methylated Tellurium, Selenium, and Sulfur Compounds and Methyldithiocarbhydrazide as a Formaldehyde Derivatization Reagent

NASA Astrophysics Data System (ADS)

Chasteen, Thomas Girard

1990-01-01

The first part of this dissertation describes capillary chromatography coupled to a fluorine-induced chemiluminescence detector as a sensitive method by which biologically methylated metalloids can be determined in the presence of high concentrations of potentially interfering molecules. With a wide linear range and excellent sensitivity, this method was applied to the detection of dimethyl selenide (DMSe), dimethyl diselenide (DMDSe), and dimethyl telluride (DMTe), often found in biological environments in the presence of interfering methylated sulfur gases, such as methanethiol, dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide. Detection limits for DMSe, DMDSe, and DMTe were 30, 9, and 7 picograms, respectively. This DMTe detection limit is the lowest reported to date for a volatile tellurium gas. A variety of selenium-resistant bacteria emitted mixtures of methylated sulfur/selenium gases when dosed with inorganic selenium salts in the presence of sulfur containing growth media. One of the gases detected was dimethyl selenenyl sulfide, CH_3SeSCH _3, reported here for the first time in headspace above microorganisms. In addition, this detector responded to reduced phosphorus compounds such as phosphine. The detection limit for this compound was 2.8 picograms. Detection limits for alkylated phosphines trimethyl and triethyl phosphine were 0.5 and 17 picograms respectively, based on the relative response of these compounds compared to dimethyl sulfide. This method can be used for the simultaneous determination of methylated sulfur, selenium, tellurium compounds found in biological systems. Part II of this dissertation describes work with methyldithiocarbhydrazide, a compound that has been synthesized for use as a derivatization reagent to capture formaldehyde in the gas phase. Chosen for its ability to react in a manner similar to 2,4-dinitrophenylhydrazine, this molecule was selected based on two structural characteristics: a hydrazine tag to react with and thereby capture carbonyls and a methyl sulfide group to allow for sensitive detection by fluorine-induced chemiluminescence. Although in the final analysis methyldithiocarbohydrazide failed as a successful means by which formaldehyde can be determined using gas chromatography in conjunction with fluorine-induced chemiluminescence, it did successfully derivatize formaldehyde in both solution and the gas phase without the need for low pH conditions.

The shadow price of substitutable sulfur in the US electric power plant: a distance function approach.

PubMed

Lee, Myunghun

2005-10-01

Given restrictions on sulfur dioxide emissions, a feasible long-run response could involve either an investment in improving boiler fuel-efficiency or a shift to a production process that is effective in removing sulfur dioxide. To allow for the possibility of substitution between sulfur and productive capital, we measure the shadow price of sulfur dioxide as the opportunity cost of lowering sulfur emissions in terms of forgone capital. The input distance function is estimated with data from 51 coal-fired US power units operating between 1977 and 1986. The indirect Morishima elasticities of substitution indicate that the substitutability of capital for sulfur is relatively high. The overall weighted average estimate of the shadow price of sulfur is -0.076 dollars per pound in constant 1976 dollars.

Fossilization of melanosomes via sulfurization.

PubMed

McNamara, Maria E; van Dongen, Bart E; Lockyer, Nick P; Bull, Ian D; Orr, Patrick J

2016-05-01

Fossil melanin granules (melanosomes) are an important resource for inferring the evolutionary history of colour and its functions in animals. The taphonomy of melanin and melanosomes, however, is incompletely understood. In particular, the chemical processes responsible for melanosome preservation have not been investigated. As a result, the origins of sulfur-bearing compounds in fossil melanosomes are difficult to resolve. This has implications for interpretations of original colour in fossils based on potential sulfur-rich phaeomelanosomes. Here we use pyrolysis gas chromatography mass spectrometry (Py-GCMS), fourier transform infrared spectroscopy (FTIR) and time of flight secondary ion mass spectrometry (ToF-SIMS) to assess the mode of preservation of fossil microstructures, confirmed as melanosomes based on the presence of melanin, preserved in frogs from the Late Miocene Libros biota (NE Spain). Our results reveal a high abundance of organosulfur compounds and non-sulfurized fatty acid methyl esters in both the fossil tissues and host sediment; chemical signatures in the fossil tissues are inconsistent with preservation of phaeomelanin. Our results reflect preservation via the diagenetic incorporation of sulfur, i.e. sulfurization (natural vulcanization), and other polymerization processes. Organosulfur compounds and/or elevated concentrations of sulfur have been reported from melanosomes preserved in various invertebrate and vertebrate fossils and depositional settings, suggesting that preservation through sulfurization is likely to be widespread. Future studies of sulfur-rich fossil melanosomes require that the geochemistry of the host sediment is tested for evidence of sulfurization in order to constrain interpretations of potential phaeomelanosomes and thus of original integumentary colour in fossils.

Elemental sulfur in Eddy County, New Mexico

USGS Publications Warehouse

Hinds, Jim S.; Cunningham, Richard R.

1970-01-01

Sulfur has been reported in Eddy County, N. Mex., in rocks ranging from Silurian to Holocene in age at depths of 0-15,020 feet. Targets of present exploration are Permian formations in the Delaware Basin and northwest shelf areas at depths of less than 4,000 feet. Most of the reported sulfur occurrences in the shelf area are in the 'Abo' (as used by some subsurface geologists), Yeso, and San Andres Formations and the Artesia Group. Sulfur deposition in the dense dolomites of the 'Abo,' Yeso, and San Andres Formations is attributed to the reduction of ionic sulfate by hydrogen sulfide in formation waters in zones of preexisting porosity and permeability. A similar origin accounts for most of the sulfur deposits in the formations of the Artesia Group, but some of the sulfur in these formations may have originated in place through the alteration of anhydrite to carbonate and sulfur by the metabolic processes of bacteria in the presence of hydrocarbons. Exploration in the Delaware Basin area is directed primarily toward the Castile Formation. Sulfur deposits in the Castile Formation are found in irregular masses of cavernous brecciated secondary carbonate rock enveloped by impermeable anhydrite. The carbonate masses, or 'castiles,' probably originated as collapse features resulting from subsurface solution and upward stopping. Formation of carbonate rock and sulfur in the castiles is attributed to the reduction of brecciated anhydrite by bacteria and hydrocarbons in the same process ascribed to the formation of carbonate and sulfur in the caprocks of salt domes.

Speciation of sulfur from filamentous microbial mats from sulfidic cave springs using X-ray absorption near-edge spectroscopy.

PubMed

Engel, Annette Summers; Lichtenberg, Henning; Prange, Alexander; Hormes, Josef

2007-04-01

Most transformations within the sulfur cycle are controlled by the biosphere, and deciphering the abiotic and biotic nature and turnover of sulfur is critical to understand the geochemical and ecological changes that have occurred throughout the Earth's history. Here, synchrotron radiation-based sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to examine sulfur speciation in natural microbial mats from two aphotic (cave) settings. Habitat geochemistry, microbial community compositions, and sulfur isotope systematics were also evaluated. Microorganisms associated with sulfur metabolism dominated the mats, including members of the Epsilonproteobacteria and Gammaproteobacteria. These groups have not been examined previously by sulfur K-edge XANES. All of the mats consisted of elemental sulfur, with greater contributions of cyclo-octasulfur (S8) compared with polymeric sulfur (Smicro). While this could be a biological fingerprint for some bacteria, the signature may also indicate preferential oxidation of Smicro and S8 accumulation. Higher sulfate content correlated to less S8 in the presence of Epsilonproteobacteria. Sulfur isotope compositions confirmed that sulfur content and sulfur speciation may not correlate to microbial metabolic processes in natural samples, thereby complicating the interpretation of modern and ancient sulfur records.

Process for removal of sulfur compounds from fuel gases

DOEpatents

Moore, Raymond H.; Stegen, Gary E.

1978-01-01

Fuel gases such as those produced in the gasification of coal are stripped of sulfur compounds and particulate matter by contact with molten metal salt. The fuel gas and salt are intimately mixed by passage through a venturi or other constriction in which the fuel gas entrains the molten salt as dispersed droplets to a gas-liquid separator. The separated molten salt is divided into a major and a minor flow portion with the minor flow portion passing on to a regenerator in which it is contacted with steam and carbon dioxide as strip gas to remove sulfur compounds. The strip gas is further processed to recover sulfur. The depleted, minor flow portion of salt is passed again into contact with the fuel gas for further sulfur removal from the gas. The sulfur depleted, fuel gas then flows through a solid absorbent for removal of salt droplets. The minor flow portion of the molten salt is then recombined with the major flow portion for feed to the venturi.

Scandium recovery from slags after oxidized nickel ore processing

NASA Astrophysics Data System (ADS)

Smyshlyaev, Denis; Botalov, Maxim; Bunkov, Grigory; Rychkov, Vladimir; Kirillov, Evgeny; Kirillov, Sergey; Semenishchev, Vladimir

2017-09-01

One of the possible sources of scandium production - waste (slags) from processing of oxidized nickel ores, has been considered in present research work. The hydrometallurgical method has been selected as the primary for scandium extraction. Different reagents for leaching of scandium, such as sulfuric acid, various carbonate salts and fluorides, have been tested. Sulfuric acid has been recognized as an optimal leaching reagent. Sulfuric acid concentration of 100 g L-1 allowed recovering up to 97 % of scandium.

Process for recovery of hydrogen and

DOEpatents

James, Brian R.; Li-Lee, Chung; Lilga, Michael A.; Nelson, David A.

1987-01-01

on of sulfur Abstract A process of abstracting sulfur from H.sub.2 S and generating hydrogen is disclosed comprising dissolving Pd.sub.2 X.sub.2 (.mu.-dppm).sub.2 in a solvent and then introducing H.sub.2 S. The palladium complex abstracts sulfur, forming hydrogen and a (.mu.-S) complex. The (.mu.-S) complex is readily oxidizable to a (.mu.-SO.sub.2) adduct which spontaneously loses SO.sub.2 and regenerates the palladium complex.

Process for purifying geothermal steam

DOEpatents

Li, Charles T.

1980-01-01

Steam containing hydrogen sulfide is purified and sulfur recovered by passing the steam through a reactor packed with activated carbon in the presence of a stoichiometric amount of oxygen which oxidizes the hydrogen sulfide to elemental sulfur which is adsorbed on the bed. The carbon can be recycled after the sulfur has been recovered by vacuum distillation, inert gas entrainment or solvent extraction. The process is suitable for the purification of steam from geothermal sources which may also contain other noncondensable gases.

Process for purifying geothermal steam

DOEpatents

Li, C.T.

Steam containing hydrogen sulfide is purified and sulfur recovered by passing the steam through a reactor packed with activated carbon in the presence of a stoichiometric amount of oxygen which oxidizes the hydrogen sulfide to elemental sulfur which is adsorbed on the bed. The carbon can be recycled after the sulfur has been recovered by vacuum distillation, inert gas entrainment or solvent extraction. The process is suitable for the purification of steam from geothermal sources which may also contain other noncondensable gases.

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2013-12-01

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable. Electronic supplementary information (ESI) available: Preparation process scheme; X-ray mapping images and EDX analysis for the surface of PMC/S-40; X-ray mapping images for the cross-section of PMC/S-40; thermogravimetric analysis (TGA) of PMC/S samples; T-plot results for PMC sample; and electrochemical measurements of lithium-sulfur batteries using PMC/S as cathode materials. See DOI: 10.1039/c3nr04532c

Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece

PubMed Central

2014-01-01

Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ34S value of H2S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H2S-rich hydrothermal fluids and oxic, sulfate-rich seawater. PMID:25183951

Warm Cleanup of Coal-Derived Syngas: Multicontaminant Removal Process Demonstration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spies, Kurt A.; Rainbolt, James E.; Li, Xiaohong S.

Warm cleanup of coal- or biomass-derived syngas requires sorbent and catalytic beds to protect downstream processes and catalysts from fouling. Sulfur is particularly harmful because even parts-per-million amounts are sufficient to poison downstream synthesis catalysts. Zinc oxide (ZnO) is a conventional sorbent for sulfur removal; however, its operational performance using real gasifier-derived syngas and in an integrated warm cleanup process is not well reported. In this paper, we report the optimal temperature for bulk desulfurization to be 450oC, while removal of sulfur to parts-per-billion levels requires a lower temperature of approximately 350oC. Under these conditions, we found that sulfur inmore » the form of both hydrogen sulfide and carbonyl sulfide could be absorbed equally well using ZnO. For long-term operation, sorbent regeneration is desirable to minimize process costs. Over the course of five sulfidation and regeneration cycles, a ZnO bed lost about a third of its initial sulfur capacity, however sorbent capacity stabilized. Here, we also demonstrate, at the bench-scale, a process and materials used for warm cleanup of coal-derived syngas using five operations: 1) Na2CO3 for HCl removal, 2) regenerable ZnO beds for bulk sulfur removal, 3) a second ZnO bed for trace sulfur removal, 4) a Ni-Cu/C sorbent for multi-contaminant inorganic removal, and 5) a Ir-Ni/MgAl2O4 catalyst employed for ammonia decomposition and tar and light hydrocarbon steam reforming. Syngas cleanup was demonstrated through successful long-term performance of a poison-sensitive, Cu-based, water-gas-shift catalyst placed downstream of the cleanup process train. The tar reformer is an important and necessary operation with this particular gasification system; its inclusion was the difference between deactivating the water-gas catalyst with carbon deposition and successful 100-hour testing using 1 LPM of coal-derived syngas.« less

Metatranscriptomic analysis of a high-sulfide aquatic spring reveals insights into sulfur cycling and unexpected aerobic metabolism

PubMed Central

Elshahed, Mostafa S.; Najar, Fares Z.; Krumholz, Lee R.

2015-01-01

Zodletone spring is a sulfide-rich spring in southwestern Oklahoma characterized by shallow, microoxic, light-exposed spring water overlaying anoxic sediments. Previously, culture-independent 16S rRNA gene based diversity surveys have revealed that Zodletone spring source sediments harbor a highly diverse microbial community, with multiple lineages putatively involved in various sulfur-cycling processes. Here, we conducted a metatranscriptomic survey of microbial populations in Zodletone spring source sediments to characterize the relative prevalence and importance of putative phototrophic, chemolithotrophic, and heterotrophic microorganisms in the sulfur cycle, the identity of lineages actively involved in various sulfur cycling processes, and the interaction between sulfur cycling and other geochemical processes at the spring source. Sediment samples at the spring’s source were taken at three different times within a 24-h period for geochemical analyses and RNA sequencing. In depth mining of datasets for sulfur cycling transcripts revealed major sulfur cycling pathways and taxa involved, including an unexpected potential role of Actinobacteria in sulfide oxidation and thiosulfate transformation. Surprisingly, transcripts coding for the cyanobacterial Photosystem II D1 protein, methane monooxygenase, and terminal cytochrome oxidases were encountered, indicating that genes for oxygen production and aerobic modes of metabolism are actively being transcribed, despite below-detectable levels (<1 µM) of oxygen in source sediment. Results highlight transcripts involved in sulfur, methane, and oxygen cycles, propose that oxygenic photosynthesis could support aerobic methane and sulfide oxidation in anoxic sediments exposed to sunlight, and provide a viewpoint of microbial metabolic lifestyles under conditions similar to those seen during late Archaean and Proterozoic eons. PMID:26417542

Metatranscriptomic analysis of a high-sulfide aquatic spring reveals insights into sulfur cycling and unexpected aerobic metabolism.

PubMed

Spain, Anne M; Elshahed, Mostafa S; Najar, Fares Z; Krumholz, Lee R

2015-01-01

Zodletone spring is a sulfide-rich spring in southwestern Oklahoma characterized by shallow, microoxic, light-exposed spring water overlaying anoxic sediments. Previously, culture-independent 16S rRNA gene based diversity surveys have revealed that Zodletone spring source sediments harbor a highly diverse microbial community, with multiple lineages putatively involved in various sulfur-cycling processes. Here, we conducted a metatranscriptomic survey of microbial populations in Zodletone spring source sediments to characterize the relative prevalence and importance of putative phototrophic, chemolithotrophic, and heterotrophic microorganisms in the sulfur cycle, the identity of lineages actively involved in various sulfur cycling processes, and the interaction between sulfur cycling and other geochemical processes at the spring source. Sediment samples at the spring's source were taken at three different times within a 24-h period for geochemical analyses and RNA sequencing. In depth mining of datasets for sulfur cycling transcripts revealed major sulfur cycling pathways and taxa involved, including an unexpected potential role of Actinobacteria in sulfide oxidation and thiosulfate transformation. Surprisingly, transcripts coding for the cyanobacterial Photosystem II D1 protein, methane monooxygenase, and terminal cytochrome oxidases were encountered, indicating that genes for oxygen production and aerobic modes of metabolism are actively being transcribed, despite below-detectable levels (<1 µM) of oxygen in source sediment. Results highlight transcripts involved in sulfur, methane, and oxygen cycles, propose that oxygenic photosynthesis could support aerobic methane and sulfide oxidation in anoxic sediments exposed to sunlight, and provide a viewpoint of microbial metabolic lifestyles under conditions similar to those seen during late Archaean and Proterozoic eons.

Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur.

PubMed

Zhang, Linji; Ren, Yang; Liu, Xiuru; Han, Fei; Evans-Lutterodt, Kenneth; Wang, Hongyan; He, Yali; Wang, Junlong; Zhao, Yong; Yang, Wenge

2018-03-14

Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the well-known λ-transition process. This discovery offers a new perspective on amorphous sulfur's structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.

Tandem sulfur chemiluminescence and flame ionization detection with planar microfluidic devices for the characterization of sulfur compounds in hydrocarbon matrices.

PubMed

Luong, J; Gras, R; Shellie, R A; Cortes, H J

2013-07-05

The detection of sulfur compounds in different hydrocarbon matrices, from light hydrocarbon feedstocks to medium synthetic crude oil feeds provides meaningful information for optimization of refining processes as well as demonstration of compliance with petroleum product specifications. With the incorporation of planar microfluidic devices in a novel chromatographic configuration, sulfur compounds from hydrogen sulfide to alkyl dibenzothiophenes and heavier distributions of sulfur compounds over a wide range of matrices spanning across a boiling point range of more than 650°C can be characterized, using one single analytical configuration in less than 25min. In tandem with a sulfur chemiluminescence detector for sulfur analysis is a flame ionization detector. The flame ionization detector can be used to establish the boiling point range of the sulfur compounds in various hydrocarbon fractions for elemental specific simulated distillation analysis as well as profiling the hydrocarbon matrices for process optimization. Repeatability of less than 3% RSD (n=20) over a range of 0.5-1000 parts per million (v/v) was obtained with a limit of detection of 50 parts per billion and a linear range of 0.5-1000 parts per million with a correlation co-efficient of 0.998. Copyright © 2013 Elsevier B.V. All rights reserved.

[Characteristics of odors and VOCs from sludge direct drying process].

PubMed

Chen, Wen-He; Deng, Ming-Jia; Luo, Hui; Zhang, Jing-Ying; Ding, Wen-Jie; Liu, Jun-Xin; Liu, Jun-Xin

2014-08-01

Co-processing sewage sludge by using the high-temperature feature of cement kiln can realize harmless disposal and energy recycling. In this paper, investigation on characteristics of the flue gas from sludge drying process was carried out in Guangzhou Heidelberg Yuexiu Cement Co., LTD. The composition and the main source of odors and volatile organic compounds (VOCs) emitted during the drying process were analyzed, aimed to provide scientific basis for the treatment of sewage sludge. Results showed that there were a large number of malodorous substances and VOCs in the flue gas. Sulfur dioxide and other sulfur-containing compounds were the main components in the malodorous substances, while benzene derivatives were predominant in VOCs. The compositions of odors and VOCs were influenced by the characteristics of the sludge and the heat medium (kiln tail gas). Total organic compounds in the sludge were significantly decreased after drying. Other organic substances such as volatile fatty acid, protein, and polysaccharide were also obviously reduced. The organic matter in sludge was the main source of VOCs in the flue gas. Part of sulfurous substances, such as sulfur dioxide, carbon disulfide, were from sulfur-containing substances in the sludge, and the rest were from the kiln tail gas itself.

SIMULTANEOUS DESTRUCTION OF ORGANICS AND STABILIZATION OF METALS IN SOILS

EPA Science Inventory

The Sulchem Process reacts the material being treated with elemental sulfur at elevated temperatures in an inert reactor system. Organic hydrocarbons react with the sulfur to form an inert fine solid of carbon and sulfur, hydrogen sulfide gas, and modest amounts of carbon disulfi...

Investigating secondary aerosol formation from agricultural amines and reduced sulfur compounds

USDA-ARS?s Scientific Manuscript database

Gas phase amines and reduced sulfur compounds are often co-emitted from agricultural processes. Amines have been recently recognized as potentially major sources of agricultural aerosol formation, while the reduced sulfur compounds are largely ignored. There is a severe lack of knowledge and under...

Investigating Sulfur as a Biosignature and Indicator of Habitability at an Arctic Analog to Europa

NASA Astrophysics Data System (ADS)

Gleeson, D. F.; Anderson, M. S.; Pappalardo, R. T.; Wright, K. W.; Templeton, A. S.

2010-03-01

Sulfur-rich materials on the icy surface of Europa have the potential to contain biosignatures representative of processes occurring within the ice shell or ocean. We explore the biogenicity of sulfur minerals from the surface of an Arctic glacier.

Study on mechanisms of different sulfuric acid leaching technologies of chromite

NASA Astrophysics Data System (ADS)

Shi, Pei-yang; Liu, Cheng-jun; Zhao, Qing; Shi, Hao-nan

2017-09-01

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.

The global sulfur cycle

NASA Technical Reports Server (NTRS)

Sagan, D. (Editor)

1985-01-01

The results of the planetary biology microbial ecology's 1984 Summer Research Program, which examined various aspects of the global sulfur cycle are summarized. Ways in which sulfur flows through the many living and chemical species that inhabit the surface of the Earth were investigated. Major topics studied include: (1) sulfur cycling and metabolism of phototropic and filamentous sulfur bacteria; (2) sulfur reduction in sediments of marine and evaporite environments; (3) recent cyanobacterial mats; (4) microanalysis of community metabolism in proximity to the photic zone in potential stromatolites; and (5) formation and activity of microbial biofilms on metal sulfides and other mineral surfaces. Relationships between the global sulfur cycle and the understanding of the early evolution of the Earth and biosphere and current processes that affect global habitability are stressed.

Removal of Sulfur from CaF2 Containing Desulfurization Slag Exhausted from Secondary Steelmaking Process by Oxidation

NASA Astrophysics Data System (ADS)

Hiraki, Takehito; Kobayashi, Junichi; Urushibata, Satomi; Matsubae, Kazuyo; Nagasaka, Tetsuya

2012-08-01

The oxidation behavior of sulfur in desulfurization slag generated from the secondary steelmaking process with air has been investigated in the temperature range of 973 K to 1373 K (700 °C to 1100 °C). Although a high removal rate of sulfur is not achieved at temperatures lower than 1273 K (1000 °C) because of the formation of CaSO4, most of the sulfur is rapidly removed from slag as SO2 gas in the 1273 K to 1373 K (700 °C to 1100 °C) range. This finding indicates that the desulfurization slag generated from the secondary steelmaking process can be reused as a desulfurized flux through air oxidation, making it possible to reduce significantly the amount of desulfurization slag for disposal.

Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream

DOEpatents

Chang, Shih-Ger; Li, Yang; Zhao, Xinglei

2014-07-08

The present invention provides a system for capturing CO.sub.2 and/or SO.sub.2, comprising: (a) a CO.sub.2 and/or SO.sub.2 absorber comprising an amine and/or amino acid salt capable of absorbing the CO.sub.2 and/or SO.sub.2 to produce a CO.sub.2- and/or SO.sub.2-containing solution; (b) an amine regenerator to regenerate the amine and/or amino acid salt; and, when the system captures CO.sub.2, (c) an alkali metal carbonate regenerator comprising an ammonium catalyst capable catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO.sub.2 gas. The present invention also provides for a system for capturing SO.sub.2, comprising: (a) a SO.sub.2 absorber comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO.sub.2 to produce an alkali metal sulfite/sulfate precipitate and CO.sub.2.

Sulfur tolerant hydrophobic ionic liquid solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luebke, David; Nulwala, Hunaid; Kail, Brian

Exemplary embodiments relate to methods for removal of CO.sub.2 and other acid gases from gaseous fuels prior to combustion. Exemplary methods may be used for CO.sub.2 capture, H.sub.2 purification and natural gas sweetening. Exemplary methods use at least one ionic liquid that has excellent CO.sub.2 solubility, selectivity over hydrogen, low viscosity, and resistance to H.sub.2S.

Using biological and physico-chemical test methods to assess the role of concrete mixture design in resistance to microbially induced corrosion

NASA Astrophysics Data System (ADS)

House, Mitchell Wayne

Concrete is the most widely used material for construction of wastewater collection, storage, and treatment infrastructure. The chemical and physical characteristics of hydrated portland cement make it susceptible to degradation under highly acidic conditions. As a result, some concrete wastewater infrastructure may be susceptible to a multi-stage degradation process known as microbially induced corrosion, or MIC. MIC begins with the production of aqueous hydrogen sulfide (H2S(aq)) by anaerobic sulfate reducing bacteria present below the waterline. H2S(aq) partitions to the gas phase where it is oxidized to sulfuric acid by the aerobic sulfur oxidizing bacteria Thiobacillus that resides on concrete surfaces above the waterline. Sulfuric acid then attacks the cement paste portion of the concrete matrix through decalcification of calcium hydroxide and calcium silica hydrate coupled with the formation of expansive corrosion products. The attack proceeds inward resulting in reduced service life and potential failure of the concrete structure. There are several challenges associated with assessing a concrete's susceptibility to MIC. First, no standard laboratory tests exist to assess concrete resistance to MIC. Straightforward reproduction of MIC in the laboratory is complicated by the use of microorganisms and hydrogen sulfide gas. Physico-chemical tests simulating MIC by immersing concrete specimens in sulfuric acid offer a convenient alternative, but do not accurately capture the damage mechanisms associated with biological corrosion. Comparison of results between research studies is difficult due to discrepancies that can arise in experimental methods even if current ASTM standards are followed. This thesis presents two experimental methods to evaluate concrete resistance to MIC: one biological and one physico-chemical. Efforts are made to address the critical aspects of each testing method currently absent in the literature. The first method presented is a new test to evaluate performance of concrete specimens under conditions designed to accelerate MIC. Concrete specimens representing 12 mixture designs were inoculated with 5 species of Thiobacillus bacteria and placed in a biological growth chamber designed to encourage bacterial growth and sulfuric acid production by optimizing temperature, delivering necessary nutrients, and providing hydrogen sulfide gas. Results indicate that using supplementary cementitious materials, limestone aggregates, and sulfate resistant cement can improve resistance to MIC. It is interesting to note that this study showed that unlike many other durability problems the role of water to cement ratio was unclear. The second method presented is a sulfuric acid immersion study designed to evaluate the resistance of 12 concrete mixture designs to 5 concentrations of sulfuric acid. Experimental protocols (like those in ASTM) previously considered trivial were found to have a dramatic effect on experimental results. It was found that using supplementary cementitious materials, limestone coarse aggregate, and sulfate resistant cement can increase concrete resistance to moderate sulfuric acid concentrations. The primary damage mechanism was observed to change depending on sulfuric acid concentration. Rapid deterioration of specimens exposed to aggressive sulfuric acid solutions indicates that degradation of concrete under the most severe MIC conditions (i.e., a pH < 1.0) cannot be prevented by strictly manipulating concrete mixture proportions. A holistic approach is needed for these situations that considers environmental conditions as well.

EMERGING TECHNOLOGY SUMMARY - SIMULTANEOUS DESTRUCTION OF ORGANICS AND STABILIZATION OF METALS IN SOILS

EPA Science Inventory

The Sulchem Process reacts the material being treated with elemental sulfur at elevated temperatures in an inert reactor system. Organic hydrocarbons react with the sulfur to form an inert fine solid of carbon and sulfur, hydrogen sulfide gas, and modest amounts of carbon disulfi...

Large sulfur isotope fractionations in Martian sediments at Gale crater

NASA Astrophysics Data System (ADS)

Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

2017-09-01

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

PubMed Central

Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

2012-01-01

The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

Effects of sulfurization time and H{sub 2}S concentration on electrical properties of Cu{sub 2}ZnSnS{sub 4} films prepared by sol–gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Bo; Cheng, Shuying, E-mail: sycheng@fzu.edu.cn; Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou 213164

2016-01-15

Highlights: • Cu{sub 2}ZnSnS{sub 4} (CZTS) films were prepared by sol–gel method following sulfurization. • The sulfurization time and H{sub 2}S concentration have the effects on the electrical properties. • The tin loss is increased with the increasing of the sulfurization time. • The secondary phases like ZnS make the electrical properties worse. • The CZTS films sulfurized at 5% H{sub 2}S for 90 min had the best electrical properties. - Abstract: Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films have been successfully deposited by a sol–gel method and sulfurization process. The properties of the films were investigated by varying sulfurization timemore » and H{sub 2}S concentration. X-ray diffraction and Raman spectra analyses revealed the formation of CZTS films with a tetragonal type kesterite structure. With increasing the sulfurization time and H{sub 2}S concentration, the intensity of the kesterite (1 1 2) peak became sharper. The stoichiometric ratios of the CZTS films were different from the precursors, which was due to Sn loss during the sulfurization process. The electrical resistivity and mobility of the films increased while the carrier concentration decreased with increasing the sulfurization time. The CZTS thin films sulfurized at 5% H{sub 2}S concentration for 90 min had the best opto-electrical properties with E{sub g} of 1.41 eV, resistivity of 3.64 Ω cm, carrier concentration of 1.11 × 10{sup 18} cm{sup −3} and mobility of 1.54 cm{sup 2}/(V s) at room temperature for PV application.« less

Quantitative Phase Fraction Detection in Organic Photovoltaic Materials through EELS Imaging

DOE PAGES

Dyck, Ondrej; Hu, Sheng; Das, Sanjib; ...

2015-11-24

Organic photovoltaic materials have recently seen intense interest from the research community. Improvements in device performance are occurring at an impressive rate; however, visualization of the active layer phase separation still remains a challenge. Our paper outlines the application of two electron energy-loss spectroscopic (EELS) imaging techniques that can complement and enhance current phase detection techniques. Specifically, the bulk plasmon peak position, often used to produce contrast between phases in energy filtered transmission electron microscopy (EFTEM), is quantitatively mapped across a sample cross section. One complementary spectrum image capturing the carbon and sulfur core loss edges is compared with themore » plasmon peak map and found to agree quite well, indicating that carbon and sulfur density differences between the two phases also allows phase discrimination. Additionally, an analytical technique for determining absolute atomic areal density is used to produce an absolute carbon and sulfur areal density map. We also show how these maps may be re-interpreted as a phase ratio map, giving quantitative information about the purity of the phases within the junction.« less

Removal of sulfur compounds from combustion product exhaust

DOEpatents

Cheng, Dah Y.

1982-01-01

A method and device are disclosed for removing sulfur containing contaminents from a combustion product exhaust. The removal process is carried out in two stages wherein the combustion product exhaust is dissolved in water, the water being then heated to drive off the sulfur containing contaminents. The sulfur containing gases are then resolublized in a cold water trap to form a concentrated solution which can then be used as a commercial product.

Sulfur Species as Redox Partners and Electron Shuttles for Ferrihydrite Reduction by Sulfurospirillum deleyianum

PubMed Central

Lohmayer, Regina; Kappler, Andreas; Lösekann-Behrens, Tina

2014-01-01

Iron(III) (oxyhydr)oxides can represent the dominant microbial electron acceptors under anoxic conditions in many aquatic environments, which makes understanding the mechanisms and processes regulating their dissolution and transformation particularly important. In a previous laboratory-based study, it has been shown that 0.05 mM thiosulfate can reduce 6 mM ferrihydrite indirectly via enzymatic reduction of thiosulfate to sulfide by the sulfur-reducing bacterium Sulfurospirillum deleyianum, followed by abiotic reduction of ferrihydrite coupled to reoxidation of sulfide. Thiosulfate, elemental sulfur, and polysulfides were proposed as reoxidized sulfur species functioning as electron shuttles. However, the exact electron transfer pathway remained unknown. Here, we present a detailed analysis of the sulfur species involved. Apart from thiosulfate, substoichiometric amounts of sulfite, tetrathionate, sulfide, or polysulfides also initiated ferrihydrite reduction. The portion of thiosulfate produced during abiotic ferrihydrite-dependent reoxidation of sulfide was about 10% of the total sulfur at maximum. The main abiotic oxidation product was elemental sulfur attached to the iron mineral surface, which indicates that direct contact between microorganisms and ferrihydrite is necessary to maintain the iron reduction process. Polysulfides were not detected in the liquid phase. Minor amounts were found associated either with microorganisms or the mineral phase. The abiotic oxidation of sulfide in the reaction with ferrihydrite was identified as rate determining. Cysteine, added as a sulfur source and a reducing agent, also led to abiotic ferrihydrite reduction and therefore should be eliminated when sulfur redox reactions are investigated. Overall, we could demonstrate the large impact of intermediate sulfur species on biogeochemical iron transformations. PMID:24632263

Origin of sulfur for elemental sulfur concentration in salt dome cap rocks, Gulf Coast Basin, USA

NASA Astrophysics Data System (ADS)

Hill, J. M.; Kyle, R.; Loyd, S. J.

2017-12-01

Calcite cap rocks of the Boling and Main Pass salt domes contain large elemental sulfur accumulations. Isotopic and petrographic data indicate complex histories of cap rock paragenesis for both domes. Whereas paragenetic complexity is in part due to the open nature of these hydrodynamic systems, a comprehensive understanding of elemental sulfur sources and concentration mechanisms is lacking. Large ranges in traditional sulfur isotope compositions (δ34S) among oxidized and reduced sulfur-bearing phases has led some to infer that microbial sulfate reduction and/or influx of sulfide-rich formation waters occurred during calcite cap rock formation. Ultimately, traditional sulfur isotope analyses alone cannot distinguish among local microbial or exogenous sulfur sources. Recently, multiple sulfur isotope (32S, 33S, 34S, 36S) studies reveal small, but measurable differences in mass-dependent behavior of microbial and abiogenic processes. To distinguish between the proposed sulfur sources, multiple-sulfur-isotope analyses have been performed on native sulfur from the Boling and Main Pass cap rocks. Similarities or deviations from equilibrium relationships indicate which pathways were responsible for native sulfur precipitation. Pathway determination provides insight into Gulf Coast cap rock development and potentially highlights the conditions that led to anomalous sulfur enrichment in Boling and Main Pass Domes.

Technological and economic aspects of coal biodesulfurisation.

PubMed

Klein, J

1998-01-01

The sulfur found in coal is either part of the molecular coal structure (organically bound sulfur), is contained in minerals such as pyrite (FeS2), or occurs in minor quantities in the form of sulfate and elemental sulfur. When pyrite crystals are finely distributed within the coal matrix, mechanical cleaning can only remove part of the pyrite. It can, however, be removed by microbial action requiring only mild conditions. The process involves simple equipment, almost no chemicals, but relatively long reaction times, and treatment of iron sulfate containing process water. Different process configurations are possible, depending on the coal particle size. Coal with particle sizes of less than 0.5 mm is preferably desulfurised in slurry reactors, while lump coal (> 0.5 mm) should be treated in heaps. Investment and operating costs are estimated for different process configurations on an industrial scale. Concerning the organically bound sulfur in coal there is up to now no promising biochemical pathway for the degradation and/or desulfurisation of such compounds.

Supercritical carbon dioxide and sulfur in the Madison Limestone: A natural analog in southwest Wyoming for geologic carbon-sulfur co-sequestration

NASA Astrophysics Data System (ADS)

Kaszuba, John P.; Navarre-Sitchler, Alexis; Thyne, Geoffrey; Chopping, Curtis; Meuzelaar, Tom

2011-09-01

The Madison Limestone on the Moxa Arch, southwest Wyoming, USA contains large volumes (65-95%) of supercritical CO 2 that it has stored naturally for 50 million years. This reservoir also contains supercritical H 2S, aqueous sulfur complexes (SO 42- and HS -), and sulfur-bearing minerals (anhydrite and pyrite). Although SO 2 is not present, these sulfur-bearing phases are known products of SO 2 disproportionation in other water-rock systems. The natural co-occurrence of SO 42-, S 2-, supercritical CO 2 and brine affords the opportunity to evaluate the fate of a carbon-sulfur co-sequestration scenario. Mineralogic data was obtained from drill core and aqueous geochemical data from wells outside and within the current supercritical CO 2-sulfur-brine-rock system. In addition to dolomite, calcite, and accessory sulfur-bearing minerals, the Madison Limestone contains accessory quartz and the aluminum-bearing minerals feldspar, illite, and analcime. Dawsonite (NaAlCO 3(OH) 2), predicted as an important carbon sink in sequestration modeling studies, is not present. After confirming equilibrium conditions for the Madison Limestone system, reaction path models were constructed with initial conditions based on data from outside the reservoir. Addition of supercritical CO 2 to the Madison Limestone was simulated and the results compared to data from inside the reservoir. The model accurately predicts the observed mineralogy and captures the fundamental changes expected in a Madison Limestone-brine system into which CO 2 is added. pH decreases from 5.7 to 4.5 at 90 °C and to 4.0 at 110 °C, as expected from dissolution of supercritical CO 2, creation of carbonic acid, and buffering by the carbonate rock. The calculated redox potential increases by 0.1 V at 90 °C and 0.15 V at 110 °C due to equilibrium among CO 2, anhydrite, and pyrite. Final calculated Eh and pH match conditions for the co-existing sulfur phases present in produced waters and core from within the reservoir. Total dissolved solids increase with reaction progress, mostly due to dissolution of calcite with an accompanying increase in dissolved bicarbonate. The Madison Limestone is a natural example of the thermodynamic end point that similar fluid-rock systems will develop following emplacement of a supercritical CO 2-sulfur mixture and is a natural analog for geologic carbon-sulfur co-sequestration.

Hybrid sulfur cycle operation for high-temperature gas-cooled reactors

DOEpatents

Gorensek, Maximilian B

2015-02-17

A hybrid sulfur (HyS) cycle process for the production of hydrogen is provided. The process uses a proton exchange membrane (PEM) SO.sub.2-depolarized electrolyzer (SDE) for the low-temperature, electrochemical reaction step and a bayonet reactor for the high-temperature decomposition step The process can be operated at lower temperature and pressure ranges while still providing an overall energy efficient cycle process.

Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas

DOEpatents

Basu, Arunabha

2015-05-05

A process for recovering sulfur from a hydrogen sulfide-bearing gas utilizes an aqueous reaction medium, a temperature of about 110-150.degree. C., and a high enough pressure to maintain the aqueous reaction medium in a liquid state. The process reduces material and equipment costs and addresses the environmental disadvantages associated with known processes that rely on high boiling point organic solvents.

Co-combustion of coal and biomass in a pressurized bubbling fluidized bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andries, J.; Verloop, M.; Hein, K.

1997-12-31

The use of biomass as an energy source in power plants has advantages compared to fossil fuel firing. Co-firing of biomass and coal offers additional advantages compared to exclusive biomass firing. The objective of the research described in this paper is to assess the effect of co-combustion of biomass (straw or Miscanthus Sinensis) and coal on the behavior of a pressurized fluidized bed combustor with regard to fuel feeding, fluidization, sintering, burnout, temperature distribution and the emission of harmful gaseous and solid components. Temperature and gas concentration profiles have been determined in the freeboard of the Delft 1.6 MW{sub th}more » PFBC test rig. The addition of up to 20% of biomass (based on heat input) has no adverse effect on the PFBC process. The feeding of the biomass is more critical than the feeding of coal, due to the more fibrous structure and the larger volumes of the biomass fuel. Dependent on the process conditions the biomass addition results locally in an increase or decrease of the temperatures. Biomass addition causes a small increase of the CO and NO and a small decrease of N{sub 2}O emissions. The influence of the biomass addition on the HCl emissions is not clear. The lower sulfur content and a larger sulfur capture efficiency result in lower SO{sub 2} emissions. The addition of biomass has a negligible influence on the combustion efficiency. A 15--30% higher cyclone catch was found for the coal/Miscanthus mixture when compared to the other fuels.« less

SOXAL combined SO{sub x}/NO{sub x} flue gas control demonstration. Quarterly report, April--June 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

AQUATECH Systems, a business unit of Allied-Signal Inc., proposes to demonstrate the technical viability and cost effectiveness of the SOXAL process a combined SO{sub x}/NO{sub x} control process on a 3 MW equivalent flue gas slip stream from Niagara Mohawk Power Corporation, Dunkirk Steam Station Boiler No. 4, a coal fired boiler. The SOXAL process combines 90+% sulfur dioxide removal from the flue gas using a sodium based scrubbing solution and regeneration of the spent scrubbing liquor using AQUATECH Systems` proprietary bipolar membrane technology. This regeneration step recovers a stream of sulfur dioxide suitable for subsequent processing to salable sulfurmore » or sulfuric acid. Additionally 90+% control of NO{sub x} gases can be achieved in combination with conventional urea/methanol injection of NO{sub 2} gas into the duct. The SOXAL process is applicable to both utility and industrial scale boilers using either high or low sulfur coal. The SOXAL demonstration Program began September 10, 1991 and is approximately 22 months in duration.« less

Thin-film sulfuric acid anodizing as a replacement for chromic acid anodizing

NASA Technical Reports Server (NTRS)

Kallenborn, K. J.; Emmons, J. R.

1995-01-01

Chromic acid has long been used to produce a thin, corrosion resistant (Type I) coating on aluminum. Following anodizing, the hardware was sealed using a sodium dichromate solution. Sealing closes up pores inherent in the anodized coating, thus improving corrosion resistance. The thinness of the brittle coating is desirable from a fatigue standpoint, and chromium was absorbed by the coating during the sealing process, further improving corrosion resistance. Unfortunately, both chromic acid and sodium dichromate contain carcinogenic hexavalent chromium. Sulfuric acid is being considered as a replacement for chromic acid. Sulfuric acid of 10-20 percent concentration has traditionally been used to produce relatively thick (Types II and III) or abrasion resistant (Type III) coatings. A more dilute, that is five weight percent, sulfuric acid anodizing process, which produces a thinner coating than Type II or III, with nickel acetate as the sealant has been developed. The process was evaluated in regard to corrosion resistance, throwing power, fatigue life, and processing variable sensitivity, and shows promise as a replacement for the chromic acid process.

Specific gravity and API gravity of biodiesel and ultra-low sulfur diesel (ULSD) blends

USDA-ARS?s Scientific Manuscript database

Biodiesel is an alternative fuel made from vegetable oils and animal fats. In 2006, the U. S. Environmental Protection Agency mandated a maximum sulfur content of 15 ppm in on-road diesel fuels. Processing to produce the new ultra-low sulfur petrodiesel (ULSD) alters specific gravity (SG) and othe...

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2013 CFR

2013-07-01

... sulfur oxides. (iii) Fossil fuel means natural gas, refinery fuel gas, coke oven gas, petroleum, coal and any form of solid, liquid, or gaseous fuel derived from such materials. (iv) Fossil fuel-fired steam generating unit means a furnace or boiler used in the process of burning fossil fuel for the purpose of...

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2014 CFR

2014-07-01

... sulfur oxides. (iii) Fossil fuel means natural gas, refinery fuel gas, coke oven gas, petroleum, coal and any form of solid, liquid, or gaseous fuel derived from such materials. (iv) Fossil fuel-fired steam generating unit means a furnace or boiler used in the process of burning fossil fuel for the purpose of...

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2010 CFR

2010-07-01

... sulfur oxides. (iii) Fossil fuel means natural gas, refinery fuel gas, coke oven gas, petroleum, coal and any form of solid, liquid, or gaseous fuel derived from such materials. (iv) Fossil fuel-fired steam generating unit means a furnace or boiler used in the process of burning fossil fuel for the purpose of...

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2012 CFR

2012-07-01

... sulfur oxides. (iii) Fossil fuel means natural gas, refinery fuel gas, coke oven gas, petroleum, coal and any form of solid, liquid, or gaseous fuel derived from such materials. (iv) Fossil fuel-fired steam generating unit means a furnace or boiler used in the process of burning fossil fuel for the purpose of...

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2011 CFR

2011-07-01

... sulfur oxides. (iii) Fossil fuel means natural gas, refinery fuel gas, coke oven gas, petroleum, coal and any form of solid, liquid, or gaseous fuel derived from such materials. (iv) Fossil fuel-fired steam generating unit means a furnace or boiler used in the process of burning fossil fuel for the purpose of...

77 FR 61308 - Outer Continental Shelf Air Regulations; Consistency Update for California

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-09

... and recordkeeping requirements, Sulfur oxides. Dated: September 13, 2012. Jared Blumenfeld, Regional...) Rule 53 Particulate Matter-Process Weight (Adopted 04/13/04) Rule 54 Sulfur Compounds (Adopted 06/14/94... Sulfur Content of Fuels (Adopted 04/13/99) Rule 67 Vacuum Producing Devices (Adopted 07/05/83) Rule 68...

Stack gas treatment

DOEpatents

Reeves, Adam A.

1977-04-12

Hot stack gases transfer contained heat to a gravity flow of pebbles treated with a catalyst, cooled stacked gases and a sulfuric acid mist is withdrawn from the unit, and heat picked up by the pebbles is transferred to air for combustion or other process. The sulfuric acid (or sulfur, depending on the catalyst) is withdrawn in a recovery unit.

Minimize Solvent Oxidation with NO X Pre-Scrubbing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sexton, Andrew; Sachde, Darshan; Vance, Austyn

A novel method to remove nitrogen dioxide (NO 2) from the flue gas of coal-fired power plants with CO 2 capture was further developed for commercial implementation. The technology leverages the equipment and chemistry in an existing (sulfur dioxide) SO 2 polishing scrubber upstream of the main CO 2 capture unit to remove the NO 2, preventing degradation of the CO 2 capture solvent and formation of nitrosamines (environmental hazards). The research in this report focuses on further evaluation of the chemical additives and operating conditions associated with the NO 2 removal process to define conditions for commercial scale testingmore » and deployment. Experimental work systematically evaluated a series of potential additives to minimize the oxidation of sulfite in a representative SO 2 pre-scrubber solution (sulfite, in turn, absorbs NO 2). The additive combinations and concentrations were varied alongside important process conditions such as temperature, oxygen concentration, and metals present in solution to mimic the conditions expected in a commercial system. Important results of the parametric experimental work include identifying a new, potent sulfite oxidation inhibitor, revealing the importance of combining inhibitors with metal chelating agents, validation of a low-cost additive process, and development of a new semi-empirical model to represent mechanisms associated with sulfite oxidation. In addition, the experimental work reveled the impact of operating at higher temperatures (representative of a field test unit), which will guide the selection and concertation of additives as well. Engineering analysis found that waste solutions from the pre-scrubber with NO 2 additives may potentially be integrated with existing processes on site (e.g., flue gas desulfurization unit). In addition, techno-economic analysis identified potential net savings as large as $1.30/tonne CO 2 captured and quantified the potential benefit of low cost additive options actively being pursued by the development team. Finally, the experimental results and engineering analysis supported the development of a detailed field testing plan and protocol to evaluate the technology at near-commercial scale. The field test preparation included development of procedures to introduce chemical additives to an existing SO 2 polishing unit and identification of representative flue gas conditions based on a review of existing plants. These activities will have direct bearing on operation and design of commercial units.« less

Effect of Methanethiol Concentration on Sulfur Production in Biological Desulfurization Systems under Haloalkaline Conditions.

PubMed

Roman, Pawel; Veltman, René; Bijmans, Martijn F M; Keesman, Karel J; Janssen, Albert J H

2015-08-04

Bioremoval of H2S from gas streams became popular in recent years because of high process efficiency and low operational costs. To expand the scope of these processes to gas streams containing volatile organic sulfur compounds, like thiols, it is necessary to provide new insights into their impact on overall biodesulfurization process. Published data on the effect of thiols on biodesulfurization processes are scarce. In this study, we investigated the effect of methanethiol on the selectivity for sulfur production in a bioreactor integrated with a gas absorber. This is the first time that the inhibition of biological sulfur formation by methanethiol is investigated. In our reactor system, inhibition of sulfur production started to occur at a methanethiol loading rate of 0.3 mmol L(-1) d(-1). The experimental results were also described by a mathematical model that includes recent findings on the mode of biomass inhibition by methanethiol. We also found that the negative effect of methanethiol can be mitigated by lowering the salinity of the bioreactor medium. Furthermore, we developed a novel approach to measure the biological activity by sulfide measurements using UV-spectrophotometry. On the basis of this measurement method, it is possible to accurately estimate the unknown kinetic parameters in the mathematical model.

Sulfur Dioxide Designations

EPA Pesticide Factsheets

This area provides information on the process EPA, the states, and the tribes follow to designate areas as attainment (meeting) or nonattainment (not meeting) the sulfur dioxide air quality standards.

Microbial desulfurization of coal

NASA Technical Reports Server (NTRS)

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

1978-01-01

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

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, J.B.L.; Gorski, A.J.; Daniels, E.J.

1993-05-18

A process is described for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is [dis]associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, John B. L.; Gorski, Anthony J.; Daniels, Edward J.

1993-01-01

A process for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Distribution, movement, and evolution of the volatile elements in the lunar regolith

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.

1975-01-01

The abundances and distributions of carbon, nitrogen, and sulfur in lunar soils are reviewed. Carbon and nitrogen have a predominantly extra-lunar origin in lunar soils and breccias, while sulfur is mostly indigeneous to the moon. The lunar processes which effect the movement, distribution, and evolution of carbon, nitrogen, and sulfur, along with the volatile alkali elements sodium, potassium, and rubidium during regolith processes are discussed. Possible mechanisms which may result in the addition to or loss from the moon of these volatile elements are considered.

An investigation of the mechanisms of calcination and sulfation in coal-water mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christofides, N.

1990-09-21

The purpose of this investigation is to study the mechanisms of sulfur capture when burning coal-water-limestone mixtures (CWLM) in fluidized beds. Special care is taken to make comparisons with to dry coal and sorbent under comparable experimental conditions. A series of experiments were performed in an eight-inch diameter bubbling fluidized bed combustor to address this problem. 33 refs., 17 figs., 5 tabs.

Using Mars's Sulfur Cycle to Constrain the Duration and Timing of Fluvial Processes

NASA Technical Reports Server (NTRS)

Blaney, D. L.

2002-01-01

Sulfur exists in high abundances at diverse locations on Mars. This work uses knowledge of the Martian sulfate system to discriminate between leading hypotheses and discusses the implications for duration and timing of fluvial processes. Additional information is contained in the original extended abstract.

Effective sulfur and energy recovery from hydrogen sulfide through incorporating an air-cathode fuel cell into chelated-iron process.

PubMed

Sun, Min; Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi

2013-12-15

The chelated-iron process is among the most promising techniques for the hydrogen sulfide (H2S) removal due to its double advantage of waste minimization and resource recovery. However, this technology has encountered the problem of chelate degradation which made it difficult to ensure reliable and economical operation. This work aims to develop a novel fuel-cell-assisted chelated-iron process which employs an air-cathode fuel cell for the catalyst regeneration. By using such a process, sulfur and electricity were effectively recovered from H2S and the problem of chelate degradation was well controlled. Experiment on a synthetic sulfide solution showed the fuel-cell-assisted chelated-iron process could maintain high sulfur recovery efficiencies generally above 90.0%. The EDTA was preferable to NTA as the chelating agent for electricity generation, given the Coulombic efficiencies (CEs) of 17.8 ± 0.5% to 75.1 ± 0.5% for the EDTA-chelated process versus 9.6 ± 0.8% to 51.1 ± 2.7% for the NTA-chelated process in the pH range of 4.0-10.0. The Fe (III)/S(2-) ratio exhibited notable influence on the electricity generation, with the CEs improved by more than 25% as the Fe (III)/S(2-) molar ratio increased from 2.5:1 to 3.5:1. Application of this novel process in treating a H2S-containing biogas stream achieved 99% of H2S removal efficiency, 78% of sulfur recovery efficiency, and 78.6% of energy recovery efficiency, suggesting the fuel-cell-assisted chelated-iron process was effective to remove the H2S from gas streams with favorable sulfur and energy recovery efficiencies. Copyright © 2013 Elsevier B.V. All rights reserved.

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: Sulfur geochemistry and reaction modeling

USGS Publications Warehouse

Alt, J.C.; Shanks, Wayne C.

2003-01-01

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated ??34Ssulfide (3.7 to 12.7???). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400??C alone cannot account for both the high sulfur contents and high ??34Ssulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (???400??C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ???300??C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5???) at temperatures above 250??C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 ?? 1012 g seawater S yr-1. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates. ?? 2003 Elsevier Science Ltd.

Estimate feedstock processability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amorelli, A.; Amos, Y.D.; Halsig, C.P.

1992-06-01

Currently, one of the major environmental pressures is to further reduce sulfur levels in middle distillate products. This paper reports that the key to this is understanding reactivities of individual sulfur components in the feedstocks to be treated. The major sulfur species in middle distillates is aromatic compounds, predominantly benzothiophenes and dibenzothiophenes. However, in straight run materials, significant quantities of aliphatic sulfur compounds and further higher boiling benzothiophenes are also expected. Simultaneous simulated distillation with a gas chromatograph microwave-induced plasma atomic emission detector (SIMDIS/AED) is used for middle distillate characterization of sulfur distribution as a function of boiling point. Itmore » is able to discriminate between middle distillate feed types such as cracked and straight run gas oils, and has shown that similar feeds, with different total sulfur contents (unevenly distributed throughout a feedstock), have the same normalized sulfur distribution.« less

A Combined Proteomic and Transcriptomic Analysis on Sulfur Metabolism Pathways of Arabidopsis thaliana under Simulated Acid Rain

PubMed Central

Wang, Wenhua; Simon, Martin; Wu, Feihua; Hu, Wenjun; Chen, Juan B.; Zheng, Hailei

2014-01-01

With rapid economic development, most regions in southern China have suffered acid rain (AR) pollution. In our study, we analyzed the changes in sulfur metabolism in Arabidopsis under simulated AR stress which provide one of the first case studies, in which the systematic responses in sulfur metabolism were characterized by high-throughput methods at different levels including proteomic, genomic and physiological approaches. Generally, we found that all of the processes related to sulfur metabolism responded to AR stress, including sulfur uptake, activation and also synthesis of sulfur-containing amino acid and other secondary metabolites. Finally, we provided a catalogue of the detected sulfur metabolic changes and reconstructed the coordinating network of their mutual influences. This study can help us to understand the mechanisms of plants to adapt to AR stress. PMID:24595051

Space-based detection of missing sulfur dioxide sources of global air pollution

NASA Astrophysics Data System (ADS)

McLinden, Chris A.; Fioletov, Vitali; Shephard, Mark W.; Krotkov, Nick; Li, Can; Martin, Randall V.; Moran, Michael D.; Joiner, Joanna

2016-07-01

Sulfur dioxide is designated a criteria air contaminant (or equivalent) by virtually all developed nations. When released into the atmosphere, sulfur dioxide forms sulfuric acid and fine particulate matter, secondary pollutants that have significant adverse effects on human health, the environment and the economy. The conventional, bottom-up emissions inventories used to assess impacts, however, are often incomplete or outdated, particularly for developing nations that lack comprehensive emission reporting requirements and infrastructure. Here we present a satellite-based, global emission inventory for SO2 that is derived through a simultaneous detection, mapping and emission-quantifying procedure, and thereby independent of conventional information sources. We find that of the 500 or so large sources in our inventory, nearly 40 are not captured in leading conventional inventories. These missing sources are scattered throughout the developing world--over a third are clustered around the Persian Gulf--and add up to 7 to 14 Tg of SO2 yr-1, or roughly 6-12% of the global anthropogenic source. Our estimates of national total emissions are generally in line with conventional numbers, but for some regions, and for SO2 emissions from volcanoes, discrepancies can be as large as a factor of three or more. We anticipate that our inventory will help eliminate gaps in bottom-up inventories, independent of geopolitical borders and source types.

Space-Based Detection of Missing Sulfur Dioxide Sources of Global Air Pollution

NASA Technical Reports Server (NTRS)

McLinden, Chris A.; Fioletov, Vitali; Shephard, Mark W.; Krotkov, Nick; Li, Can; Martin, Randall V.; Moran, Michael D.; Joiner, Joanna

2016-01-01

Sulfur dioxide is designated a criteria air contaminant (or equivalent) by virtually all developed nations. When released into the atmosphere, sulfur dioxide forms sulfuric acid and fine particulate matter, secondary pollutants that have significant adverse effects on human health, the environment and the economy. The conventional, bottom-up emissions inventories used to assess impacts, however, are often incomplete or outdated, particularly for developing nations that lack comprehensive emission reporting requirements and infrastructure. Here we present a satellite-based, global emission inventory for SO2 that is derived through a simultaneous detection, mapping and emission-quantifying procedure, and thereby independent of conventional information sources. We find that of the 500 or so large sources in our inventory, nearly 40 are not captured in leading conventional inventories. These missing sources are scattered throughout the developing world-over a third are clustered around the Persian Gulf-and add up to 7 to 14 Tg of SO2 yr(exp -1), or roughly 6-12% of the global anthropogenic source. Our estimates of national total emissions are generally in line with conventional numbers, but for some regions, and for SO2 emissions from volcanoes, discrepancies can be as large as a factor of three or more. We anticipate that our inventory will help eliminate gaps in bottom-up inventories, independent of geopolitical borders and source types.

The NOXSO clean coal project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Black, J.B.; Woods, M.C.; Friedrich, J.J.

1997-12-31

The NOXSO Clean Coal Project will consist of designing, constructing, and operating a commercial-scale flue-gas cleanup system utilizing the NOXSO Process. The process is a waste-free, dry, post-combustion flue-gas treatment technology which uses a regenerable sorbent to simultaneously adsorb sulfur dioxide (SO{sub 2}) and nitrogen oxides (NO{sub x}) from flue gas from coal-fired boilers. The NOXSO plant will be constructed at Alcoa Generating Corporation`s (AGC) Warrick Power Plant near Evansville, Indiana and will treat all the flue gas from the 150-MW Unit 2 boiler. The NOXSO plant is being designed to remove 98% of the SO{sub 2} and 75% ofmore » the NO{sub x} when the boiler is fired with 3.4 weight percent sulfur, southern-Indiana coal. The NOXSO plant by-product will be elemental sulfur. The elemental sulfur will be shipped to Olin Corporation`s Charleston, Tennessee facility for additional processing. As part of the project, a liquid SO{sub 2} plant has been constructed at this facility to convert the sulfur into liquid SO{sub 2}. The project utilizes a unique burn-in-oxygen process in which the elemental sulfur is oxidized to SO{sub 2} in a stream of compressed oxygen. The SO{sub 2} vapor will then be cooled and condensed. The burn-in-oxygen process is simpler and more environmentally friendly than conventional technologies. The liquid SO{sub 2} plant produces 99.99% pure SO{sub 2} for use at Olin`s facilities. The $82.8 million project is co-funded by the US Department of Energy (DOE) under Round III of the Clean Coal Technology program. The DOE manages the project through the Pittsburgh Energy Technology Center (PETC).« less

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

USGS Publications Warehouse

Poulin, Brett A.; Ryan, Joseph N.; Nagy, Kathryn L.; Stubbins, Aron; Dittmar, Thorsten; Orem, William H.; Krabbenhoft, David P.; Aiken, George R.

2017-01-01

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Process development for production of coal/sorbent agglomerates. Final technical report, September 1, 1990--August 31, 1991

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rapp, D.M.

1991-12-31

The goal of this work was to develop a process flow diagram to economically produce a clean-burning fuel from fine Illinois coal. To accomplish this, the process of pelletizing fine coal with calcium hydroxide, a sulfur capturing sorbent, was investigated. Carbonation, which is the reaction of calcium hydroxide with carbon dioxide (in the presence of moisture) to produce a bonding matrix of calcium carbonate, was investigated as a method for improving pellet quality and reducing binder costs. Proper moisture level is critical to allow the reaction to occur. If too much moisture is present in a pellet, the pore spacesmore » are filled and carbon dioxide must diffuse through the water to reach the calcium hydroxide and react. This severely slows or stops the reaction. The ideal situation is when there is just enough moisture to coat the calcium hydroxide allowing for the reaction to proceed. The process has been successfully demonstrated on a pilot-scale as a method of hardening iron ore pellets (Imperato, 1966). Two potential combustion options are being considered for the coal/calcium hydroxide pellets: fluidized bed combustors and industrial stoker boilers.« less

Separation Process of Fine Coals by Ultrasonic Vibration Gas-Solid Fluidized Bed

PubMed Central

Wei, Hua; Xie, Weining

2017-01-01

Ultrasonic vibration gas-solid fluidized bed was proposed and introduced to separate fine coals (0.5–0.125 mm fraction). Several technological methods such as XRF, XRD, XPS, and EPMA were used to study the composition of heavy products to evaluate the separation effect. Results show that the ultrasonic vibration force field strengthens the particle separation process based on density when the vibration frequency is 35 kHz and the fluidization number is 1.8. The ash difference between the light and heavy products and the recovery of combustible material obtain the maximum values of 47.30% and 89.59%, respectively. The sulfur content of the heavy product reaches the maximum value of 6.78%. Chemical state analysis of sulfur shows that organic sulfur (-C-S-), sulfate-sulfur (-SO4), and pyrite-sulfur (-S2) are confirmed in the original coal and heavy product. Organic sulfur (-C-S-) is mainly concentrated in the light product, and pyrite-sulfur (-S2) is significantly enriched in the heavy product. The element composition, phase composition, backscatter imagery, and surface distribution of elements for heavy product show concentration of high-density minerals including pyrite, quartz, and kaolinite. Some harmful elements such as F, Pb, and As are also concentrated in the heavy product. PMID:28845160

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

A soft approach to encapsulate sulfur: polyaniline nanotubes for lithium-sulfur batteries with long cycle life.

PubMed

Xiao, Lifen; Cao, Yuliang; Xiao, Jie; Schwenzer, Birgit; Engelhard, Mark H; Saraf, Laxmikant V; Nie, Zimin; Exarhos, Gregory J; Liu, Jun

2012-03-02

A novel vulcanized polyaniline nanotube/sulfur composite was prepared successfully via an in situ vulcanization process by heating a mixture of polyaniline nanotube and sulfur at 280 °C. The electrode could retain a discharge capacity of 837 mAh g(-1) after 100 cycles at a 0.1 C rate and manifested 76% capacity retention up to 500 cycles at a 1 C rate. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Project Summary: Increased Fuel Affordability Through Deployable Refining Technology (Briefing Charts)

DTIC Science & Technology

2016-05-01

distribution is unlimited. PA Clearance #16274 2 Overall Process DISTRIBUTION A. Approved for public release; distribution unlimited. 3 Sulfur in Fuels...Mercaptans (Thiols) The presence of sulfur in fuels leads to many detrimental effects: • Coking on rocket engine injector plates • Deposit formation in... Sulfur Compounds by GC-SCD ( Sulfur Speciation) Concentration (ppm) C2 Thiophenes 0.3 C3-C4 Thiophenes 1.4 C5 Thiophenes 3.7 C6 Thiophenes 3.5 C7

Neutralization and Biodegradation of Sulfur Mustard.

DTIC Science & Technology

1997-02-01

public release; distribution is unlimited. 13. ABSTRACT (Maximum 200 words) The chemical warfare agent sulfur mustard was hydrolyzed to products that...scale bioreactors processing hydrolyzed munitions-grade sulfur mustard obtained directly from the U.S. Chemical Stockpile. The bioreactor effluent was...Hydrolysis has been previously utili ed for the detoxification of Canadian HD stockpiles (Reichert, 1975). Biodegradation has widespread application in

Hydrometallurgical process for recovering iron sulfate and zinc sulfate from baghouse dust

DOEpatents

Zaromb, Solomon; Lawson, Daniel B.

1994-01-01

A process for recovering zinc/rich and iron-rich fractions from the baghouse dust that is generated in various metallurgical operations, especially in steel-making and other iron-making plants, comprises the steps of leaching the dust by hot concentrated sulfuric acid so as to generate dissolved zinc sulfate and a precipitate of iron sulfate, separating the precipitate from the acid by filtration and washing with a volatile liquid, such as methanol or acetone, and collecting the filtered acid and the washings into a filtrate fraction. The volatile liquid may be recovered distillation, and the zinc may be removed from the filtrate by alternative methods, one of which involves addition of a sufficient amount of water to precipitate hydrated zinc sulfate at 10.degree. C., separation of the precipitate from sulfuric acid by filtration, and evaporation of water to regenerate concentrated sulfuric acid. The recovery of iron may also be effected in alternative ways, one of which involves roasting the ferric sulfate to yield ferric oxide and sulfur trioxide, which can be reconverted to concentrated sulfuric acid by hydration. The overall process should not generate any significant waste stream.

Hydrometallurgical process for recovering iron sulfate and zinc sulfate from baghouse dust

DOEpatents

Zaromb, S.; Lawson, D.B.

1994-02-15

A process for recovering zinc-rich and iron-rich fractions from the baghouse dust that is generated in various metallurgical operations, especially in steel-making and other iron-making plants, comprises the steps of leaching the dust by hot concentrated sulfuric acid so as to generate dissolved zinc sulfate and a precipitate of iron sulfate, separating the precipitate from the acid by filtration and washing with a volatile liquid, such as methanol or acetone, and collecting the filtered acid and the washings into a filtrate fraction. The volatile liquid may be recovered by distillation, and the zinc may be removed from the filtrate by alternative methods, one of which involves addition of a sufficient amount of water to precipitate hydrated zinc sulfate at 10 C, separation of the precipitate from sulfuric acid by filtration, and evaporation of water to regenerate concentrated sulfuric acid. The recovery of iron may also be effected in alternative ways, one of which involves roasting the ferric sulfate to yield ferric oxide and sulfur trioxide, which can be reconverted to concentrated sulfuric acid by hydration. The overall process should not generate any significant waste stream. 1 figure.

Bacterial Synthesis of Unusual Sulfonamide and Sulfone Antibiotics by Flavoenzyme-Mediated Sulfur Dioxide Capture.

PubMed

Baunach, Martin; Ding, Ling; Willing, Karsten; Hertweck, Christian

2015-11-02

Sulfa drugs, such as sulfonilamide and dapsone, are classical antibiotics that have been in clinical use worldwide. Despite the relatively simple architectures, practically no natural products are known to feature such aromatic sulfonamide or diarylsulfone substructures. We report the unexpected discovery of three fully unprecedented, sulfonyl-bridged alkaloid dimers (sulfadixiamycins A-C) from recombinant Streptomyces species harboring the entire xiamycin biosynthesis gene cluster. Sulfadixiamycins exhibit moderate antimycobacterial activities and potent antibiotic activities even against multidrug-resistant bacteria. Gene inactivation, complementation, and biotransformation experiments revealed that a flavin-dependent enzyme (XiaH) plays a key role in sulfadixiamycin biosynthesis. XiaH mediates a radical-based, three-component reaction involving two equivalents of xiamycin and sulfur dioxide, which is reminiscent of radical styrene/SO2 copolymerization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The GA sulfur-iodine water-splitting process - A status report

NASA Astrophysics Data System (ADS)

Besenbruch, G. E.; Chiger, H. D.; McCorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

The GA sulfur-iodine water-splitting process - A status report

NASA Technical Reports Server (NTRS)

Besenbruch, G. E.; Chiger, H. D.; Mccorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

1981-01-01

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

Simultaneous stack gas scrubbing wastewater purification

NASA Technical Reports Server (NTRS)

1978-01-01

Variations of a process for removing sulfur dioxide from stack gases and using it to treat municipal waste water are described. The once-through system lowers the pH of the scrubbing water from minor depressions to a pH of about 2.5 under certain conditions. A recycle system uses iron for catalytic oxidation of sulfurous acid to sulfuric acid allowing very large amounts of sulfur dioxide to be absorbed in a small portion of water. The partial recycle system uses municipal wastewater and iron as a scrubbing medium, followed by neutralization of the wastewater with lime to produce an iron hydroxide precipitation which, when removed, produces tertiary quality treated wastewater. The SO2 scrubber is described, test results are analyzed, and a preliminary capital cost estimate for the three processes is included.

PROCESS FOR THE RECOVERY OF URANIUM

DOEpatents

Morris, G.O.

1955-06-21

This patent relates to a process for the recovery of uranium from impure uranium tetrafluoride. The process consists essentially of the steps of dissolving the impure uranium tetrafluoride in excess dilute sulfuric acid in the presence of excess hydrogen peroxide, precipitating ammonium uranate from the solution so formed by adding an excess of aqueous ammonia, dissolving the precipitate in sulfuric acid and adding hydrogen peroxide to precipitate uranium peroxdde.

An investigation of the efficacy of biological additives for the suppression of pyritic sulphur during simulated froth flotation of coal.

PubMed

Stainthorpe, A C

1989-02-05

The biological molecule responsible for the suppression of pyritic sulfur in fine coal simulated froth flotation treated with bacteria was identified. Protein was found to be the most effective agent in pyrite suppression of the three cell components (protein, lipid, and carbohydrate) assayed. Coal recovery and ash removal of the flotation process were only slightly reduced by this treatment. Other protein-containing materials were evaluated for their ability to suppress pyrite flotation. Whey was found to be the most cost-effective flotation additive of those assayed. The sulfur content of the whey-treated float was reduced by 84.0% in a synthetically prepared fractionated coal (10.7% sulfur), by a raw whey dosage of 20 microL/g coal. The inorganic sulfur component of a natural high sulfur coal fraction (10.9%) was completely depressed by this whey addition. The effect of particle size and pulp density upon the process were investigated.

Formation of pyrite (FeS{sub 2}) thin films by thermal sulfurization of dc magnetron sputtered iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soukup, R. J.; Prabukanthan, P.; Ianno, N. J.

2011-01-15

Iron films deposited by direct current magnetron sputtering onto glass substrates were converted into FeS{sub 2} films by thermal sulfurization. Experiments were carried out to optimize the sulfurization process, and the formation of FeS{sub 2} thin films was investigated under different annealing temperatures and times. High quality FeS{sub 2} films were fabricated using this process, and single phase pyrite films were obtained after sulfurization in a sulfur and nitrogen atmosphere at 450 deg. C for 1 h. Film crystallinity and phase identification were determined by using x-ray diffraction. The cubic phase pyrite films prepared were p-type, and scanning electron microscopymore » studies exhibited a homogeneous surface of pyrite. The authors have found that the best Ohmic contact for their pyrite thin films, using inexpensive metals, was Ni. The following were chosen for the study: Al, Mo, Fe, and Ni, and the one that led to the lowest resistance, 333 {Omega}, was Ni.« less

Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

PubMed

Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

2018-06-08

Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

Two-stage, dilute sulfuric acid hydrolysis of wood : an investigation of fundamentals

Treesearch

John F. Harris; Andrew J. Baker; Anthony H. Conner; Thomas W. Jeffries; James L. Minor; Roger C. Pettersen; Ralph W. Scott; Edward L Springer; Theodore H. Wegner; John I. Zerbe

1985-01-01

This paper presents a fundamental analysis of the processing steps in the production of methanol from southern red oak (Quercus falcata Michx.) by two-stage dilute sulfuric acid hydrolysis. Data for hemicellulose and cellulose hydrolysis are correlated using models. This information is used to develop and evaluate a process design.

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...

UV-light-driven prebiotic synthesis of iron-sulfur clusters

NASA Astrophysics Data System (ADS)

Bonfio, Claudia; Valer, Luca; Scintilla, Simone; Shah, Sachin; Evans, David J.; Jin, Lin; Szostak, Jack W.; Sasselov, Dimitar D.; Sutherland, John D.; Mansy, Sheref S.

2017-12-01

Iron-sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron-sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron-sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe-2S] and [4Fe-4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron-sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron-sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron-sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron-sulfur-cluster-dependent metabolism.

[Diversity of culturable sulfur-oxidizing bacteria in deep-sea hydrothermal vent environments of the South Atlantic].

PubMed

Xu, Hongxiu; Jiang, Lijing; Li, Shaoneng; Zhong, Tianhua; Lai, Qiliang; Shao, Zongze

2016-01-04

To investigate the diversity of culturable sulfur-oxidizing bacteria in hydrothermal vent environments of the South Atlantic, and analyze their characteristics of sulfur oxidation. We enriched and isolated sulfur-oxidizing bacteria from hydrothermal vent samples collected from the South Atlantic. The microbial diversity in enrichment cultures was analyzed using the Denatural Gradient Gel Electrophoresis method. Sulfur-oxidizing characteristics of the isolates was further studied by using ion chromatography. A total of 48 isolates were obtained from the deep-sea hydrothermal vent samples, which belonged to 23 genera and mainly grouped into alpha-Proteobacteria (58.3%), Actinobacteria (22.9%) and gama-Proteobacteria (18.8%). Among them, the genus Thalassospira, Martelella and Microbacterium were dominant. About 60% of the isolates exibited sulfur-oxidizing ability and strain L6M1-5 had a higher sulfur oxidation rate by comparison analysis. The diversity of sulfur-oxidizing bacteria in hydrothermal environments of the South Atlantic was reported for the first time based on culture-dependent methods. The result will help understand the biogechemical process of sulfur compounds in the deep-sea hydrothermal environments.

Sulfur assimilation and the role of sulfur in plant metabolism: a survey.

PubMed

Droux, Michel

2004-01-01

Sulfur occurs in two major amino-acids, cysteine (Cys) and methionine (Met), essential for the primary and secondary metabolism of the plant. Cys, as the first carbon/nitrogen-reduced sulfur product resulting from the sulfate assimilation pathway, serves as a sulfur donor for Met, glutathione, vitamins, co-factors, and sulfur compounds that play a major role in the growth and development of plant cells. This sulfur imprinting occurs in a myriad of fundamental processes, from photosynthesis to carbon and nitrogen metabolism. Cys and Met occur in proteins, with the former playing a wide range of functions in proteins catalysis. In addition, the sulfur atom in proteins forms part of a redox buffer, as for glutathione, through specific detoxification/protection mechanisms. In this review, a survey of sulfur assimilation from sulfate to Cys, Met and glutathione is presented with highlights on open questions on their respective biosynthetic pathways and regulations that derived from recent findings. These are addressed at the biochemical and molecular levels with respect to the fate of Cys and Met throughout the plant-cell metabolism.

Effect of inoculum and sulfide type on simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry and microbial mechanism.

PubMed

Wang, Lan; Wei, Benping; Chen, Ziai; Deng, Liangwei; Song, Li; Wang, Shuang; Zheng, Dan; Liu, Yi; Pu, Xiaodong; Zhang, Yunhong

2015-12-01

Four reactors were initiated to study the effect of inoculum and sulfide type on the simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry (Ssu-Nir) process. Anaerobic sludge, aerobic sludge, and water were used as inocula, and Na2S and biogas were used as a sulfide substrate, respectively. Additionally, 454 pyrosequencing of the 16S rRNA gene was used to explore the bacterial diversity. The results showed that sulfur-oxidizing bacteria (Thiobacillus, 42.2-84.4 %) were dominant in Ssu-Nir process and led to the excellent performance. Aerobic sludge was more suitable for inoculation of the Ssu-Nir process because it is better for rapidly enriching dominant sulfur-oxidizing bacteria (Thiobacillus, 54.4 %), denitrifying sulfur-oxidizing bacteria (40.0 %) and denitrifiers (23.9 %). Lower S(2-) removal efficiency (72.6 %) and NO3 (-) removal efficiency (<90 %) of the Ssu-Nir process were obtained using biogas as a sulfide substrate than when Na2S was used. For the Ssu-Nir process with biogas as the sulfide substrate, limiting H2S absorption caused a high relative abundance of sulfur-oxidizing bacteria, Thiobacillus (84.8 %) and Thiobacillus sayanicus (39.6 %), which in turn led to low relative abundance of denitrifiers (1.6 %) and denitrifying sulfur-oxidizing bacteria (24.4 %), low NO3 (-) removal efficiency, and eventually poor performance.

77 FR 24200 - Clean Air Act Operating Permit Program; Petitions for Objection to State Operating Permits for...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-23

... without requiring preconstruction monitoring for particulate matter less than 10 microns (PM 10 ), sulfur dioxide (SO 2 ), hydrogen sulfide (H 2 S), total reduced sulfur (TRS) and sulfuric acid mist; and (5) LDEQ... in the decision-making process. In the 2011 Petition for the modified title V pig iron permit and for...

Sulfur transformations in pilot-scale constructed wetland treating high sulfate-containing contaminated groundwater: a stable isotope assessment.

PubMed

Wu, Shubiao; Jeschke, Christina; Dong, Renjie; Paschke, Heidrun; Kuschk, Peter; Knöller, Kay

2011-12-15

Current understanding of the dynamics of sulfur compounds inside constructed wetlands is still insufficient to allow a full description of processes involved in sulfur cycling. Experiments in a pilot-scale horizontal subsurface flow constructed wetland treating high sulfate-containing contaminated groundwater were carried out. Application of stable isotope approach combined with hydro-chemical investigations was performed to evaluate the sulfur transformations. In general, under inflow concentration of about 283 mg/L sulfate sulfur, sulfate removal was found to be about 21% with a specific removal rate of 1.75 g/m(2)·d. The presence of sulfide and elemental sulfur in pore water about 17.3 mg/L and 8.5 mg/L, respectively, indicated simultaneously bacterial sulfate reduction and re-oxidation. 70% of the removed sulfate was calculated to be immobilized inside the wetland bed. The significant enrichment of (34)S and (18)O in dissolved sulfate (δ(34)S up to 16‰, compared to average of 5.9‰ in the inflow, and δ(18)O up to 13‰, compared to average of 6.9‰ in the inflow) was observed clearly correlated to the decrease of sulfate loads along the flow path through experimental wetland bed. This enrichment also demonstrated the occurrence of bacterial sulfate reduction as well as demonstrated by the presence of sulfide in the pore water. Moreover, the integral approach shows that bacterial sulfate reduction is not the sole process controlling the isotopic composition of dissolved sulfate in the pore water. The calculated apparent enrichment factor (ɛ = -22‰) for sulfur isotopes from the δ(34)S vs. sulfate mass loss was significantly smaller than required to produce the observed difference in δ(34)S between sulfate and sulfide. It indicated some potential processes superimposing bacterial sulfate reduction, such as direct re-oxidation of sulfide to sulfate by oxygen released from plant roots and/or bacterial disproportionation of elemental sulfur. Furthermore, 41% of residual sulfate was calculated to be from sulfide re-oxidation, which demonstrated that the application of stable isotope approach combined with the common hydro-chemical investigations is not only necessary for a general qualitative evaluation of sulfur transformations in constructed wetlands, but also leads to a quantitative description of intermediate processes. Copyright © 2011 Elsevier Ltd. All rights reserved.

Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory

NASA Astrophysics Data System (ADS)

Ksionzek, Kerstin B.; Lechtenfeld, Oliver J.; McCallister, S. Leigh; Schmitt-Kopplin, Philippe; Geuer, Jana K.; Geibert, Walter; Koch, Boris P.

2016-10-01

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. Although molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (sulfur/nitrogen ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 petagrams of sulfur, exceeding all other marine organic sulfur reservoirs by an order of magnitude.

Method for removing elemental sulfur in sour gas wells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sample, T.E. Jr.

1975-09-30

A process is described for removing sulfur deposits from sour gas wells. The formation, well, and surface equipment are contacted with a chemical composition whose aqueous solution will solubilize the sulfur by primary chemical reaction and contains a wetting agent to facilitate and accelerate the sulfur dissolution and removal. The wetting agent or surfactant may be any of a wide variety of surface-active substances such as soaps, sodium or ammonium salts of alkyl or alkyl-aryl sulfates and sulfonates. Nonionic surfactants are preferred, such as ethoxylated substituted phenols. The aqueous solvents are capable of chemically reacting with sulfur to form water-solublemore » sulfur derivatives and include aqueous solutions of alkalies, bases (both inorganic and organic), ammonia, sulfites, bisulfites, etc. (6 claims)« less

Method for the production of cementitious compositions and aggregate derivatives from said compositions, and cementitious compositions and aggregates produced thereby

DOEpatents

Minnick, L. John

1983-01-01

The present invention relates to a method for preparing synthetic shaped cementitious compositions having high quality even without the addition of high energy binders, such as portland cement, through the use of the spent residue from a fluidized combustion bed of the type wherein limestone particles are suspended in a fluidized medium and sulfur oxides are captured, and pulverized coal fly ash.

Developing an energy efficient steam reforming process to produce hydrogen from sulfur-containing fuels

NASA Astrophysics Data System (ADS)

Simson, Amanda

Hydrogen powered fuel cells have the potential to produce electricity with higher efficiency and lower emissions than conventional combustion technology. In order to realize the benefits of a hydrogen fuel cell an efficient method to produce hydrogen is needed. Currently, over 90% of hydrogen is produced from the steam reforming of natural gas. However, for many applications including fuel cell vehicles, the use of a liquid fuel rather than natural gas is desirable. This work investigates the feasibility of producing hydrogen efficiently by steam reforming E85 (85% ethanol/15% gasoline), a commercially available sulfur-containing transportation fuel. A Rh-Pt/SiO2-ZrO2 catalyst has demonstrated good activity for the E85 steam reforming reaction. An industrial steam reforming process is often run less efficiently, with more water and at higher temperatures, in order to prevent catalyst deactivation. Therefore, it is desirable to develop a process that can operate without catalyst deactivation at more energy efficient conditions. In this study, the steam reforming of a sulfur-containing fuel (E85) was studied at near stoichiometric steam/carbon ratios and at 650C, conditions at which catalyst deactivation is normally measured. At these conditions the catalyst was found to be stable steam reforming a sulfur-free E85. However, the addition of low concentrations of sulfur significantly deactivated the catalyst. The presence of sulfur in the fuel caused catalyst deactivation by promoting ethylene which generates surface carbon species (coke) that mask catalytic sites. The amount of coke increased during time on stream and became increasingly graphitic. However, the deactivation due to both sulfur adsorption and coke formation was reversible with air treatment at 650°C. However, regenerations were found to reduce the catalyst life. Air regenerations produce exotherms on the catalyst surface that cause structural changes to the catalyst. During regenerations the accessibility of the precious metal particles is reduced which causes the catalyst to deactivate more rapidly during subsequent steam reforming cycles. Changes to the carrier morphology also occur at these conditions. Regenerating the catalyst before significant deactivation is measured can improve the stability of the catalyst. Thus a process with preemptive controlled air regenerations is proposed in order to run a steam reforming process with sulfur containing fuels.

Free-Standing Porous Carbon Nanofiber/Carbon Nanotube Film as Sulfur Immobilizer with High Areal Capacity for Lithium-Sulfur Battery.

PubMed

Zhang, Ye-Zheng; Zhang, Ze; Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2018-03-14

Low sulfur utilization and poor cycle life of the sulfur cathode with high sulfur loadings remain a great challenge for lithium-sulfur (Li-S) battery. Herein, the free-standing carbon film consisting of porous carbon nanofibers (PCNFs) and carbon nanotubes (CNTs) is successfully fabricated by the electrospinning technology. The PCNF/CNT film with three-dimensional and interconnected structure is promising for the uniformity of the high-loading sulfur, good penetration of the electrolyte, and reliable accommodation of volumetric expansion of the sulfur cathode. In addition, the abundant N/O-doped elements in PCNF/CNT film are helpful to chemically trap soluble polysulfides in the charge-discharge processes. Consequently, the obtained monolayer S/PCNF/CNT film as the cathode shows high specific capacity, excellent cycle stability, and rate stability with the sulfur loading of 3.9 mg cm -2 . Moreover, the high areal capacity of 13.5 mA h cm -2 is obtained for the cathode by stacking three S/PCNF/CNT layers with the high sulfur loading of 12 mg cm -2 . The stacking-layered cathode with high sulfur loading provides excellent cycle stability, which is beneficial to fabricate high-energy-density Li-S battery in future.

The use of ethanol to remove sulfur from coal. Final report, September 1991--December 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-04-15

In developing the new Ohio University procedure the thermodynamic limitations of the reactions for removal of both pyritic and organic sulfur from coal at 400--600{degrees}C were studied using copper as a very strong H{sub 2}S-acceptor. Copper serves as a catalyst for ethanol dehydrogenation to form nascent hydrogen. Copper also serves as a scavenger to form copper sulfide from the hydrogen sulfide evolved during the reaction. Copper sulfide in turn serves as a catalyst for organic sulfur hydrodesulfurization reactions. If the coal to be desulfurized contains pyrite (FeS{sub 2}) or FeS, the copper scavenger effect reduces any back reaction of hydrogenmore » sulfide with the iron and increases the removal of sulfur from the carbonaceous material. The desired effect of using copper can be achieved by using copper or copper containing alloys as materials of construction or as liners for a regenerable reactor. During the time period that Ohio Coal Development Office supported this work, small scale (560 grams) laboratory experiments with coals containing about 3.5% sulfur have achieved up to 90% desulfurization at temperatures of 500{degrees}C when using a copper reactor. Results from the autoclave experiments have identified the nature of the chemical reactions taking place. Because the process removes both pyritic and organic sulfur in coal, the successful scale up of the process would have important economic significance to the coal industry. Even though this and other chemical processes may be relatively expensive and far from being commercial, the reason for further development is that this process may hold the promise of achieving much greater sulfur reduction and of producing a cleaner coal than other methods. This would be especially important for small or older power plants and industrial boilers.« less

A mesoporous carbon–sulfur composite as cathode material for high rate lithium sulfur batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Hyunji; Zhao, Xiaohui; Kim, Dul-Sun

2014-10-15

Highlights: • CMK-3 mesoporous carbon was synthesized as conducting reservoir for housing sulfur. • Sulfur/CMK-3 composites were prepared by two-stage thermal treatment. • The composite at 300 °C for 20 h shows improved electrochemical properties. - Abstract: Sulfur composite was prepared by encapsulating sulfur into CMK-3 mesoporous carbon with different heating times and then used as the cathode material for lithium sulfur batteries. Thermal treatment at 300 °C plays an important role in the sulfur encapsulation process. With 20 h of heating time, a portion of sulfur remained on the surface of carbon, whereas with 60 h of heating time,more » sulfur is confined deeply in the small pores of carbon that cannot be fully exploited in the redox reaction, thus causing low capacity. The S/CMK-3 composite with thermal treatment for 40 h at 300 °C contained 51.3 wt.% sulfur and delivered a high initial capacity of 1375 mA h g{sup −1} at 0.1 C. Moreover, it showed good capacity retention of 704 mA h g{sup −1} at 0.1 C and 578 mA h g{sup −1} at 2 C even after 100 cycles, which proves its potential as a cathode material for high capability lithium sulfur batteries.« less

Tracing Archean sulfur across stitched lithospheric blocks

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Fiorentini, Marco; Lindsay, Mark; Wing, Boswell; Selvaraja, Vikraman; Occhipinti, Sandra; Johnson, Simon; Bui, Hao Thi

2017-04-01

Craton margins are loci for volatile exchange among lithospheric geochemical reservoirs during crust formation processes. Here, we seek to revolutionise the current understanding of the planetary flux and lithospheric transfer of volatiles during supercontinent formation by tracing sulfur from the atmosphere-hydrosphere through to the lithosphere during crust formation. To do so, we trace the transfer of sulfur by following mass independently fractionated sulfur at ancient tectonic boundaries has the potential to. Mass independent fractionation of sulfur (MIF-S) is a signature (quantified as Δ33S and Δ36S) that is unique to the Archean sedimentary rock record and imparted to sulfur reservoirs that interacted with the oxygen-poor atmosphere before the Great Oxidation Event (GOE) at ca. 2.4 Ga. Here we present multiple sulfur isotopes from across a Proterozoic post-GOE orogenic belt, formed when Archean cratons were stitched together during supercontinent amalgamation. For the first time, multiple sulfur isotope data are presented spatially to elucidate volatile pathways across lithospheric blocks. Across the orogenic belt, the Proterozoic granitoid and hydrothermal rock records proximal to Archean cratons preserve values of Δ33S up to +0.8\\permil and a Δ33S-Δ36S array of -1.2, whereas magmatic and hydrothermal systems located more distally from the margin do not display any evidence of MIF-S. This is the first study to identify MIF-S in a Proterozoic orogen indicates that tectonic processes controlling lithospheric evolution and crust formation at tectonic boundaries are able to transfer sulfur from Archean supracrustal rock reservoirs to newly formed Proterozoic granitoid crust. The observation of MIF-S in the Proterozoic granitoid rock record has the potential to revolutionise our understanding of secular changes in the evolution of crust formation mechanisms through time.

Highlights of the Salt Extraction Process

NASA Astrophysics Data System (ADS)

Abbasalizadeh, Aida; Seetharaman, Seshadri; Teng, Lidong; Sridhar, Seetharaman; Grinder, Olle; Izumi, Yukari; Barati, Mansoor

2013-11-01

This article presents the salient features of a new process for the recovery of metal values from secondary sources and waste materials such as slag and flue dusts. It is also feasible in extracting metals such as nickel and cobalt from ores that normally are difficult to enrich and process metallurgically. The salt extraction process is based on extraction of the metals from the raw materials by a molten salt bath consisting of NaCl, LiCl, and KCl corresponding to the eutectic composition with AlCl3 as the chlorinating agent. The process is operated in the temperature range 973 K (700°C) to 1173 K (900°C). The process was shown to be successful in extracting Cr and Fe from electric arc furnace (EAF) slag. Electrolytic copper could be produced from copper concentrate based on chalcopyrite in a single step. Conducting the process in oxygen-free atmosphere, sulfur could be captured in the elemental form. The method proved to be successful in extracting lead from spent cathode ray tubes. In order to prevent the loss of AlCl3 in the vapor form and also chlorine gas emission at the cathode during the electrolysis, liquid aluminum was used. The process was shown to be successful in extracting Nd and Dy from magnetic scrap. The method is a highly promising process route for the recovery of strategic metals. It also has the added advantage of being environmentally friendly.

Novel polymer membrane process for pre-combustion CO{sub 2} capture from coal-fired syngas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merkel, Tim

2011-09-14

This final report describes work conducted for the Department of Energy (DOE NETL) on development of a novel polymer membrane process for pre-combustion CO{sub 2} capture from coalfired syngas (award number DE-FE0001124). The work was conducted by Membrane Technology and Research, Inc. (MTR) from September 15, 2009, through December 14, 2011. Tetramer Technologies, LLC (Tetramer) was our subcontract partner on this project. The National Carbon Capture Center (NCCC) at Wilsonville, AL, provided access to syngas gasifier test facilities. The main objective of this project was to develop a cost-effective membrane process that could be used in the relatively near-term tomore » capture CO{sub 2} from shifted syngas generated by a coal-fired Integrated Gasification Combined Cycle (IGCC) power plant. In this project, novel polymeric membranes (designated as Proteus™ membranes) with separation properties superior to conventional polymeric membranes were developed. Hydrogen permeance of up to 800 gpu and H{sub 2}/CO{sub 2} selectivity of >12 was achieved using a simulated syngas mixture at 150°C and 50 psig, which exceeds the original project targets of 200 gpu for hydrogen permeance and 10 for H{sub 2}/CO{sub 2} selectivity. Lab-scale Proteus membrane modules (with a membrane area of 0.13 m{sup 2}) were also developed using scaled-up Proteus membranes and high temperature stable module components identified during this project. A mixed-gas hydrogen permeance of about 160 gpu and H{sub 2}/CO{sub 2} selectivity of >12 was achieved using a simulated syngas mixture at 150°C and 100 psig. We believe that a significant improvement in the membrane and module performance is likely with additional development work. Both Proteus membranes and lab-scale Proteus membrane modules were further evaluated using coal-derived syngas streams at the National Carbon Capture Center (NCCC). The results indicate that all module components, including the Proteus membrane, were stable under the field conditions (feed pressures: 150-175 psig and feed temperatures: 120-135°C) for over 600 hours. The field performance of both Proteus membrane stamps and Proteus membrane modules is consistent with the results obtained in the lab, suggesting that the presence of sulfur-containing compounds (up to 780 ppm hydrogen sulfide), saturated water vapor, carbon monoxide and heavy hydrocarbons in the syngas feed stream has no adverse effect on the Proteus membrane or module performance. We also performed an economic analysis for a number of membrane process designs developed in this project (using hydrogen-selective membranes, alone or in the combination with CO{sub 2}- selective membranes). The current field performance for Proteus membranes was used in the design analysis. The study showed the current best design has the potential to reduce the increase in Levelized Cost of Electricity (LCOE) caused by 90% CO{sub 2} capture to about 15% if co-sequestration of H{sub 2}S is viable. This value is still higher than the DOE target for increase in LCOE (10%); however, compared to the base-case Selexol process that gives a 30% increase in LCOE at 90% CO2 capture, the membrane-based process appears promising. We believe future improvements in membrane performance have the potential to reach the DOE target.« less

Synthesis and characterization of electrospun molybdenum dioxide-carbon nanofibers as sulfur matrix additives for rechargeable lithium-sulfur battery applications.

PubMed

Zhuang, Ruiyuan; Yao, Shanshan; Jing, Maoxiang; Shen, Xiangqian; Xiang, Jun; Li, Tianbao; Xiao, Kesong; Qin, Shibiao

2018-01-01

One-dimensional molybdenum dioxide-carbon nanofibers (MoO 2 -CNFs) were prepared using an electrospinning technique followed by calcination, using sol-gel precursors and polyacrylonitrile (PAN) as a processing aid. The resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Brunauer-Emmet-Teller (BET) surface area measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). MoO 2 -CNFs with an average diameter of 425-575 nm obtained after heat treatment were used as a matrix to prepare sulfur/MoO 2 -CNF cathodes for lithium-sulfur (Li-S) batteries. The polysulfide adsorption and electrochemical performance tests demonstrated that MoO 2 -CNFs did not only act as polysulfide reservoirs to alleviate the shuttle effect, but also improve the electrochemical reaction kinetics during the charge-discharge processes. The effect of MoO 2 -CNF heat treatment on the cycle performance of sulfur/MoO 2 -CNFs electrodes was examined, and the data showed that MoO 2 -CNFs calcined at 850 °C delivered optimal performance with an initial capacity of 1095 mAh g -1 and 860 mAh g -1 after 50 cycles. The results demonstrated that sulfur/MoO 2 -CNF composites display a remarkably high lithium-ion diffusion coefficient, low interfacial resistance and much better electrochemical performance than pristine sulfur cathodes.

Inhibiting polysulfides diffusion of lithium-sulfur batteries using an acetylene black-CoS2 modified separator: Mechanism research and performance improvement

NASA Astrophysics Data System (ADS)

Zeng, Pan; Huang, Liwu; Zhang, Xinling; Han, Yamiao; Chen, Yungui

2018-01-01

Lithium-sulfur (Li-S) batteries are considered as one of the most promising chemistries in secondary energy storage field owing to their high energy density. However, the poor electrochemical performance mainly associated with the polysulfides shuttle has greatly hampered their practical application. Herein, a simple acetylene black (AB)-CoS2 coated separator is first designed to suppress the migration of polysulfides. The AB-CoS2 modified separator can not only efficiently capture the polysulfides by forming strong chemical bonding but also guarantee the rapid lithium ions diffusion. Moreover, the AB-CoS2 coating could serve as an upper current collector to accelerate electron transport for reinforcing the utilization of sulfur and ensuring the reactivation of the trapped active material. Consequently, the Li-S cell using AB-CoS2 modified separator shows a long-term cycling stability with an extremely low decay rate (0.09% per cycle) up to 450 cycles at a high rate of 2 C (3350 mA g-1). It also exhibits excellent rate capabilities, which maintains a capacity of 475 mAh g-1 even at 4.0 C rate.

A fuel-cell-assisted iron redox process for simultaneous sulfur recovery and electricity production from synthetic sulfide wastewater.

PubMed

Zhai, Lin-Feng; Song, Wei; Tong, Zhong-Hua; Sun, Min

2012-12-01

Sulfide present in wastewaters and waste gases should be removed due to its toxicity, corrosivity, and malodorous property. Development of effective, stable, and feasible methods for sulfur recovery from sulfide attains a double objective of waste minimization and resource recovery. Here we report a novel fuel-cell-assisted iron redox (FC-IR) process for simultaneously recovering sulfur and electricity from synthetic sulfide wastewater. The FC-IR system consists of an oxidizing reactor where sulfide is oxidized to elemental sulfur by Fe(III), and a fuel cell where Fe(III) is regenerated from Fe(II) concomitantly with electricity producing. The oxidation of sulfide by Fe(III) is significantly dependent on solution pH. Increasing the pH from 0.88 to 1.96 accelerates the oxidation of sulfide, however, lowers the purity of the produced elemental sulfur. The performance of fuel cell is also a strong function of solution pH. Fe(II) is completely oxidized to Fe(III) when the fuel cell is operated at a pH above 6.0, whereas only partially oxidized below pH 6.0. At pH 6.0, the highest columbic efficiency of 75.7% is achieved and electricity production maintains for the longest time of 106 h. Coupling operation of the FC-IR system obtains sulfide removal efficiency of 99.90%, sulfur recovery efficiency of 78.6 ± 8.3%, and columbic efficiency of 58.6 ± 1.6%, respectively. These results suggest that the FC-IR process is a promising tool to recover sulfur and energy from sulfide. Copyright © 2012 Elsevier B.V. All rights reserved.

Fe-S cluster biogenesis in isolated mammalian mitochondria: coordinated use of persulfide sulfur and iron and requirements for GTP, NADH, and ATP.

PubMed

Pandey, Alok; Pain, Jayashree; Ghosh, Arnab K; Dancis, Andrew; Pain, Debkumar

2015-01-02

Iron-sulfur (Fe-S) clusters are essential cofactors, and mitochondria contain several Fe-S proteins, including the [4Fe-4S] protein aconitase and the [2Fe-2S] protein ferredoxin. Fe-S cluster assembly of these proteins occurs within mitochondria. Although considerable data exist for yeast mitochondria, this biosynthetic process has never been directly demonstrated in mammalian mitochondria. Using [(35)S]cysteine as the source of sulfur, here we show that mitochondria isolated from Cath.A-derived cells, a murine neuronal cell line, can synthesize and insert new Fe-(35)S clusters into aconitase and ferredoxins. The process requires GTP, NADH, ATP, and iron, and hydrolysis of both GTP and ATP is necessary. Importantly, we have identified the (35)S-labeled persulfide on the NFS1 cysteine desulfurase as a genuine intermediate en route to Fe-S cluster synthesis. In physiological settings, the persulfide sulfur is released from NFS1 and transferred to a scaffold protein, where it combines with iron to form an Fe-S cluster intermediate. We found that the release of persulfide sulfur from NFS1 requires iron, showing that the use of iron and sulfur for the synthesis of Fe-S cluster intermediates is a highly coordinated process. The release of persulfide sulfur also requires GTP and NADH, probably mediated by a GTPase and a reductase, respectively. ATP, a cofactor for a multifunctional Hsp70 chaperone, is not required at this step. The experimental system described here may help to define the biochemical basis of diseases that are associated with impaired Fe-S cluster biogenesis in mitochondria, such as Friedreich ataxia. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levendis, Y.A.; Zhu, W.; Wise, D.L.

A fundamental study was conducted on the effectiveness of the chemical calcium magnesium acetate (CMA) as a sulfur capture agent during combustion of pulverized coal. It was based on high-temperature laboratory-bench experiments with the scope of exploring the use of CMA as a dry scrubbing'' medium for in-boiler injection. Two methods of CMA introduction in the furnace were considered: dry-spraying fine powders of the chemical and wet-spraying aqueous solutions to generate fine aerosols. It considered conditions pertinent to post-flame in-boiler injection of CMA to identify optimum temperatures and residence times. In addition to the versatility of the water-soluble CMA tomore » enable spray drying injection and therefore eliminate grinding costs, there are other attractive features. Mainly, its ability to form highly cenospheric, popcorn''-like, oxide particles on heating to high temperatures. These cenospheres possess thin, porous walls with blowholes that enable penetration of the SO[sub 2] in the interior of the particle which promotes high sorbent utilization. SO[sub 2] captures in the order of 90% were achieved with dry-injection of the chemical at furnace gas temperatures of about 1,000[degree]C, a Ca/S ratio of 2, and particle size of [approximately] 50[mu]m. Moreover, CMA was superior (by over 40%) to either CaCO[sub 3] or Ca(OH)[sub 2] in sulfur capture effectiveness per unit mass of calcium. This commercially obtained CMA was even superior to reagent-grade calcium acetate (by as much as 30%), again per unit mass of calcium. The utilization of CMA and calcium acetate depended on the cenosphere wall thickness, rather than the particle size and, thus, outperformed other sorbents regardless of the size of the resulting oxide particles.« less

Migration and transformation of sulfur in the municipal sewage sludge during disposal in cement kiln.

PubMed

Huang, Yuyan; Li, Haoxin; Jiang, Zhengwu; Yang, Xiaojie; Chen, Qing

2018-05-07

The aim of this work was to investigate the migration and transformation of sulfur in the municipal sewage sludge during disposal in cement kiln, and better understand the emission of the sulfur related pollutants in this process. In consideration of the temperature conditions in the practical operation, municipal sewage sludge was pre-dried at 105 °C, and then dried at 210, 260 and 310 °C, co-combusted with cement raw mill at 800, 900 and 1000 °C, and 1350, 1400 and 1450 °C respectively in the laboratory. X-ray photoelectron spectroscopy (XPS) was used to determine the S2p spectral lines of the municipal sewage sludge treated in the different process. Besides, The Thermal Analysis-Thermogravimetry (DTA-TG), Back Scattered Electron (BSE) and Energy Dispersive Spectrometer (EDS) were also employed to explore the mechanism of sulfur subsistence at 1450 °C. The results indicate that sulfide, thiophene, sulfone and sulfate are mainly sulfur compound in the municipal sewage sludge dried at 105 °C. Sulfoxide, a new sulfur compound, appears after it is further dried at 210 °C. The relative contents of sulfide and thiophene are continuously declined as the drying temperature increases due to their evaporation, decomposition and transformation in this process. The transformation of sulfide and thiophene makes the relative contents of sulfoxide and sulfate accordingly increased. However, the relative content of sulfone experiences an elevating-lowering process while the dry temperature elevated from 210 to 310 °C. This case is related to its evaporation and decomposition, as well as its production for the transformation of sulfide and thiophene. In the co-combustion process, sulfide, thiophene and sulfone are entirely vanished for their evaporation, decomposition and transformation. Sulfone is still contained at 800 °C, but when the temperature unceasingly rises, it is completely decomposed or evaporated and sulfate is the only sulfur compound. The microstructures left by the gas release are also observed in the mixtures sintered at 1450 °C, however sulfate still exists even at 1450 °C. The BSE and EDS results show that the melt phase is the important contribution to the appearance of sulfate at the high temperature. These results will sever as a theoretically reference for the pollution control of the sulfur related pollutants in the disposal process of the municipal sewage sludge in cement kiln. Copyright © 2018 Elsevier Ltd. All rights reserved.

Surface passivation process of compound semiconductor material using UV photosulfidation

DOEpatents

Ashby, Carol I. H.

1995-01-01

A method for passivating compound semiconductor surfaces by photolytically disrupting molecular sulfur vapor with ultraviolet radiation to form reactive sulfur which then reacts with and passivates the surface of compound semiconductors.

Impregnating Coal With Calcium Carbonate

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Voecks, Gerald E.; Gavalas, George R.

1991-01-01

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Understanding the role of different conductive polymers in improving the nanostructured sulfur cathode performance.

PubMed

Li, Weiyang; Zhang, Qianfan; Zheng, Guangyuan; Seh, Zhi Wei; Yao, Hongbin; Cui, Yi

2013-01-01

Lithium sulfur batteries have brought significant advancement to the current state-of-art battery technologies because of their high theoretical specific energy, but their wide-scale implementation has been impeded by a series of challenges, especially the dissolution of intermediate polysulfides species into the electrolyte. Conductive polymers in combination with nanostructured sulfur have attracted great interest as promising matrices for the confinement of lithium polysulfides. However, the roles of different conductive polymers on the electrochemical performances of sulfur electrode remain elusive and poorly understood due to the vastly different structural configurations of conductive polymer-sulfur composites employed in previous studies. In this work, we systematically investigate the influence of different conductive polymers on the sulfur cathode based on conductive polymer-coated hollow sulfur nanospheres with high uniformity. Three of the most well-known conductive polymers, polyaniline (PANI), polypyrrole (PPY), and poly(3,4-ethylenedioxythiophene) (PEDOT), were coated, respectively, onto monodisperse hollow sulfur nanopsheres through a facile, versatile, and scalable polymerization process. The sulfur cathodes made from these well-defined sulfur nanoparticles act as ideal platforms to study and compare how coating thickness, chemical bonding, and the conductivity of the polymers affected the sulfur cathode performances from both experimental observations and theoretical simulations. We found that the capability of these three polymers in improving long-term cycling stability and high-rate performance of the sulfur cathode decreased in the order of PEDOT > PPY > PANI. High specific capacities and excellent cycle life were demonstrated for sulfur cathodes made from these conductive polymer-coated hollow sulfur nanospheres.

Sulfur metabolism in Escherichia coli and related bacteria: facts and fiction.

PubMed

Sekowska, A; Kung, H F; Danchin, A

2000-04-01

Living organisms are composed of macromolecules made of hydrogen, carbon, nitrogen, oxygen, phosphorus and sulfur. Much work has been devoted to the metabolism of the first five elements, but much remains to be understood about sulfur metabolism. We review here the situation in Escherichia coli and related bacteria, where more than one hundred genes involved in sulfur metabolism have already been discovered in this organism. Examination of the genome suggests that many more will be found, especially genes involved in regulation, scavenging of sulfur containing molecules and synthesis of coenzymes or prosthetic groups. Furthermore, the involvement of methionine as the universal start of proteins as well as that of its derivative S-adenosylmethionine in a vast variety of cell processes argue in favour of a major importance of sulfur metabolism in all organisms.

Direct measurement of polysulfide shuttle current: A window into understanding the performance of lithium-sulfur cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moy, Derek; Manivannan, A.; Narayanan, S. R.

2014-11-04

The shuttling of polysulfide ions between the electrodes in a lithium-sulfur battery is a major technical issue limiting the self-discharge and cycle life of this high-energy rechargeable battery. Although there have been attempts to suppress the shuttling process, there has not been a direct measurement of the rate of shuttling. We report here a simple and direct measurement of the rate of the shuttling (that we term “shuttle current”), applicable to the study of any type of lithium-sulfur cell. We demonstrate the effectiveness of this measurement technique using cells with and without lithium nitrate (a widely-used shuttle suppressor additive). Wemore » present a phenomenological analysis of the shuttling process and simulate the shuttle currents as a function of the state-of-charge of a cell. We also demonstrate how the rate of decay of the shuttle current can be used to predict the capacity fade in a lithium-sulfur cell due to the shuttle process. As a result, we expect that this new ability to directly measure shuttle currents will provide greater insight into the performance differences observed with various additives and electrode modifications that are aimed at suppressing the rate of shuttling of polysulfide ions and increasing the cycle life of lithium-sulfur cells.« less

New insight into the mechanism of peroxymonosulfate activation by sulfur-containing minerals: Role of sulfur conversion in sulfate radical generation.

PubMed

Zhou, Yang; Wang, Xiaolei; Zhu, Changyin; Dionysiou, Dionysios D; Zhao, Guangchao; Fang, Guodong; Zhou, Dongmei

2018-06-04

Peroxymonosulfate (PMS) or persulfate activation by sulfur-containing minerals has been applied extensively for the degradation of contaminants; however, the role of sulfur conversion in this process has not been fully explored. In this study, pyrite (FeS 2 )-based PMS activation process was developed for diethyl phthalate (DEP) degradation, and its underlying mechanisms were elucidated. PMS was found to be efficiently activated by FeS 2 for DEP degradation and mineralization, achieving 58.9% total organic carbon removal using 0.5 g/L FeS 2 and 2.0 mM PMS. Sulfides were the dominant electron donor for PMS activation, and mediated Fe(II) regeneration to activate PMS on the surface of FeS 2 particles. Meanwhile, different sulfur conversion intermediates, such as S 5 2- , S 8 0 , S 2 O 3 2- , and SO 3 2- , were formed from the oxidation of sulfides by Fe(III) and PMS, and determined by X-ray photoelectron spectroscopy and in-situ attenuated total reflectance Fourier transform infrared spectroscopy analysis. SO 3 2- was the dominant sulfur species responsible for sulfate radicals (SO 4 - ) generation by activating PMS directly or activating Fe(III) to initiate a radical chain reaction, which was supported by the electron paramagnetic resonance results. This study highlights the important role of sulfur conversion in PMS activation by pyrite and provides new insights into the mechanism of oxidant activation by sulfur-containing minerals. Copyright © 2018. Published by Elsevier Ltd.

Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring

NASA Astrophysics Data System (ADS)

Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Leandro, Luana Di; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

2016-03-01

Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials.Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08632a

Toward understanding the effect of low-activity waste glass composition on sulfur solubility

DOE PAGES

Vienna, John D.; Kim, Dong -Sang; Muller, Isabelle S.; ...

2014-07-24

The concentration of sulfur in nuclear waste glass melter feed must be maintained below the point where salt accumulates on the melt surface. The allowable concentrations may range from 0.37 to over 2.05 weight percent (of SO 3 on a calcined oxide basis) depending on the composition of the melter feed and processing conditions. If the amount of sulfur exceeds the melt tolerance level, a molten salt will accumulate, which may upset melter operations and potentially shorten the useful life of the melter. At the Hanford site, relatively conservative limits have been placed on sulfur loading in melter feed, whichmore » in turn significantly increases the amount of glass that will be produced. Crucible-scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. A model was developed to predict the solubility of SO 3 in glass based on 252 simulated Hanford low-activity waste (LAW) glass compositions. This model represents the data well, accounting for over 85% of the variation in data, and was well validated. The model was also found to accurately predict the tolerance for sulfur in melter feed for 13 scaled melter tests of simulated LAW glasses. The model can be used to help estimate glass volumes and make informed decisions on process options. The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that most increase sulfur solubility are Li 2O > V 2O 5> CaO ≈ P 2O 5 > Na 2O ≈ B 2O 3 > K 2O. The components that most decrease sulfur solubility are Cl > Cr 2O 3 > Al 2O 3 > ZrO 2 ≈ SnO 2 > Others ≈ SiO 2. As a result, the order of component effects is similar to previous literature data, in most cases.« less

Influence of pressure on pyrolysis of black liquor: 2. Char yields and component release.

PubMed

Whitty, Kevin; Kullberg, Mika; Sorvari, Vesa; Backman, Rainer; Hupa, Mikko

2008-02-01

This is the second in a series of papers concerning the behavior of black liquor during pyrolysis at elevated pressures. Two industrial black liquors were pyrolyzed under pressurized conditions in two laboratory-scale devices, a pressurized single-particle reactor and a pressurized grid heater. Temperatures ranging between 650 and 1100 degrees C and pressures in the range 1-20 bar were studied. Char yields were calculated and based on analysis of some of the chars the fate of carbon, sodium, potassium and sulfur was determined as a function of pyrolysis pressure. At temperatures below 800 degrees C little variation in char yield was observed at different pressures. At higher temperatures char yield increased with pressure due to slower decomposition of sodium carbonate. For the same reason, sodium release decreased with pressure. Sulfur release, however, increased with pressure primarily because there was less opportunity for its capture in the less-swollen chars.

Expanding lipid proxies to the next dimension: Developing methods for determination of oxygen isotope ratios in plant waxes

NASA Astrophysics Data System (ADS)

Mason, P. R. D.; Roerdink, D. L.; Galic, A.; Martin, W.

2014-12-01

The Archean oceans are thought to have been depleted in sulfate, reflecting widespread anoxic conditions and limited input of oxidized sulfur species from atmospheric photolysis. This is supported by the paucity of sulfate-bearing minerals and the relatively limited mass-dependent sulfur isotope fractionation in the majority of the Archean geological record. An exception to this is the occurrence of barite deposits in the Palaeoarchean (3.5-3.2 Ga) which indicate spatial or temporal increases in sulfate concentration. The origin and extent of these enrichments remains controversial and has been difficult to assess due to limited and highly variable data. Here we compile an extensive new database of SIMS multiple sulfur isotope data for pyrite and barite from across the Barberton Greenstone Belt in South Africa in order to further investigate the extent and origin of any sulfate enrichment. Individual pyrites were measured with good stratigraphic and petrographic control. Pyrite δ56Fe was used to further delineate pyrite populations and pathways of pyrite formation. Our new sulfur isotope data support conventional models where a positive Δ33S was derived from heterogeneous photolytic elemental S, with negative Δ33S capturing a homogenized marine sulfate reservoir. Pyrite multiple S isotope data closely track the abundance of barite, suggesting that marine sulfate levels were generally low and that sulfate increases were sporadic and localized. We speculate that the subsequent Neoarchean scarcity was controlled by biological evolution.

Optimization of Limestone Feed Size of a Pressurized Fluidized Bed Combustor

NASA Astrophysics Data System (ADS)

Shimizu, Tadaaki; Saastamolnen, Jaakko

Limestone attrition is a major cause of loss of limestone during pressurized fluidized bed combustion. In the authors' previous works, the analysis of published results of solid attrition and desulfurization was conducted to determine the attrition rate expression. The specific attrition rate (rate of decrease in diameter) was estimated to be second order with respect to particle diameter in the previous work. This rate expression implies that reduction of feed size of limestone is effective for suppression of loss of limestone by attrition. However, too much grinding of raw limestone will increase the content of fine particles that are readily elutriated by gas stream and do not contribute to the sulfur capture. In this work, modeling works are conducted for particle attrition and desulfurization in order to predict the effect of feed size of limestone on total consumption of limestone and desulfurization is discussed. Optimum particle size to suppress limestone consumption was approximately 0.7 mm (as D p50 ). However, the control of solid drain rate from the bottom was found to have more influence on total limestone consumption rate. Emissions of SO2 from low sulfur coal (S=0.33%) could be sufficiently low irrespective of limestone feed size but SO2 emissions from coals with higher sulfur content than 0.5% were anticipated to increase drastically. Such drastic change in SO2 emissions with the change in sulfur content is attributable to non-linear nature of reaction rate for attrition-enhanced desulfurization by limestone.

Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

NASA Astrophysics Data System (ADS)

Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

2018-03-01

In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

Nitrogen-doped graphene aerogel as both a sulfur host and an effective interlayer for high-performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Sui, Zhu-Yin; Yang, Quan-Sheng; Zhou, Hang-Yu; Li, Xin; Sun, Ya-Nan; Xiao, Pei-Wen; Wei, Zhi-Xiang; Han, Bao-Hang

2017-12-01

Lithium-sulfur batteries have attracted great concern because of the high theoretical capacity of sulfur (1675 mA h g-1). However, the poor electrical conductivity and volumetric expansion of sulfur along with the dissolution of lithium polysulfides largely limit their practical application. In this study, nitrogen-doped graphene aerogel (NGA) with high nitrogen content and porosity is used as a host for the impregnation of sulfur. The effects of sulfur impregnation on the specific surface area, pore volume, and microstructure of NGA supported sulfur composite (S@NGA) are well investigated. Furthermore, NGA is also processed into a NGA film, which is sandwiched between a separator and S@NGA cathode. The lithium-sulfur battery with such a configuration delivers a high reversible capacity of 1514 mA h g-1 at 0.1 C, excellent rate performance (822 mA h g-1 at 2.0 C), and good cycling stability (946 mA h g-1 at 0.5 C even after 100 cycles). The enhanced electrochemical performance can be ascribed to the introduction of the NGA interlayer, the unique interconnected porous structure, and strong interaction between the three-dimensional nitrogen-doped graphene network and the homogeneously dispersed sulfur and/or lithium polysulfides.

Nitrogen-doped graphene aerogel as both a sulfur host and an effective interlayer for high-performance lithium-sulfur batteries.

PubMed

Sui, Zhu-Yin; Yang, Quan-Sheng; Zhou, Hang-Yu; Li, Xin; Sun, Ya-Nan; Xiao, Pei-Wen; Wei, Zhi-Xiang; Han, Bao-Hang

2017-12-08

Lithium-sulfur batteries have attracted great concern because of the high theoretical capacity of sulfur (1675 mA h g -1 ). However, the poor electrical conductivity and volumetric expansion of sulfur along with the dissolution of lithium polysulfides largely limit their practical application. In this study, nitrogen-doped graphene aerogel (NGA) with high nitrogen content and porosity is used as a host for the impregnation of sulfur. The effects of sulfur impregnation on the specific surface area, pore volume, and microstructure of NGA supported sulfur composite (S@NGA) are well investigated. Furthermore, NGA is also processed into a NGA film, which is sandwiched between a separator and S@NGA cathode. The lithium-sulfur battery with such a configuration delivers a high reversible capacity of 1514 mA h g -1 at 0.1 C, excellent rate performance (822 mA h g -1 at 2.0 C), and good cycling stability (946 mA h g -1 at 0.5 C even after 100 cycles). The enhanced electrochemical performance can be ascribed to the introduction of the NGA interlayer, the unique interconnected porous structure, and strong interaction between the three-dimensional nitrogen-doped graphene network and the homogeneously dispersed sulfur and/or lithium polysulfides.

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries.

PubMed

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2014-01-21

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g(-1) and capacity retention at 70.7% (904 mA h g(-1)) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.

Elimination of ethanethiol released from municipal wastes by absorption sequencing electrochemical oxidation.

PubMed

Gong, Xiao; Yang, Xu; Zheng, Haoyue; Wu, Zucheng

2017-07-01

As a typical municipal waste landfill gas, ethanethiol can become an air pollutant because of its low odor threshold concentration and toxicity to human beings. A hybrid process of absorption combined with electrochemical oxidation to degrade ethanethiol was investigated. The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF 4 ) was employed as an absorbent to capture ethanethiol from the air stream. Electrochemical oxidation demonstrated that ethanethiol could be oxidized on a β-PbO 2 anode modified with fluoride, while [BMIM]BF 4 was used as an electrolyte. After a reaction time of 90 min under a current density of 50 mA/cm 2 , ethanethiol could be thoroughly destructed by the successive attack of hydroxyl radicals (·OH) electrogenerated on the surface of the β-PbO 2 anode, while the sulfur atoms in ethanethiol were ultimately converted to sulfate ions [Formula: see text]. The reaction mechanism is proposed, and the operating condition is also estimated with a kinetic model. This hybrid process could be a promising way to remove thiol compounds from municipal waste landfill gases.

Nitrogen-Doped Mesoporous Carbon: A Top-Down Strategy to Promote Sulfur Immobilization for Lithium-Sulfur Batteries.

PubMed

Zhao, Xiaohui; Liu, Ying; Manuel, James; Chauhan, Ghanshyam S; Ahn, Hyo-Jun; Kim, Ki-Won; Cho, Kwon-Koo; Ahn, Jou-Hyeon

2015-10-12

The loss of active sulfur material is a challenge in the application of lithium-sulfur (Li-S) batteries. To immobilize sulfur, a nitrogen-doped mesoporous carbon (PMC) was synthesized with polyaniline (PANi) as the carbon source, which was used for development of Li-S batteries. The nitrogen content and pore system of the PMCs were modulated by varying the pyrolysis temperature to impart good electrochemical properties to the Li-S cells. As a result, the optimal capacity reversibility was obtained with the PMC synthesized at 700 °C that consisted of 12.8 % nitrogen. The enhanced cycle performance of Li-S cells was also validated at high sulfur contents up to 70 % and high C-rates up to 2 C. Furthermore, such sulfur/PMC cathodes could alleviate volume expansion during the discharge process. The results suggest that our synthesized nitrogen-doped PMCs prepared by this top-down strategy are promising materials to immobilize active sulfur in Li-S batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel designs of fluidized bed combustors for low pollutant emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, W.; Bleek, C.M. van den; Dam-Johansen, K.

1995-12-31

It is known that NH{sub 3}, released during the devolatilization of fuel, is an important precursor for NO formation in fluidized bed combustors. On the other hand, NH{sub 3} may be used as a reducing agent in the thermal DeNO{sub x} process to reduce NO{sub x} emission levels. In this paper, a new concept of fluidized bed combustors is proposed based on the idea of in situ reduction of NO{sub x} by self-produced NH{sub 3} from fuel without lowering the sulfur capture level. This design is intended to separate the NH{sub 3} release process under reducing conditions from the charmore » combustion process under oxidizing conditions; this self-released NH{sub 3}, together with some combustibles, is mixed with gaseous combustion products in the upper part of the combustor for a further reduction of the NO{sub x} formed during combustion. Furthermore, the combustion of the combustibles may cause the temperature to rise in this upper zone and thereby reduce the emission of N{sub 2}O. The applications of this design to bubbling and circulating fluidized bed combustors are described and the mechanisms of the main reactions involved discussed.« less

Cathode Loading Effect on Sulfur Utilization in Lithium–Sulfur Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ke; Liu, Helen; Gan, Hong

The Lithium-Sulfur (Li-S) battery is under intensive research in recent years due to its potential to provide higher energy density and lower cost than the current state-of-the-art lithium-ion battery technology. To meet cost target for transportation application, high sulfur loading up to 8 mAh cm -2 is predicted by modeling. In this work, we have investigated the sulfur loading effect on the galvanostatic charge/discharge cycling performance of Li-S cells with theoretical sulfur loading ranging from 0.5 mAh cm -2 to 7.5 mAh cm -2. We found that the low sulfur utilization of electrodes with sulfur loading of > 3.0 mAhmore » cm-2 is due to their inability to deliver capacities at the 2.1V voltage plateau, which corresponds to the conversion of soluble Li 2S 4 to insoluble Li 2S 2/Li 2S. This electrochemical conversion process recovers to deliver the expected sulfur utilization after several activation cycles for electrodes with sulfur loading up to 4.5 mAh cm -2. For electrodes with 7.0 mAh cm -2 loading, no sulfur utilization recovery was observed for 100 cycles. The root cause of this phenomenon is elucidated by SEM/EDS and EIS investigation. Carbon interlayer cell design and low rate discharge activation are demonstrated to be effective mitigation methods.« less

Cathode Loading Effect on Sulfur Utilization in Lithium–Sulfur Battery

DOE PAGES

Sun, Ke; Liu, Helen; Gan, Hong

2016-05-01

The Lithium-Sulfur (Li-S) battery is under intensive research in recent years due to its potential to provide higher energy density and lower cost than the current state-of-the-art lithium-ion battery technology. To meet cost target for transportation application, high sulfur loading up to 8 mAh cm -2 is predicted by modeling. In this work, we have investigated the sulfur loading effect on the galvanostatic charge/discharge cycling performance of Li-S cells with theoretical sulfur loading ranging from 0.5 mAh cm -2 to 7.5 mAh cm -2. We found that the low sulfur utilization of electrodes with sulfur loading of > 3.0 mAhmore » cm-2 is due to their inability to deliver capacities at the 2.1V voltage plateau, which corresponds to the conversion of soluble Li 2S 4 to insoluble Li 2S 2/Li 2S. This electrochemical conversion process recovers to deliver the expected sulfur utilization after several activation cycles for electrodes with sulfur loading up to 4.5 mAh cm -2. For electrodes with 7.0 mAh cm -2 loading, no sulfur utilization recovery was observed for 100 cycles. The root cause of this phenomenon is elucidated by SEM/EDS and EIS investigation. Carbon interlayer cell design and low rate discharge activation are demonstrated to be effective mitigation methods.« less

Sulfur Geochemistry of a Lacustrine Record from Taiwan Reveals Enhanced Marine Aerosol Input during the Early Holocene

PubMed Central

Ding, Xiaodong; Li, Dawei; Zheng, Liwei; Bao, Hongyan; Chen, Huei-Fen; Kao, Shuh-Ji

2016-01-01

Lacustrine record of marine aerosol input has rarely been documented. Here, we present the sulfur geochemistry during the last deglaciation and early Holocene of a sediment core retrieved from the Dongyuan Lake in southern Taiwan. An unusually high sulfur peak accompanying pyrite presence is observed at 10.5 ka BP. Such high sulfur content in lacustrine record is unusual. The δ34S of sulfur varied from +9.5 to + 17.1‰ with two significant positive shifts at 10.5 and 9.4 ka BP. The sources of sulfur and potential processes involving the sulfur isotope variation including bacterial sulfate reduction, volcanic emissions, in-catchment sulfide oxidation and marine aerosol input are discussed. Enhanced marine aerosol input is the most likely explanation for such sulfur peaks and δ34S shifts. The positive δ34S shifts appeared concurrently with the maximum landslide events over Taiwan resulted from enhanced typhoon activities. The synchronicity among records suggests that increased typhoon activities promoted sea spray, and consequently enhanced the marine aerosol input with 34S-enriched sulfate. Our sulfur geochemistry data revealed sea spray history and marine influence onto terrestrial environment at coastal regions. Wider coverage of spatial-temporal lacustrine sulfur geochemistry record is needed to validate the applicability of sulfur proxy in paleoenvironmental research. PMID:27941864

Flash pyrolysis of coal, coal maceral, and coal-derived pyrite with on-line characterization of volatile sulfur compounds

USGS Publications Warehouse

Chou, I.-Ming; Lake, M.A.; Griffin, R.A.

1988-01-01

A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.

Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

2011-12-15

A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Graphene/Sulfur/Carbon Nanocomposite for High Performance Lithium-Sulfur Batteries

PubMed Central

Jin, Kangke; Zhou, Xufeng; Liu, Zhaoping

2015-01-01

Here, we report a two-step synthesis of graphene/sulfur/carbon ternary composite with a multilayer structure. In this composite, ultrathin S layers are uniformly deposited on graphene nanosheets and covered by a thin layer of amorphous carbon derived from β-cyclodextrin on the surface. Such a unique microstructure, not only improves the electrical conductivity of sulfur, but also effectively inhibits the dissolution of polysulfides during charging/discharging processes. As a result, this ternary nanocomposite exhibits excellent electrochemical performance. It can deliver a high initial discharge and charge capacity of 1410 mAh·g−1 and 1370 mAh·g−1, respectively, and a capacity retention of 63.8% can be achieved after 100 cycles at 0.1 C (1 C = 1675 mA·g−1). A relatively high specific capacity of 450 mAh·g−1 can still be retained after 200 cycles at a high rate of 2 C. The synthesis process introduced here is simple and broadly applicable to the modification of sulfur cathode for better electrochemical performance. PMID:28347077

Sulfur and oxygen isotope fractionation during benzene, toluene, ethyl benzene, and xylene degradation by sulfate-reducing bacteria.

PubMed

Knöller, Kay; Vogt, Carsten; Richnow, Hans-Herrmann; Weise, Stephan M

2006-06-15

We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

PubMed

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

Nitrogen-Doped Single-Walled Carbon Nanohorns as a Cost-Effective Carbon Host toward High-Performance Lithium-Sulfur Batteries.

PubMed

Gulzar, Umair; Li, Tao; Bai, Xue; Colombo, Massimo; Ansaldo, Alberto; Marras, Sergio; Prato, Mirko; Goriparti, Subrahmanyam; Capiglia, Claudio; Proietti Zaccaria, Remo

2018-02-14

Nitrogen-doped single-walled carbon nanohorns (N-SWCNHs) are porous carbon material characterized by unique horn-shape structures with high surface areas and good conductivity. Moreover, they can be mass-produced (tons/year) using a novel proprietary process technology making them an attractive material for various industrial applications. One of the applications is the encapsulation of sulfur, which turns them as promising conductive host materials for lithium-sulfur batteries. Therefore, we explore for the first time the electrochemical performance of industrially produced N-SWCNHs as a sulfur-encapsulating conductive material. Fabrication of lithium-sulfur cells based on N-SWCNHs with sulfur composite could achieve a remarkable initial gravimetric capacity of 1650 mA h g -1 , namely equal to 98.5% of the theoretical capacity (1675 mA h g -1 ), with an exceptional sulfur content as high as 80% in weight. Using cyclic chronopotentiometry and impedance spectroscopy, we also explored the dissolution mechanism of polysulfides inside the electrolyte.

Sulfur and Its Role In Modern Materials Science.

PubMed

Boyd, Darryl A

2016-12-12

Although well-known and studied for centuries, sulfur continues to be at the center of an extensive array of scientific research topics. As one of the most abundant elements in the Universe, a major by-product of oil refinery processes, and as a common reaction site within biological systems, research involving sulfur is both broad in scope and incredibly important to our daily lives. Indeed, there has been renewed interest in sulfur-based reactions in just the past ten years. Sulfur research spans the spectrum of topics within the physical sciences including research on improving energy efficiency, environmentally friendly uses for oil refinery waste products, development of polymers with unique optical and mechanical properties, and materials produced for biological applications. This Review focuses on some of the latest exciting ways in which sulfur and sulfur-based reactions are being utilized to produce materials for application in energy, environmental, and other practical areas. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

DOE PAGES

Wang, Qiang; Zheng, Jianming; Walter, Eric; ...

2015-01-09

Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-Smore » cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.« less

Hubble Captures Celestial Fireworks Within the Large Magellanic Cloud

NASA Technical Reports Server (NTRS)

2000-01-01

This is a color Hubble Space Telescope (HST) heritage image of supernova remnant N49, a neighboring galaxy, that was taken with Hubble's Wide Field Planetary Camera 2. Color filters were used to sample light emitted by sulfur, oxygen, and hydrogen. The color image was superimposed on a black and white image of stars in the same field also taken with Hubble. Resembling a fireworks display, these delicate filaments are actually sheets of debris from a stellar explosion.

Low Level Exposure to Sulfur Mustard: Development of a SOP for Analysis of Albumin Adducts and of a System for Non-Invasive Diagnosis on Skin

DTIC Science & Technology

2007-08-01

of fluorinated amino acid derivatives under Electron Capture Atmospheric Pressure Chemical Ionization (EC APCI) conditions results in far better...Figure 6). Mass spectrometric analyses indicated that at least for the synthetic reference compound, the fluorinated derivative could be determined... fluorinated amino acid derivatives under EC APCI conditions (vide supra) results in far better detection limits, when compared to normal electrospray MS

Low temperature oxidation using support molten salt catalysts

DOEpatents

Weimer, Alan W.; Czerpak, Peter J.; Hilbert, Patrick M.

2003-05-20

Molten salt reactions are performed by supporting the molten salt on a particulate support and forming a fluidized bed of the supported salt particles. The method is particularly suitable for combusting hydrocarbon fuels at reduced temperatures, so that the formation NO.sub.x species is reduced. When certain preferred salts are used, such as alkali metal carbonates, sulfur and halide species can be captured by the molten salt, thereby reducing SO.sub.x and HCl emissions.

Product layer development during sulfation and sulfidation of uncalcined limestone particles at elevated pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven, C.A.P.; Yrjas, K.P.; Hupa, M.M.

1998-07-01

Fluidized bed combustion or gasification allows for in-bed sulfur capture with a calcium-based sorbent such as limestone or dolomite. Sorbent particle size, porosity, internal surface, and their variation during conversion have great influence on the conversion of the sorbent. The uptake of SO{sub 2} and H{sub 2}S by five physically different limestones is discussed, for typical pressurized fluidized bed combustor or gasifier conditions: 850/950 C, 15/20 bar. Tests were done in a pressurized thermogravimetric apparatus (P-TGA), the size of the limestone particles was 250--300 {micro}m. It is stressed that the limestones remain uncalcined. A changing internal structure (CIS) model ismore » presented in which reaction kinetics and product layer diffusion are related to the intraparticle surface of reaction, instead of the outer particle surface as in unreacted shrinking core (USC)-type models. The random pore model was used for describing the changing internal pore and reaction surfaces. Rate parameters were extracted for all five limestones using the CIS model and a USC model with variable effective diffusivity. Differences in the sulfur capture performance of the limestones were evaluated. Plots of the CaSO{sub 4} or CaS product layer thickness as a function of conversion are given, and the relative importance of limestone porosity and internal surface is discussed.« less

Behavior or Nonmetallic Materials in Shale Oil Derived Jet Fuels and in High Aromatic and High Sulfur Petroleum Fuels

DTIC Science & Technology

1978-07-01

degrades thermal stability and forms undesirable sulfur dioxide emissions . Although the original premises for controlling total sulfur may not still...eliminate corrosive trace contamination, presence of surfactants which deactivate filter/ separators, carry-over of refinery processing materials, and...increase raw vapor emissions from ground fuel handling facilities and during refueling operations. Controlling raw vapor emissions is difficult at 3

76 FR 41698 - Approval and Promulgation of Air Quality Implementation Plans; New Mexico; Section 110(a)(2...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-15

.../30/1995 9/26/1997, 62 FR 50514 Part 11 Asphalt Process 11/30/1995 9/26/1997, 62 FR 50514 Equipment..., 62 FR 50514 Equipment-Sulfur Dioxide. Part 32 Coal Burning 11/30/1995 9/26/1997, 62 FR 50514... Sulfuric Acid 11/30/1995 9/26/1997, 62 FR 50514 Production Units- Sulfur Dioxide, Acid Mist and Visible...

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

NASA Astrophysics Data System (ADS)

Liu, C.; Jiang, S. Y.; Su, X.

2017-12-01

Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

Emission characteristics of nitrogen- and sulfur-containing odorous compounds during different sewage sludge chemical conditioning processes.

PubMed

Liu, Huan; Luo, Guang-Qian; Hu, Hong-Yun; Zhang, Qiang; Yang, Jia-Kuan; Yao, Hong

2012-10-15

Chemical conditioners are often used to enhance sewage sludge dewaterability through altering sludge properties and flocs structure, both affect odorous compounds emissions not only during sludge conditioning but also in subsequent sludge disposal. This study was to investigate emission characteristics of ammonia (NH(3)), sulfur dioxide (SO(2)), hydrogen sulfide (H(2)S) and carbonyl sulfide (COS) generated from sewage sludge conditioned by three representative conditioners, i.e., organic polymers, iron salts and skeleton builders, F-S (Fenton's reagent and skeleton builders) composite conditioner. The results demonstrate that polyacrylamide (PAM) has an insignificant effect on emission characteristics of nitrogen- and sulfur-containing odorous compounds, because the properties, sulfur and nitrogen speciations are similar in PAM-conditioned sludge and raw sludge (RS). Significant increases of SO(2) and H(2)S emissions in the H(2)SO(4) conditioning process were observed due to the accelerated decomposition of sulfur-containing amino acids in acidic environment. Fenton peroxidation facilitates the formation of COS. CaO can reduce sulfur-containing gases emission via generation of calcium sulfate. However, under strong alkaline conditions, free ammonia or protonated amine in sludge can be easily converted to volatile ammonia, resulting in a significant release of NH(3). Copyright © 2012 Elsevier B.V. All rights reserved.

Near-Zero Emissions Oxy-Combustion Flue Gas Purification Task 2: SOx/Nox/Hg Removal for High Sulfur Coal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nick Degenstein; Minish Shah; Doughlas Louie

2012-05-01

The goal of this project is to develop a near-zero emissions flue gas purification technology for existing PC (pulverized coal) power plants that are retrofitted with oxy-combustion technology. The objective of Task 2 of this project was to evaluate an alternative method of SOx, NOx and Hg removal from flue gas produced by burning high sulfur coal in oxy-combustion power plants. The goal of the program was not only to investigate a new method of flue gas purification but also to produce useful acid byproduct streams as an alternative to using a traditional FGD and SCR for flue gas processing.more » During the project two main constraints were identified that limit the ability of the process to achieve project goals. 1) Due to boiler island corrosion issues >60% of the sulfur must be removed in the boiler island with the use of an FGD. 2) A suitable method could not be found to remove NOx from the concentrated sulfuric acid product, which limits sale-ability of the acid, as well as the NOx removal efficiency of the process. Given the complexity and safety issues inherent in the cycle it is concluded that the acid product would not be directly saleable and, in this case, other flue gas purification schemes are better suited for SOx/NOx/Hg control when burning high sulfur coal, e.g. this project's Task 3 process or a traditional FGD and SCR.« less

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200–350°C

USGS Publications Warehouse

Shanks, Wayne C.; Bischoff, James L.; Rosenbauer, Robert J.

1981-01-01

Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.

Sulfur Speciation in Peat: a Time-zero Signature for the " Spruce and Peatland Responses Under Climate and Environmental Change" Experiment

NASA Astrophysics Data System (ADS)

Furman, O.; Toner, B. M.; Sebestyen, S. D.; Kolka, R. K.; Nater, E. A.

2014-12-01

As part of the "Spruce and Peatland Responses Under Climate and Environmental Change" (SPRUCE) experiment, we made initial measurements of sulfur speciation in peat. These observations represent a "time-zero" relative to the intended soil warming experiment which begins in 2015. Total sulfur and sulfur speciation were measured in peat cores (solid phase) from nine plots (hollows and hummocks) to a depth of 2 m. Peat samples were packed under nitrogen and frozen in the field immediately after collection. All subsequent sample storage, handling, and processing were conducted under inert gas. Sulfur speciation was measured using bulk sulfur 1s X-ray absorption near edge structure (XANES) spectroscopy at the SXRMB instrument at the Canadian Light Source, Saskatoon, SK, Canada and at the 9-BM instrument, Advanced Photon Source, Argonne National Laboratory, IL, USA. Total sulfur concentrations ranged from 968 to 4077 mg sulfur / kg dry peat. Sulfur content increased with depth from 2 g sulfur / m2 in the 0-10 cm increment to a maximum value of 38 g sulfur / m2 in the 50-60 cm increment. These sulfur loadings produced high quality XANES spectra. The nine cores exhibited reproducible trends with depth in both total sulfur and specific sulfur species; however, variability in sulfur speciation was greatest in the top 40 cm. All sulfur detected within the peat solids was in an organic form. The most abundant sulfur species group was composed of organic mono-sulfide and thiol forms, representing approximately half of the total sulfur at all depths. Sulfonate and ester-sulfate species were 10-15 mol% of sulfur and exhibited low variability with depth. A subsurface maximum in organic di-sulfide was observed in the 20-30 cm depth increment, which is the transition zone between transiently oxidized acrotelm and permanently saturated anaerobic catotelm. Quantification of major sulfur pools is important for the SPRUCE experiment as they are likely to be indicators of changes in the oxidation-reduction (redox) status, and mercury methylation potential, of the peat in response to warming and enhanced carbon dioxide.

Characterization of coals for circulating fluidized bed combustion by pilot scale tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, L.A.; Cabanillas, A.C.; Becerra, J.O. de

1995-12-31

The major part of the Spanish coal supply is low range coal with both high ash (20--40%) and sulfur (1--8%) content. The use of this coal, by conventional combustion processes in power and industrial plants, implies a very high environmental impact. The Circulating Fluidized Bed Combustion process enables an efficient use of this coal. The Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas is carrying out a program with the intention of assisting companies in evaluating fuel quality impact, using atmospheric fluidized bed combustion. This paper reviews the major results of the fuel program in order to determine the fluidized bedmore » combustion performance of four fuels. Two lignites, a bituminous coal and an anthracite. The two lignites have very high sulfur content (7% and 8%) but the sulfur is organic in one case and pyritic in the other. The bituminous coal and the anthracite have 1% and 2% sulfur content respectively and the sulfur is pyritic in these cases. In order to reduce the sulfur in the flue gases, a high calcium content limestone has been used as sorbent. The combustion trials have been done in a circulating fluidized bed pilot plant with a 200 mm inside diameter and a height of 6.5 m. The influence of temperature, fluidization velocity, oxygen excess, Ca/S ratio and coal properties have been studied in relation to the combustion efficiency, sulfur retention, CO and NO{sub x} emissions.« less

URANIUM PRECIPITATION PROCESS

DOEpatents

Thunaes, A.; Brown, E.A.; Smith, H.W.; Simard, R.

1957-12-01

A method for the recovery of uranium from sulfuric acid solutions is described. In the present process, sulfuric acid is added to the uranium bearing solution to bring the pH to between 1 and 1.8, preferably to about 1.4, and aluminum metal is then used as a reducing agent to convert hexavalent uranium to the tetravalent state. As the reaction proceeds, the pH rises amd a selective precipitation of uranium occurs resulting in a high grade precipitate. This process is an improvement over the process using metallic iron, in that metallic aluminum reacts less readily than metallic iron with sulfuric acid, thus avoiding consumption of the reducing agent and a raising of the pH without accomplishing the desired reduction of the hexavalent uranium in the solution. Another disadvantage to the use of iron is that positive ferric ions will precipitate with negative phosphate and arsenate ions at the pH range employed.

Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

PubMed

Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

2013-06-25

Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

Biodesulfurization of refractory organic sulfur compounds in fossil fuels.

PubMed

Soleimani, Mehran; Bassi, Amarjeet; Margaritis, Argyrios

2007-01-01

The stringent new regulations to lower sulfur content in fossil fuels require new economic and efficient methods for desulfurization of recalcitrant organic sulfur. Hydrodesulfurization of such compounds is very costly and requires high operating temperature and pressure. Biodesulfurization is a non-invasive approach that can specifically remove sulfur from refractory hydrocarbons under mild conditions and it can be potentially used in industrial desulfurization. Intensive research has been conducted in microbiology and molecular biology of the competent strains to increase their desulfurization activity; however, even the highest activity obtained is still insufficient to fulfill the industrial requirements. To improve the biodesulfurization efficiency, more work is needed in areas such as increasing specific desulfurization activity, hydrocarbon phase tolerance, sulfur removal at higher temperature, and isolating new strains for desulfurizing a broader range of sulfur compounds. This article comprehensively reviews and discusses key issues, advances and challenges for a competitive biodesulfurization process.

Anodizing And Sealing Aluminum In Nonchromated Solutions

NASA Technical Reports Server (NTRS)

Emmons, John R.; Kallenborn, Kelli J.

1995-01-01

Improved process for anodizing and sealing aluminum involves use of 5 volume percent sulfuric acid in water as anodizing solution, and 1.5 to 2.0 volume percent nickel acetate in water as sealing solution. Replaces process in which sulfuric acid used at concentrations of 10 to 20 percent. Improved process yields thinner coats offering resistance to corrosion, fatigue life, and alloy-to-alloy consistency equal to or superior to those of anodized coats produced with chromated solutions.

Grinding into Soft, Powdery Rock

NASA Technical Reports Server (NTRS)

2004-01-01

This hole in a rock dubbed 'Clovis' is the deepest hole drilled so far in any rock on Mars. NASA's Mars Exploration Rover Spirit captured this view with its microscopic imager on martian sol 217 (Aug. 12, 2004) after drilling 8.9 millimeters (0.35 inch) into the rock with its rock abrasion tool. The view is a mosaic of four frames taken by the microscopic imager. The hole is 4.5 centimeters (1.8 inches) in diameter. Clovis is key to a developing story about environmental change on Mars, not only because it is among the softest rocks encountered so far in Gusev Crater, but also because it contains mineral alterations that extend relatively deep beneath its surface. In fact, as evidenced by its fairly crumbly texture, it is possibly the most highly altered volcanic rock ever studied on Mars.

Scientific analysis shows that the rock contains higher levels of the elements sulfur, chlorine, and bromine than are normally encountered in basaltic rocks, such as a rock dubbed 'Humphrey' that Spirit encountered two months after arriving on Mars. Humphrey showed elevated levels of sulfur, chlorine, and bromine only in the outermost 2 millimeters (less than 0.1 inch) of its surface. Clovis shows elevated levels of the same elements along with the associated softness of the rock within a borehole that is 4 times as deep. Scientists hope to compare Clovis to other, less-altered rocks in the vicinity to assess what sort of water-based processes altered the rock. Hypotheses include transport of sulfur, chlorine, and bromine in water vapor in volcanic gases; hydrothermal circulation (flow of volcanically heated water through rock); or saturation in a briny soup containing the same elements.

In this image, very fine-grained material from the rock has clumped together by electrostatic attraction and fallen into the borehole. NASA/JPL/Cornell/USGS

Sulfur amino acids and alanine on pyrite (100) by X-ray photoemission spectroscopy: Surface or molecular role?

NASA Astrophysics Data System (ADS)

Sanchez-Arenillas, M.; Galvez-Martinez, S.; Mateo-Marti, E.

2017-08-01

This paper describes the first successful adsorption of the cysteine, cystine, methionine and alanine amino acids on the pyrite (100) surface under ultra-high vacuum conditions with crucial chemical adsorption parameters driving the process. We have demonstrated by X-ray photoemission spectroscopy (XPS) that the surface pretreatment annealing process on pyrite surfaces is a critical parameter driving surface reactivity. The presence of enriched monosulfide species on the pyrite (100) surface favours the amino acid NH2 chemical form, whereas a longer annealing surface pretreatment of over 3 h repairs the sulfur vacancies in the pyrite, enriching disulfide species on the pyrite surface, which promotes NH3+ adsorption due to the sulfur vacancies in the pyrite being replaced by sulfur atom dimers (S22-) on the surface. Furthermore, even if the surface chemistry (monosulfide or disulfide species enrichment) is the main factor promoting a partial conversion from NH2 to NH3+ species, the unique chemical structure of each amino acid provides a particular fingerprint in the process.

Comparative techno-economic analysis of steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological pretreatments of corn stover.

PubMed

Baral, Nawa Raj; Shah, Ajay

2017-05-01

Pretreatment is required to destroy recalcitrant structure of lignocelluloses and then transform into fermentable sugars. This study assessed techno-economics of steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological pretreatments, and identified bottlenecks and operational targets for process improvement. Techno-economic models of these pretreatment processes for a cellulosic biorefinery of 113.5 million liters butanol per year excluding fermentation and wastewater treatment sections were developed using a modelling software-SuperPro Designer. Experimental data of the selected pretreatment processes based on corn stover were gathered from recent publications, and used for this analysis. Estimated sugar production costs ($/kg) via steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological methods were 0.43, 0.42, 0.65 and 1.41, respectively. The results suggest steam explosion and sulfuric acid pretreatment methods might be good alternatives at present state of technology and other pretreatment methods require research and development efforts to be competitive with these pretreatment methods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fe-S Cluster Biogenesis in Isolated Mammalian Mitochondria

PubMed Central

Pandey, Alok; Pain, Jayashree; Ghosh, Arnab K.; Dancis, Andrew; Pain, Debkumar

2015-01-01

Iron-sulfur (Fe-S) clusters are essential cofactors, and mitochondria contain several Fe-S proteins, including the [4Fe-4S] protein aconitase and the [2Fe-2S] protein ferredoxin. Fe-S cluster assembly of these proteins occurs within mitochondria. Although considerable data exist for yeast mitochondria, this biosynthetic process has never been directly demonstrated in mammalian mitochondria. Using [35S]cysteine as the source of sulfur, here we show that mitochondria isolated from Cath.A-derived cells, a murine neuronal cell line, can synthesize and insert new Fe-35S clusters into aconitase and ferredoxins. The process requires GTP, NADH, ATP, and iron, and hydrolysis of both GTP and ATP is necessary. Importantly, we have identified the 35S-labeled persulfide on the NFS1 cysteine desulfurase as a genuine intermediate en route to Fe-S cluster synthesis. In physiological settings, the persulfide sulfur is released from NFS1 and transferred to a scaffold protein, where it combines with iron to form an Fe-S cluster intermediate. We found that the release of persulfide sulfur from NFS1 requires iron, showing that the use of iron and sulfur for the synthesis of Fe-S cluster intermediates is a highly coordinated process. The release of persulfide sulfur also requires GTP and NADH, probably mediated by a GTPase and a reductase, respectively. ATP, a cofactor for a multifunctional Hsp70 chaperone, is not required at this step. The experimental system described here may help to define the biochemical basis of diseases that are associated with impaired Fe-S cluster biogenesis in mitochondria, such as Friedreich ataxia. PMID:25398879

Table of Historical Sulfur Dioxide National Ambient Air Quality Standards (NAAQS)

EPA Pesticide Factsheets

See the history of limits to the level of sulfur dioxide (SO2) in ambient air, set through the NAAQS review and rulemaking process under the Clean Air Act. This includes both primary and secondary standards.

Treatment of high-strength sulfate wastewater using an autotrophic biocathode in view of elemental sulfur recovery.

PubMed

Blázquez, Enric; Gabriel, David; Baeza, Juan Antonio; Guisasola, Albert

2016-11-15

Treatment of high-strength sulfate wastewaters is becoming a research issue not only for its optimal management but also for the possibility of recovering elemental sulfur. Moreover, sulfate-rich wastewater production is expected to grow due to the increased SO 2 emission contained in flue gases which are treated by chemical absorption in water. Bioelectrochemical systems (BESs) are a promising alternative for sulfate reduction with a lack of electron donor, since hydrogen can be generated in situ from electricity. However, complete sulfate reduction leads to hydrogen sulfide as final sulfur compound. This work is the first to demonstrate that, in addition to an efficient sulfate-rich wastewater treatment, elemental sulfur could be recovered in a biocathode of a BES under oxygen limiting conditions. The key of the process is the biological oxidation of sulfide to elemental sulfur simultaneously to the sulfate reduction in the cathode using the oxygen produced in the anode that diffuses through the membrane. High sulfate reduction rates (up to 388 mg S-SO 4 2-  L -1  d -1 ) were observed linked to a low production of sulfide. Accumulation of elemental sulfur over graphite fibers of the biocathode was demonstrated by energy dispersive spectrometry, discarding the presence of metal sulfides. Microbial community analysis of the cathode biofilm demonstrated the presence of sulfate-reducing bacteria (mainly Desulfovibrio sp.) and sulfide-oxidizing bacteria (mainly Sulfuricurvum sp.). Hence, this biocathode allows simultaneous biological sulfate reduction and biological sulfide oxidation to elemental sulfur, opening up a novel process for recovering sulfur from sulfate-rich wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sulfur poisoning of CeO[subscript 2]-Al[subscript 2]O[subscript 3]-supported mono- and bi-metallic Ni and Rh catalysts in steam reforming of liquid hydrocarbons at low and high temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Chao; Chen, Yongsheng; Li, Yan

2010-12-01

In order to develop a better understanding on sulfur poisoning of reforming catalysts in fuel processing for hydrogen production, steam reforming of liquid hydrocarbons was performed over CeO{sub 2}-Al{sub 2}O{sub 3} supported monometallic Ni and Rh and bimetallic Rh-Ni catalysts at 550 and 800 C. XANES was used to identify the sulfur species in the used catalysts and to study their impacts on the metal surface properties probed by XPS. It was found that both monometallic catalysts rapidly deactivated at 550 C, and showed poor sulfur tolerance. Although ineffective for the Ni catalyst, increasing the temperature to 800 C dramaticallymore » improved the sulfur tolerance of the Rh catalyst. XANES revealed that metal sulfide and organic sulfide are the dominant sulfur species on the used Ni catalyst, while sulfonate and sulfate predominate on the used Rh catalyst. The presence of sulfur induced severe carbon deposition on the Ni catalyst at 800 C. The superior sulfur tolerance of the Rh catalyst at 800 C may be associated with its capability in sulfur oxidation. It is likely that the formation of the oxygen-shielded sulfur structure of sulfonate and sulfate can suppress the poisoning impact of sulfur on Rh by inhibiting direct rhodium-sulfur interaction. Moreover, XPS indicated that the metal surface properties of the Rh catalysts after the reaction without and with sulfur at 800 C are similar, suggesting that sulfur poisoning on Rh was mitigated under the high-temperature condition. Although the Rh-Ni catalyst exhibited better sulfur tolerance than the monometallic catalysts at 550 C, its catalytic performance was inferior compared with the Rh catalyst in the sulfur-containing reaction at 800 C probably due to the severe carbon deposition on the bimetallic catalyst.« less

Reactor Experiments at the University of Minnesota.

DTIC Science & Technology

1987-07-15

metallurgy; zinc, zinc oxide; solar thermal,’ solar Pi% thermoelectrochemical’ water splitting, separation devices; reactors e, ? 20. AeSiRACT (Continue oe...reported. Water splitting, recovery of hydrogen 4. and sulfur from hydrogen sulfide, electrolysis of zinc oxide in vapor and liquid phases, oil...CH4-CO2 reforming process. 2. Hydrogen production from water and the production of hydrogen and sulfur (or ammonia and sulfuric acid) from H2S. 3

N and S co-doped porous carbon spheres prepared using L-cysteine as a dual functional agent for high-performance lithium-sulfur batteries.

PubMed

Niu, Shuzhang; Lv, Wei; Zhou, Guangmin; He, Yanbing; Li, Baohua; Yang, Quan-Hong; Kang, Feiyu

2015-12-28

Nitrogen and sulfur co-doped porous carbon spheres (NS-PCSs) were prepared using L-cysteine to control the structure and functionalization during the hydrothermal reaction of glucose and the subsequent activation process. As the sulfur hosts in Li-S batteries, NS-PCSs combine strong physical confinement and surface chemical interaction to improve the affinity of polysulfides to the carbon matrix.

An Evaluation of Coal Water Slurry Fuel Burners and Technology

DTIC Science & Technology

1992-11-01

treatment) processes, such as froth flotation , which reduce ash and pyritic sulphur content (4). Unlike pulverized coal, there is no need for expensive drying...physical beneficiation (froth flotation ) to reduce pyrite , biotechnological and other methods to remove more sulfur (especially the organic portion...of limited effectiveness since only some of the pyritic sulfur (about 40 to 60 percent of the total sulfur) is removed for some coals, since 90 to 95

Ovarian structure and oogenesis of the extremophile viviparous teleost Poecilia mexicana (Poeciliidae) from an active sulfur spring cave in Southern Mexico.

PubMed

Torres-Martínez, Aarón; Hernández-Franyutti, Arlette; Uribe, Mari Carmen; Contreras-Sánchez, Wilfrido Miguel

2017-12-01

The structure of the ovary and oogenesis of Poecilia mexicana from an active sulfur spring cave is documented. Poecilia mexicana is the only poeciliid adapted to a subterranean environment with high hydrogen sulfide levels and extreme hypoxic conditions. Twenty females were captured throughout one year at Cueva del Azufre, located in the State of Tabasco in Southern Mexico. Ovaries were processed with histological techniques. P. mexicana has a single, ovoid ovary with ovigerous lamella that project to the ovarian lumen. The ovarian wall presents abundant loose connective tissue, numerous melanomacrophage centers and large blood vessels, possibly associated with hypoxic conditions. The germinal epithelium bordering the ovarian lumen contains somatic and germ cells forming cell nests projecting into the stroma. P. mexicana stores sperm in ovarian folds associated with follicles at different developmental phases. Oogenesis in P. mexicana consisted of the following stages: (i) oogonial proliferation, (ii) chromatin nucleolus, (iii) primary growth, subdivided into: (a) one nucleolus, (b) multiple nucleoli, (c) droplet oils-cortical alveoli steps; (iv) secondary growth, subdivided in: (a) early secondary growth, (b) late secondary growth, and (c) full grown. Follicular atresia was present in all stages of follicular development; it was characterized by oocyte degeneration, where follicle cells hypertrophy and differentiate in phagocytes. The ovary and oogenesis are similar to these seen in other poeciliids, but we found frequent atretic follicles, melanomacrophage centers, reduced fecundity and increased of offspring size. © 2017 Wiley Periodicals, Inc.

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.

Pilot test of Pickliq{reg_sign} process to determine energy and environmental benefits & economic feasibility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olsen, D.R.

Green Technology Group (GTG) was awarded Grant No. DE-FG01-96EE 15657 in the amount of $99,904 for a project to advance GTG`s Pickliq{reg_sign} Process in the Copper and Steel Industries. The use of the Pickliq{reg_sign} Process can significantly reduce the production of waste acids containing metal salts. The Pickliq{reg_sign} Process can save energy and eliminate hazardous waste in a typical copper rod or wire mill or a typical steel wire mill. The objective of this pilot project was to determine the magnitude of the economic, energy and environmental benefits of the Pickliq{reg_sign} Process in two applications within the metal processing industry.more » The effectiveness of the process has already been demonstrated at facilities cleaning iron and steel with sulfuric acid. 9207 companies are reported to use sulfuric and hydrochloric acid in the USA. The USEPA TRI statistics of acid not recycled in the US is 2.4 x 10{sup 9} lbs (net) for Hydrochloric Acid and 2.0 x 10{sup 9} lbs (net) for Sulfuric Acid. The energy cost of not reclaiming acid is 10.7 x 10{sup 6} BTU/ton for Hydrochloric Acid and 21.6 x 10{sup 6} BTU/Ton for Sulfuric Acid. This means that there is a very large market for the application of the Pickliq{reg_sign} Process and the widespread use of the process will bring significant world wide savings of energy to the environment.« less

Inverse Vulcanization of Sulfur using Natural Dienes as Sustainable Materials for Lithium-Sulfur Batteries.

PubMed

Gomez, Iñaki; Leonet, Olatz; Blazquez, J Alberto; Mecerreyes, David

2016-12-20

Lithium-sulfur batteries are among the most promising next-generation battery systems due to the high capacity of sulfur as cathodic material. Beyond its interesting intrinsic properties, sulfur possesses a very low conductivity and complex electrochemistry, which involves the high solubility of the lithium sulfides in the electrolyte. These two characteristics are at the core of a series of limitations of its performance as active cathode material, which leads to batteries with low cyclability. Recently, inverse vulcanized sulfur was shown to retain capacity far better than elemental sulfur, leading to batteries with excellent cyclability. Nevertheless, the diene co-monomers used so far in the inverse vulcanization process are man-made molecules. Herein, a tentative work on exploring inverse vulcanization using two naturally available monomers, diallyl sulfide and myrcene, is presented. The inverse vulcanization of sulfur was successfully completed, and the resulting polymers were characterized by FTIR, NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Afterwards these polymers were tested as cathodic materials in lithium-sulfur cells. The sulfur-natural dienes materials exhibited high capacity at different C rates and high lifetime over 200 cycles with very high capacity retention at a moderate C rate of C/5. Altogether, these materials made from inexpensive and abundant chemicals are an excellent option as sustainable materials for electrochemical energy storage. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal and energetic processing of astrophysical ice analogues rich in SO2

NASA Astrophysics Data System (ADS)

Kaňuchová, Z.; Boduch, Ph.; Domaracka, A.; Palumbo, M. E.; Rothard, H.; Strazzulla, G.

2017-08-01

Context. Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the solar system. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (I.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Aims: Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. Methods: We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment (30 keV He+) of the same mixtures. We used in situ Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results: The results indicate that ionic species such as HSO, HSO, and S2O are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions: The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets.

A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process for decentralized wastewater treatment.

PubMed

Krayzelova, Lucie; Lynn, Thomas J; Banihani, Qais; Bartacek, Jan; Jenicek, Pavel; Ergas, Sarina J

2014-09-15

Nitrogen discharges from decentralized wastewater treatment (DWT) systems contribute to surface and groundwater contamination. However, the high variability in loading rates, long idle periods and lack of regular maintenance presents a challenge for biological nitrogen removal in DWT. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process was developed that combines nitrate (NO3(-)) adsorption to scrap tire chips with sulfur-oxidizing denitrification. This allows the tire chips to adsorb NO3(-) when the influent loading exceeds the denitrification capacity of the biofilm and release it when NO3(-) loading rates are low (e.g. at night). Three waste products, scrap tire chips, elemental sulfur pellets and crushed oyster shells, were used as a medium in adsorption, leaching, microcosm and up-flow packed bed bioreactor studies of NO3(-) removal from synthetic nitrified DWT wastewater. Adsorption isotherms showed that scrap tire chips have an adsorption capacity of 0.66 g NO3(-)-N kg(-1) of scrap tires. Leaching and microcosm studies showed that scrap tires leach bioavailable organic carbon that can support mixotrophic metabolism, resulting in lower effluent SO4(2-) concentrations than sulfur oxidizing denitrification alone. In column studies, the T-SHAD process achieved high NO3(-)-N removal efficiencies under steady state (90%), variable flow (89%) and variable concentration (94%) conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sulfur Embedded in a Mesoporous Carbon Nanotube Network as a Binder-Free Electrode for High-Performance Lithium-Sulfur Batteries.

PubMed

Sun, Li; Wang, Datao; Luo, Yufeng; Wang, Ke; Kong, Weibang; Wu, Yang; Zhang, Lina; Jiang, Kaili; Li, Qunqing; Zhang, Yihe; Wang, Jiaping; Fan, Shoushan

2016-01-26

Sulfur-porous carbon nanotube (S-PCNT) composites are proposed as cathode materials for advanced lithium-sulfur (Li-S) batteries. Abundant mesopores are introduced to superaligned carbon nanotubes (SACNTs) through controlled oxidation in air to obtain porous carbon nanotubes (PCNTs). Compared to original SACNTs, improved dispersive behavior, enhanced conductivity, and higher mechanical strength are demonstrated in PCNTs. Meanwhile, high flexibility and sufficient intertube interaction are preserved in PCNTs to support binder-free and flexible electrodes. Additionally, several attractive features, including high surface area and abundant adsorption points on tubes, are introduced, which allow high sulfur loading, provide dual protection to sulfur cathode materials, and consequently alleviate the capacity fade especially during slow charge/discharge processes. When used as cathodes for Li-S batteries, a high sulfur loading of 60 wt % is achieved, with excellent reversible capacities of 866 and 526 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at a slow charge/discharge rate of 0.1C, revealing efficient suppression of polysulfide dissolution. Even with a high sulfur loading of 70 wt %, the S-PCNT composite maintains capacities of 760 and 528 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at 0.1C, outperforming the current state-of-the-art sulfur cathodes. Improved high-rate capability is also delivered by the S-PCNT composites, revealing their potentials as high-performance carbon-sulfur composite cathodes for Li-S batteries.

Process and system for removing sulfur from sulfur-containing gaseous streams

DOEpatents

Basu, Arunabha; Meyer, Howard S.; Lynn, Scott; Leppin, Dennis; Wangerow, James R.

2012-08-14

A multi-stage UCSRP process and system for removal of sulfur from a gaseous stream in which the gaseous stream, which contains a first amount of H.sub.2S, is provided to a first stage UCSRP reactor vessel operating in an excess SO.sub.2 mode at a first amount of SO.sub.2, producing an effluent gas having a reduced amount of SO.sub.2, and in which the effluent gas is provided to a second stage UCSRP reactor vessel operating in an excess H.sub.2S mode, producing a product gas having an amount of H.sub.2S less than said first amount of H.sub.2S.

Synthesis of the sulfur amino acids: cysteine and methionine.

PubMed

Wirtz, Markus; Droux, Michel

2005-12-01

This review will assess new features reported for the molecular and biochemical aspects of cysteine and methionine biosynthesis in Arabidopsis thaliana with regards to early published data from other taxa including crop plants and bacteria (Escherichia coli as a model). By contrast to bacteria and fungi, plant cells present a complex organization, in which the sulfur network takes place in multiple sites. Particularly, the impact of sulfur amino-acid biosynthesis compartmentalization will be addressed in respect to localization of sulfur reduction. To this end, the review will focus on regulation of sulfate reduction by synthesis of cysteine through the cysteine synthase complex and the synthesis of methionine and its derivatives. Finally, regulatory aspects of sulfur amino-acid biosynthesis will be explored with regards to interlacing processes such as photosynthesis, carbon and nitrogen assimilation.

[Corrosion of pipe steel samples and conjugated conversion of sulfur compounds by thiobacteria Halothiobacillus neapolitanus DSM 15147].

PubMed

Vatsurina, A V; Esikova, T Z; Kholodenko, V P; Vaĭnshteĭn, M B; Dubkova, V I

2005-01-01

The kinetics of conversion of sulfur compounds by Halothiobacillus neapolitanus DSM 15147 bacteria was studied in the presence of steel samples. It was shown that the presence of steel altered the known pathway of sulfur compound oxidation by thiobacteria. Production of atomic hydrogen via the interaction between biogenic sulfuric acid and steel enhanced secondary production of intermediates and decreased the content of sulfate produced previously. The process was accompanied by pH elevation and continuation of intense growth of the thiobacterium culture. Thiobacteria formed a corrosive medium, which caused metal destruction. The protective properties of anticorrosive coatings 225 LS and 640 mk were tested. It was shown that these coatings protected steel from the destructive effect of biogenic sulfuric acid.

Microbial biocatalyst developments to upgrade fossil fuels.

PubMed

Kilbane, John J

2006-06-01

Steady increases in the average sulfur content of petroleum and stricter environmental regulations concerning the sulfur content have promoted studies of bioprocessing to upgrade fossil fuels. Bioprocesses can potentially provide a solution to the need for improved and expanded fuel upgrading worldwide, because bioprocesses for fuel upgrading do not require hydrogen and produce far less carbon dioxide than thermochemical processes. Recent advances have demonstrated that biodesulfurization is capable of removing sulfur from hydrotreated diesel to yield a product with an ultra-low sulfur concentration that meets current environmental regulations. However, the technology has not yet progressed beyond laboratory-scale testing, as more efficient biocatalysts are needed. Genetic studies to obtain improved biocatalysts for the selective removal of sulfur and nitrogen from petroleum provide the focus of current research efforts.

Thiophenic Sulfur Compounds Released During Coal Pyrolysis

PubMed Central

Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

2013-01-01

Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

High sulfur-containing carbon polysulfide polymer as a novel cathode material for lithium-sulfur battery.

PubMed

Zhang, Yiyong; Peng, Yueying; Wang, Yunhui; Li, Jiyang; Li, He; Zeng, Jing; Wang, Jing; Hwang, Bing Joe; Zhao, Jinbao

2017-09-12

The lithium-sulfur battery, which offers a high energy density and is environmental friendly, is a promising next generation of rechargeable energy storage system. However, despite these attractive attributes, the commercialization of lithium-sulfur battery is primarily hindered by the parasitic reactions between the Li metal anode and dissolved polysulfide species from the cathode during the cycling process. Herein, we synthesize the sulfur-rich carbon polysulfide polymer and demonstrate that it is a promising cathode material for high performance lithium-sulfur battery. The electrochemical studies reveal that the carbon polysulfide polymer exhibits superb reversibility and cycle stability. This is due to that the well-designed structure of the carbon polysulfide polymer has several advantages, especially, the strong chemical interaction between sulfur and the carbon framework (C-S bonds) inhibits the shuttle effect and the π electrons of the carbon polysulfide compound enhance the transfer of electrons and Li + . Furthermore, as-prepared carbon polysulfide polymer-graphene hybrid cathode achieves outstanding cycle stability and relatively high capacity. This work highlights the potential promise of the carbon polysulfide polymer as the cathode material for high performance lithium-sulfur battery.

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

PubMed

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jin-Woo; Kim, Icpyo; Kim, Ki-Won

Highlights: • The sulfur/activated carbon composite is fabricated using commercial activated carbons. • The sulfur/activated carbon composite with coal shows the best performance. • The Li/S battery has capacities of 1240 mAh g{sup −1} at 1 C and 567 mAh g{sup −1} at 10 C. - Abstract: We prepared sulfur/active carbon composites via a simple solution-based process using the following commercial activated carbon-based materials: coal, coconut shells, and sawdust. Although elemental sulfur was not detected in any of the sulfur/activated carbon composites based on Thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy, Energy-dispersive X-ray spectroscopy results confirmed its presence in themore » activated carbon. These results indicate that sulfur was successfully impregnated in the activated carbon and that all of the activated carbons acted as sulfur reservoirs. The sulfur/activated carbon composite cathode using coal exhibited the highest discharge capacity and best rate capability. The first discharge capacity at 1 C (1.672 A g{sup −1}) was 1240 mAh g{sup −1}, and a large reversible capacity of 567 mAh g{sup −1} was observed at 10 C (16.72 A g{sup −1}).« less

Oxidation Resistance and Critical Sulfur Content of Single-Crystal Superalloys

NASA Technical Reports Server (NTRS)

Smialek, James L.

1997-01-01

The high-temperature components of a jet turbine engine are made from nickel-base superalloys. These components must be able to withstand high stresses, fatigue, and corrosive reactions with high-temperature gases. Such oxidation resistance is associated with slow-growing Al2O3 scales that remain adherent to superalloy components after many thermal cycles. Historically, good oxidation resistance has been obtained by coating these components with Ni-Cr-Al-Y coatings, where small additions of yttrium (Y) were necessary for scale adhesion. Subsequently, it was found that the Y aids scale adhesion by preventing sulfur from segregating to the scale metal interface and thus preventing the sulfur from weakening the oxide-metal bonds. Y is a difficult element to incorporate in single-crystal superalloy castings, but it was shown in early work at the NASA Lewis Research Center that good adhesion could be obtained for low-sulfur, uncoated, singlecrystal superalloys, without Y additions. Low sulfur contents for these uncoated superalloys were achieved in the laboratory by a high-temperature hydrogen annealing process. This process allows segregation and surface cleaning of sulfur monolayers in a reducing environment. Another approach is to remove sulfur from the alloy in the melting process. The present study was designed to establish a guideline for the minimum level of desulfurization needed to achieve maximum performance. Coupons of various thicknesses of the superalloy PWA 1480 were hydrogen annealed at various times (8 to 100 hr) and temperatures (1000 to 1300 C), resulting in coupons with sulfur contents ranging from about 0.05 to 5 ppm. Cyclic oxidation tests at 1100 C were then used to assess adhesion and spalling. The weight change of one set of 20-mil (0.5-mm) samples, annealed for 20 hr at 1000, 1100, 1200, and 1300 C, is shown in the following figure. Clearly, the effect of the annealing temperature is quite dramatic in that the higher temperatures produced scales that spalled very little, whereas the lower temperatures resulted in severe weight losses comparable to those for the as-received, unannealed sample.

Facile synthesis and application of a carbon foam with large mesopores.

PubMed

Fu, Liling; Qi, Genggeng; Sahore, Ritu; Sougrat, Rachid; DiSalvo, Francis J; Giannelis, Emmanuel P

2013-11-28

By combining elements of hard- and soft-templating, a facile synthesis method for carbon foams with large mesopores has been demonstrated. A commercial Pluronic surfactant was used as the structure-directing agent as well as the carbon precursor. No micelle swelling agent or post treatment is necessary to enlarge mesopores. As such this method requires fewer synthesis steps and is highly scalable. The as-synthesized meso-carbons showed potential applications in the fields of carbon oxide capture and lithium-sulfur batteries.

Loss of oxygen, silicon, sulfur, and potassium from the lunar regolith

NASA Technical Reports Server (NTRS)

Clayton, R. N.; Mayeda, T. K.; Hurd, J. M.

1974-01-01

The processes of formation and maturation of lunar soils lead to enrichments in the heavy stable isotopes of oxygen, silicon, sulfur, and potassium. The isotopic enrichment implies substantial losses of these elements from the moon. Vaporization by micrometeorite impact and by ion sputtering have removed at least 1% of the mass of the regolith. The losses of sulfur and potassium amount to at least 20-30% of their original abundance in the regolith.

Sulfur Chemistry in the Early and Present Atmosphere of Mars

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Summers, M. E.

2011-01-01

Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

Desulfurization of fuel gases in fluidized bed gasification and hot fuel gas cleanup systems

DOEpatents

Steinberg, M.; Farber, G.; Pruzansky, J.; Yoo, H.J.; McGauley, P.

1983-08-26

A problem with the commercialization of fluidized bed gasification is that vast amounts of spent sorbent are generated if the sorbent is used on a once-through basis, especially if high sulfur coals are burned. The requirements of a sorbent for regenerative service in the FBG process are: (1) it must be capable of reducing the sulfur containing gas concentration of the FBG flue gas to within acceptable environmental standards; (2) it must not lose its reactivity on cyclic sulfidation and regeneration; (3) it must be capable of regeneration with elimination of substantially all of its sulfur content; (4) it must have good attrition resistance; and, (5) its cost must not be prohibitive. It has now been discovered that calcium silicate pellets, e.g., Portland cement type III pellets meet the criteria aforesaid. Calcium silicate removes COS and H/sub 2/S according to the reactions given to produce calcium sulfide silicate. The sulfur containing product can be regenerated using CO/sub 2/ as the regenerant. The sulfur dioxide can be conveniently reduced to sulfur with hydrogen or carbon for market or storage. The basic reactions in the process of this invention are the reactions with calcium silicate given in the patent. A convenient and inexpensive source of calcium silicate is Portland cement. Portland cement is a readily available, widely used construction meterial.

Composition of Irradiation Residue from Jupiter Trojan Laboratory Simulations

NASA Astrophysics Data System (ADS)

Poston, Michael; Mahjoub, Ahmed; Blacksberg, Jordana; Brown, Michael E.; Carlson, Robert W.; Ehlmann, Bethany; Eiler, John; Hand, Kevin P.; Hodyss, Robert; Wong, Ian

2016-10-01

Today's Jupiter Trojan asteroids may have originated in the Kuiper Belt (eg. Morbidelli et al. Nature 2005, Nesvorny et al. ApJ 2013) and migrated to capture at their present locations. If this is the case, it is expected that their surfaces will contain chemical traces of this history. Our work broadly considers laboratory simulations of this history. In this work we report on the refractory residue left behind when irradiated mixed ice samples were brought to Earth-normal conditions and removed from the vacuum system. Ices that will be discussed include a 3:3:3:1 mixture of H2S:NH3:CH3OH:H2O and a 3:3:1 mixture of NH3:CH3OH:H2O. After deposition at 50K, the ices were irradiated with a beam of 10 keV electrons to form a processed crust mixed with unreacted ices. The films were then warmed to 142K under irradiation over several days. After stopping irradiation, the mixtures were slowly heated through the desorption temperatures of the unreacted ices (about 150-180K), leaving only more-stable compounds behind, and up to room temperature. Some of the reaction products were seen to desorb during heating to room temperature, while a significant amount remained as a refractory residue. After backfilling the vacuum system with nitrogen gas, residues were analyzed by Fourier Transform Infrared Spectroscopy, Secondary Ion Mass Spectrometry, and Gas Chromatograph Mass Spectrometry. Results indicate a complex chemistry including aliphatic and aromatic hydrocarbons, and nitrogen and sulfur-containing organics. Notably, when sulfur is not present, a number of nitrogen-containing organic candidates are identified, however, in the mixtures containing sulfur, sulfur-containing compounds appear to dominate the chemistry. While these experiments were conducted with Trojan asteroids in mind, the results are also relevant to comets and other cold locations in the solar system that have experienced large swings in temperature.This work has been supported by the Keck Institute for Space Studies (KISS). The research described here was carried out at the Jet Propulsion Laboratory, Caltech, under a contract with the National Aeronautics and Space Administration (NASA) and at the Caltech Division of Geological and Planetary Sciences.

Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

PubMed

Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

2013-11-01

Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

Proceedings: Fourteenth annual EPRI conference on fuel science

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1990-05-01

EPRI's Fourteenth Annual Contractors' Conference on Fuel Science was held on May 18--19, 1989 in Palo Alto, CA. The conference featured results of work on coal science, coal liquefaction, methanol production, and coal oil coprocessing and coal upgrading. The following topics were discussed: recent development in coal liquefaction at the Wilsonville Clean Coal Research Center; British coal's liquid solvent extraction (LSE) process; feedstock reactivity in coal/oil co-processing; utility applications for coal-oil coprocessed fuels; effect of coal rank and quality on two-stage liquefaction; organic sulfur compounds in coals; the perchloroethylene refining process of high-sulfur coals; extraction of sulfur coals; extraction ofmore » sulfur from coal; agglomeration of bituminous and subbituminous coals; solubilization of coals by cell-free extracts derived from polyporus versicolor; remediation technologies and services; preliminary results from proof-of-concept testing of heavy liquid cyclone cleaning technology; clean-up of soil contaminated with tarry/oily organics; midwest ore processing company's coal benefication technology: recent prep plant, scale and laboratory activities; combustion characterization of coal-oil agglomerate fuels; status report on the liquid phase methanol project; biomimetic catalysis; hydroxylation of C{sub 2} {minus} C{sub 3} and cycloc{sub 6} hydrocarbons with Fe cluster catalysts as models for methane monooxygenase enzyme; methanol production scenarios; and modeling studies of the BNL low temperature methanol catalyst. Individual projects are processed separately for the data bases.« less

Long-distance electron transport occurs globally in marine sediments

NASA Astrophysics Data System (ADS)

Burdorf, Laurine D. W.; Tramper, Anton; Seitaj, Dorina; Meire, Lorenz; Hidalgo-Martinez, Silvia; Zetsche, Eva-Maria; Boschker, Henricus T. S.; Meysman, Filip J. R.

2017-02-01

Recently, long filamentous bacteria have been reported conducting electrons over centimetre distances in marine sediments. These so-called cable bacteria perform an electrogenic form of sulfur oxidation, whereby long-distance electron transport links sulfide oxidation in deeper sediment horizons to oxygen reduction in the upper millimetres of the sediment. Electrogenic sulfur oxidation exerts a strong impact on the local sediment biogeochemistry, but it is currently unknown how prevalent the process is within the seafloor. Here we provide a state-of-the-art assessment of its global distribution by combining new field observations with previous reports from the literature. This synthesis demonstrates that electrogenic sulfur oxidation, and hence microbial long-distance electron transport, is a widespread phenomenon in the present-day seafloor. The process is found in coastal sediments within different climate zones (off the Netherlands, Greenland, the USA, Australia) and thrives on a range of different coastal habitats (estuaries, salt marshes, mangroves, coastal hypoxic basins, intertidal flats). The combination of a widespread occurrence and a strong local geochemical imprint suggests that electrogenic sulfur oxidation could be an important, and hitherto overlooked, component of the marine cycle of carbon, sulfur and other elements.

Detection and Identification of Sulfur Compounds in an Australian Jet Fuel

DTIC Science & Technology

2010-06-01

from a number of Australian and south-east Asian refineries that have different fuel finishing processes and methods for sweetening or desulfurising ...comparison to sulfur species that remain in deep hydrodesulfurised or alternate desulfurisation processed AVTUR/FSII fuels of the future. This work...Schmitz, C., Wasserscheid, P. (2001) Deep desulfurisation of diesel fuel by extraction with ionic liquids. Chem. Commun. 2494-2495 39. Dirk, D

40 CFR 372.3 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., roasters, and foundry furnaces). (8) Titanium dioxide chloride process oxidation reactors. (9) Methane... sulfur values from spent sulfuric acid. (12) Halogen acid furnaces (HAFs) for the production of acid from halogenated hazardous waste generated by chemical production facilities where the furnace is located on the...

40 CFR 372.3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., roasters, and foundry furnaces). (8) Titanium dioxide chloride process oxidation reactors. (9) Methane... sulfur values from spent sulfuric acid. (12) Halogen acid furnaces (HAFs) for the production of acid from halogenated hazardous waste generated by chemical production facilities where the furnace is located on the...

Understanding chemistry behind secondary aerosol production from nitrogen and sulfur compounds from agriculture

USDA-ARS?s Scientific Manuscript database

Agricultural emissions impact particulate mass concentrations through both primary and secondary processes. Evidence from laboratory and field work suggest that not only does ammonia produce secondary particulate matter, but nitrogen and sulfur containing volatile organic compounds also contribute. ...

Weathering of Olivine during Interaction of Sulfate Aerosols with Mars Soil under Current Climate Conditions

NASA Astrophysics Data System (ADS)

Niles, P. B.; Golden, D. C.; Michalski, J. R.; Ming, D. W.

2017-12-01

Sulfur concentrations in the Mars soils are elevated above 1 wt% in nearly every location visited by landed spacecraft. This observation was first made by the Viking landers, and has been confirmed by subsequent missions. The wide distribution of sulfur in martian soils has been attributed to volcanic degassing, formation of sulfate aerosols, and later incorporation into martian soils during gravitational sedimentation. However, later discoveries of more concentrated sulfur bearing sediments by the Opportunity rover has led some to believe that sulfates may instead be a product of evaporation and aeolian redistribution. One question that has not been addressed is whether the modern surface conditions are too cold for weathering of volcanic materials by sulfate aerosols. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. Laboratory experiments were conducted to simulate weathering of olivine under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40°C. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment for olivine weathering despite the very low temperatures. The likelihood of substantial sulfur-rich volcanism on Mars and creation of abundant sulfate aerosols suggests that this process would have been important during formation of martian soils and sediments. Future work modeling sulfur release rates during volcanic eruptions and aerosol distribution over the surface will help understand how well this process could concentrate sulfate minerals in nearby surface materials or whether this process would simply result in widespread globally distributed sulfur materials.

[The sources of inorganic sulfur in the process of cluster protein Fnr[4Fe-4S]2+ reconstruction in Escherichia coli cells cultivated with NO-donating agents].

PubMed

Vasil'eva, S V; Strel'tsova, D A; Vlaskina, A V; Mikoian, V D; Vanin, A F

2012-01-01

Dinitrosyl iron complexes (DNICs) with thiol ligands--binuclear and mononuclear--inhibited aidB gene expression in E. coli cells. This process is due to the nitrosylation of the active center in iron-sulfur protein Fnr [4Fe-4S]2+ by low-molecular DNICs. The next step is transformation of the above DNICs into the DNICs with the thiol groups in the apo-form of Fnr protein. These nitrosylated proteins are characterized by the EPR signal with g perpendicular = 2.04 and g parallel 1 = 2,014. An addition of sulfur containing L-Cys or N-A-L-Cys as well as Na2S to the cells lead to the increasing in the aidB gene expression simultaneously with an appearance of the EPR signal with g perpendicular = 2.04 and g parallel = 2.02 as the characteristics of the DNICs with persulfide (R-S-S-) ligands. We suppose that the recovery of the aidB gene activity was due to the accumulation of inorganic sulfur in the cells and reconstruction of the active center in Fnr[4Fe-4S]2+. It appears that the above process is the function of L-cysteine-desulfurase protein which repaired the active center of Fnr[4Fe-4S]2+ protein using the sulfur from L-Cys or N-A-L-Cys after its deacetylation. On the other side the ions of inorganic sulfur being reacted with SH-groups led to the transformation of DNIC with thiol ligands into the persulfides. Na2S was the most potent activator of the aidB gene expression in our experiments.

Effects of H ₂SO₄ and O ₂ on Hg⁰ uptake capacity and reversibility of sulfur-impregnated activated carbon under dynamic conditions.

PubMed

Wei, Yuanyang; Yu, Danqing; Tong, Shitang; Jia, Charles Q

2015-02-03

Powder activated carbon (AC) injection is widely considered as the most viable technology for removing gaseous elemental mercury (Hg(0)) in flue gases of coal-fired power plants. However, sulfuric acid (H2SO4) can form on the external and internal surfaces of AC particles due to the presence of sulfur oxides, nitrogen oxides, oxygen, and moisture in flue gases. This work focuses on the effects of H2SO4 and O2 on the Hg(0) uptake capacity and reversibility of sulfur impregnated activated carbon (SIAC) under dynamic conditions. Experiments were conducted with 25 μg-Hg(0)/m(3) of nitrogen or air, using a semicontinuous flow fixed-bed reactor kept at 120 or 180 °C. H2SO4 had a profound hindering effect on Hg(0) uptake due to pore blockage. O2 significantly enhanced Hg(0) uptake and its reversibility, via the oxidation of Hg(0) which facilitated chemisorption and the subsequent physisorption onto chemically adsorbed Hg. Absorption of Hg in H2SO4 was unlikely a significant contributor, when Hg(0) concentrations were at levels of typical power plants (tens of ppb). The reversibility of and relative contributions of physisorption and chemisorption to Hg(0) uptake would change with Hg(0) concentrations in flue gases. These findings could be significant in developing a complete solution for Hg capture where the handling of spent sorbent materials and the possible secondary pollution need to be considered.

Sulfur in zircons: A new window into melt chemistry

NASA Astrophysics Data System (ADS)

Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

2017-12-01

The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

Microbial community structure and sulfur biogeochemistry in mildly-acidic sulfidic geothermal springs in Yellowstone National Park.

PubMed

Macur, R E; Jay, Z J; Taylor, W P; Kozubal, M A; Kocar, B D; Inskeep, W P

2013-01-01

Geothermal and hydrothermal waters often contain high concentrations of dissolved sulfide, which reacts with oxygen (abiotically or biotically) to yield elemental sulfur and other sulfur species that may support microbial metabolism. The primary goal of this study was to elucidate predominant biogeochemical processes important in sulfur biogeochemistry by identifying predominant sulfur species and describing microbial community structure within high-temperature, hypoxic, sulfur sediments ranging in pH from 4.2 to 6.1. Detailed analysis of aqueous species and solid phases present in hypoxic sulfur sediments revealed unique habitats containing high concentrations of dissolved sulfide, thiosulfate, and arsenite, as well as rhombohedral and spherical elemental sulfur and/or sulfide phases such as orpiment, stibnite, and pyrite, as well as alunite and quartz. Results from 16S rRNA gene sequencing show that these sediments are dominated by Crenarchaeota of the orders Desulfurococcales and Thermoproteales. Numerous cultivated representatives of these lineages, as well as the Thermoproteales strain (WP30) isolated in this study, require complex sources of carbon and respire elemental sulfur. We describe a new archaeal isolate (strain WP30) belonging to the order Thermoproteales (phylum Crenarchaeota, 98% identity to Pyrobaculum/Thermoproteus spp. 16S rRNA genes), which was obtained from sulfur sediments using in situ geochemical composition to design cultivation medium. This isolate produces sulfide during growth, which further promotes the formation of sulfide phases including orpiment, stibnite, or pyrite, depending on solution conditions. Geochemical, molecular, and physiological data were integrated to suggest primary factors controlling microbial community structure and function in high-temperature sulfur sediments. © 2012 Blackwell Publishing Ltd.

LIGNOSULFONATE-MODIFIED CALCIUM HYDROXIDE FOR SULFUR DIOXIDE CONTROL

EPA Science Inventory

The article discusses the use of lignosulfonate-modified calcium hydroxide Ca(OH)2 for sulfur dioxide (SO2) control. The limestone injection multistage burner (LIMB) process is currently being developed at the U.S. EPA as a low cost retrofittable technology for controlling oxides...

Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

NASA Astrophysics Data System (ADS)

Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

2017-12-01

Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

Determination of sulfuric acid concentration for anti-cavitation characteristics of Al alloy by two step anodizing process to forming nano porous.

PubMed

Lee, Seung-Jun; Kim, Seong-Kweon; Jeong, Jae-Yong; Kim, Seong-Jong

2014-12-01

Al alloy is a highly active metal but forms a protective oxide film having high corrosion resistance in atmosphere environment. However, the oxide film is not suitable for practical use, since the thickness of the film is not uniform and it is severly altered with formation conditions. This study focused on developing an aluminum anodizing layer having hardness, corrosion resistance and abrasion resistance equivalent to a commercial grade protective layer. Aluminum anodizing layer was produced by two-step aluminum anodizing oxide (AAO) process with different sulfuric acid concentrations, and the cavitation characteristics of the anodized coating layer was investigated. In hardness measurement, the anodized coating layer produced with 15 vol.% of sulfuric acid condition had the highest value of hardness but exhibited poor cavitation resistance due to being more brittle than those with other conditions. The 10 vol.% of sulfuric acid condition was thus considered to be the optimum condition as it had the lowest weight loss and damage depth.

Autotrophic processes in meromictic Big Soda Lake, Nevada.

USGS Publications Warehouse

Cloern, J.E.; Cole, B.E.; Oremland, R.S.

1983-01-01

Daily rates of oxygenic photosynthesis (OP) by phytoplankton, anoxygenic photosynthesis (AP) by purple sulfur bacteria, and chemoautotrophic productivity (CP = dark CO2 assimilation) were measured once each season. Total daily productivity and the relative importance of each autotrophic process varied with seasonal changes in vertical mixing, light availability, and the biomass of phototrophs. Daily productivity was highest (2830 mg C.m-2) and was dominated by OP in winter when the mixolimnion was isothermal, the biomass of phytoplankton was high, and the biomass of purple sulfur bacteria was low. During the summer-fall period of thermal stratification, phytoplankton biomass decreased, a plate of purple sulfur bacteria formed below the oxycline, and daily rates of dark CO2 assimilation (CP = 390-680 mg C.m-2) exceeded phototrophic productivity (OP + AP = 200-370 mg C.m-2). Total annual productivity was approx 500 g C.m-2, of which 60% was produced by phytoplankton (mostly in winter), 30% by chemoautotrophs (nitrifying and sulfur-oxidizing bacteria), and only 10% by photosynthetic bacteria. -Authors

Case study, comparison of trial burn results from similar sulfuric acid regeneration plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milaszewski, M.; Johns, T.; Dickerson, W.F.

The primary business of Rhodia Eco Services (Rhodia) is the regeneration of sulfuric acid. Sulfuric acid regeneration requires thermal decomposition of acid to sulfur dioxide, and remaking the acid through chemical reaction. The sulfuric acid regeneration furnace is the ideal place to process pumpable wastes for energy recovery and for thermal destruction. Rhodia is regulated by the Boiler and Industrial Furnace (BIF) regulations (40 CFR 266, Subpart H). The Hammond, Indiana plant is an interim status BIF facility and the Houston, Texas facility is renewing its RCRA incineration permit as a BIF facility. Both plants have conducted BIF Trial Burnsmore » with very similar results. The performance levels demonstrated were at levels better than RCRA/BIF standards for destruction and removal efficiency, metal, HCl/Cl, particulate, dioxin/furan, and organic emissions.« less

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.

Self-assembly of biomorphic carbon/sulfur microstructures in sulfidic environments

PubMed Central

Cosmidis, Julie; Templeton, Alexis S.

2016-01-01

In natural and laboratory-based environments experiencing sustained counter fluxes of sulfide and oxidants, elemental sulfur (S0)—a key intermediate in the sulfur cycle—can commonly accumulate. S0 is frequently invoked as a biomineralization product generated by enzymatic oxidation of hydrogen sulfide and polysulfides. Here we show the formation of S0 encapsulated in nanometre to micrometre-scale tubular and spherical organic structures that self-assemble in sulfide gradient environments in the absence of any direct biological activity. The morphology and composition of these carbon/sulfur microstructures so closely resemble microbial cellular and extracellular structures that new caution must be applied to the interpretation of putative microbial biosignatures in the fossil record. These reactions between sulfide and organic matter have important implications for our understanding of S0 mineralization processes and sulfur interactions with organic carbon in the environment. They furthermore provide a new pathway for the synthesis of carbon-sulfur nanocomposites for energy storage technologies. PMID:27628108

Sulfur and iron accumulation in three marine-archaeological shipwrecks in the Baltic Sea: The Ghost, the Crown and the Sword

NASA Astrophysics Data System (ADS)

Fors, Yvonne; Grudd, Håkan; Rindby, Anders; Jalilehvand, Farideh; Sandström, Magnus; Cato, Ingemar; Bornmalm, Lennart

2014-02-01

Sulfur and iron concentrations in wood from three 17th century shipwrecks in the Baltic Sea, the Ghost wreck, the Crown and the Sword, were obtained by X-ray fluorescence (XRF) scanning. In near anaerobic environments symbiotic microorganisms degrade waterlogged wood, reduce sulfate and promote accumulation of low-valent sulfur compounds, as previously found for the famous wrecks of the Vasa and Mary Rose. Sulfur K-edge X-ray absorption near-edge structure (XANES) analyses of Ghost wreck wood show that organic thiols and disulfides dominate, together with elemental sulfur probably generated by sulfur-oxidizing Beggiatoa bacteria. Iron sulfides were not detected, consistent with the relatively low iron concentration in the wood. In a museum climate with high atmospheric humidity oxidation processes, especially of iron sulfides formed in the presence of corroding iron, may induce post-conservation wood degradation. Subject to more general confirmation by further analyses no severe conservation concerns are expected for the Ghost wreck wood.

Self-assembly of biomorphic carbon/sulfur microstructures in sulfidic environments

NASA Astrophysics Data System (ADS)

Cosmidis, Julie; Templeton, Alexis S.

2016-09-01

In natural and laboratory-based environments experiencing sustained counter fluxes of sulfide and oxidants, elemental sulfur (S0)--a key intermediate in the sulfur cycle--can commonly accumulate. S0 is frequently invoked as a biomineralization product generated by enzymatic oxidation of hydrogen sulfide and polysulfides. Here we show the formation of S0 encapsulated in nanometre to micrometre-scale tubular and spherical organic structures that self-assemble in sulfide gradient environments in the absence of any direct biological activity. The morphology and composition of these carbon/sulfur microstructures so closely resemble microbial cellular and extracellular structures that new caution must be applied to the interpretation of putative microbial biosignatures in the fossil record. These reactions between sulfide and organic matter have important implications for our understanding of S0 mineralization processes and sulfur interactions with organic carbon in the environment. They furthermore provide a new pathway for the synthesis of carbon-sulfur nanocomposites for energy storage technologies.

Reduction of the potential energy barrier and resistance at wafer-bonded n-GaAs/n-GaAs interfaces by sulfur passivation

NASA Astrophysics Data System (ADS)

Jackson, Michael J.; Jackson, Biyun L.; Goorsky, Mark S.

2011-11-01

Sulfur passivation and subsequent wafer-bonding treatments are demonstrated for III-V semiconductor applications using GaAs-GaAs direct wafer-bonded structures. Two different sulfur passivation processes are addressed. A dry sulfur passivation method that utilizes elemental sulfur vapor activated by ultraviolet light in vacuum is compared with aqueous sulfide and native-oxide-etch treatments. The electrical conductivity across a sulfur-treated 400 - °C-bonded n-GaAs/n-GaAs interface significantly increased with a short anneal (1-2 min) at elevated temperatures (500-600 °C). Interfaces treated with the NH4OH oxide etch, on the other hand, exhibited only mild improvement in accordance with previously published studies in this area. TEM and STEM images revealed similar interfacial microstructure changes with annealing for both sulfur-treated and NH4OH interfaces, whereby some areas have direct semiconductor-semiconductor contact without any interfacial layer. Fitting the observed temperature dependence of zero-bias conductance using a model for tunneling through a grain boundary reveals that the addition of sulfur at the interface lowered the interfacial energy barrier by 0.2 eV. The interface resistance for these sulfur-treated structures is 0.03 Ω.cm at room temperature. These results emphasize that sulfur-passivation techniques reduce interface states that otherwise limit the implementation of wafer bonding for high-efficiency solar cells and other devices.

Understanding Sulfur Systematics in Large Igneous Provinces Using Sulfur Isotopes

NASA Astrophysics Data System (ADS)

Novikova, S.; Edmonds, M.; Turchyn, A. V.; Maclennan, J.; Svensen, H.; Frost, D. J.; Yallup, C.

2013-12-01

The eruption of the Siberian Traps coincided with perhaps the greatest environmental catastrophe in Earth's history, at the Permo-Triassic boundary. The source and magnitude of the volatile emissions, including sulfur, associated with the eruption remain poorly understood yet were critical in forcing environmental change. Two of the primary questions are how much sulfur gases were emitted during the eruptions and from where they were sourced. Primary melts carry dissolved sulfur from the mantle. Magmas ponding in sills and ascending through dykes may also assimilate sulfur from country rocks, as well as heat the country rocks and generate fluids through contact metamorphism. If the magmas interacted thermally, for prolonged periods, with sulfur-rich country rocks then it is probable that the sulfur budget of these eruptions might have been augmented considerably. This is exactly what we have shown recently for a basaltic sill emplaced in oil shale that fed eruptions of the British Tertiary Province, where surrounding sediments showed extensive desulfurization (Yallup et al. Geoch. Cosmochim. Acta, online, 2013). In the current study sulfur isotopes and trace element abundances are used to discriminate sulfur sources and to model magmatic processes for a suite of Siberian Traps sill and lava samples. Our bulk rock and pyrite geochemical analyses illustrate clearly their high abundance of 34S over 32S. The high 34S/32S has been noted previously and linked to assimilation of sulfur from sediments but may alternatively be inherited from the mantle plume source. With the aim of investigating the sulfur isotopic signature in the melt prior to devolatilization, we use secondary ion mass spectrometry (SIMS), for which a specific set of glass standards was synthesised. In order to understand how sulfur isotopes fractionate during degassing we have also conducted a parallel study of well-characterized tephras from Kilauea Volcano, where sulfur degassing behavior is well known.

Assessment of nanofiltration and reverse osmosis potentialities to recover metals, sulfuric acid, and recycled water from acid gold mining effluent.

PubMed

Ricci, Bárbara C; Ferreira, Carolina D; Marques, Larissa S; Martins, Sofia S; Amaral, Míriam C S

This work assessed the potential of nanofiltration (NF) and reverse osmosis (RO) to treat acid streams contaminated with metals, such as effluent from the pressure oxidation process (POX) used in refractory gold ore processing. NF and RO were evaluated in terms of rejections of sulfuric acid and metals. Regarding NF, high sulfuric acid permeation (∼100%), was observed, while metals were retained with high efficiencies (∼90%), whereas RO led to high acid rejections (<88%) when conducted in pH values higher than 1. Thus, sequential use of NF and RO was proved to be a promising treatment for sulfuric acid solutions contaminated by metals, such as POX effluent. In this context, a purified acid stream could be recovered in NF permeate, which could be further concentrated in RO. Recovered acid stream could be reused in the gold ore processing or commercialized. A metal-enriched stream could be also recovered in NF retentate and transferred to a subsequent metal recovery stage. In addition, considering the high acid rejection obtained through the proposed system, RO permeate could be used as recycling water.

Inhibition of microbiological sulfide oxidation by methanethiol and dimethyl polysulfides at natron-alkaline conditions.

PubMed

van den Bosch, Pim L F; de Graaff, Marco; Fortuny-Picornell, Marc; van Leerdam, Robin C; Janssen, Albert J H

2009-06-01

To avoid problems related to the discharge of sulfidic spent caustics, a biotechnological process is developed for the treatment of gases containing both hydrogen sulfide and methanethiol. The process operates at natron-alkaline conditions (>1 mol L(-1) of sodium- and potassium carbonates and a pH of 8.5-10) to enable the treatment of gases with a high partial CO(2) pressure. In the process, methanethiol reacts with biologically produced sulfur particles to form a complex mixture predominantly consisting of inorganic polysulfides, dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effect of these organic sulfur compounds on the biological oxidation of sulfide to elemental sulfur was studied with natron-alkaliphilic bacteria belonging to the genus Thioalkalivibrio. Biological oxidation rates were reduced by 50% at 0.05 mM methanethiol, while for DMDS and DMTS, this was estimated to occur at 1.5 and 1.0 mM, respectively. The inhibiting effect of methanethiol on biological sulfide oxidation diminished due to its reaction with biologically produced sulfur particles. This reaction increases the feasibility of biotechnological treatment of gases containing both hydrogen sulfide and methanethiol at natron-alkaline conditions.

Proteomic analysis of hydrogen photoproduction in sulfur-deprived Chlamydomonas cells.

PubMed

Chen, Mei; Zhao, Le; Sun, Yong-Le; Cui, Su-Xia; Zhang, Li-Fang; Yang, Bin; Wang, Jie; Kuang, Ting-Yun; Huang, Fang

2010-08-06

The green alga Chlamydomonas reinhardtii is a model organism to study H(2) metabolism in photosynthetic eukaryotes. To understand the molecular mechanism of H(2) metabolism, we used 2-DE coupled with MALDI-TOF and MALDI-TOF/TOF-MS to investigate proteomic changes of Chlamydomonas cells that undergo sulfur-depleted H(2) photoproduction process. In this report, we obtained 2-D PAGE soluble protein profiles of Chlamydomonas at three time points representing different phases leading to H(2) production. We found over 105 Coomassie-stained protein spots, corresponding to 82 unique gene products, changed in abundance throughout the process. Major changes included photosynthetic machinery, protein biosynthetic apparatus, molecular chaperones, and 20S proteasomal components. A number of proteins related to sulfate, nitrogen and acetate assimilation, and antioxidative reactions were also changed significantly. Other proteins showing alteration during the sulfur-depleted H(2) photoproduction process were proteins involved in cell wall and flagella metabolisms. In addition, among these differentially expressed proteins, 11 were found to be predicted proteins without functional annotation in the Chlamydomonas genome database. The results of this proteomic analysis provide new insight into molecular basis of H(2) photoproduction in Chlamydomonas under sulfur depletion.

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

NASA Technical Reports Server (NTRS)

Rillema, D. P.

1981-01-01

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Polysulfide Anchoring Mechanism Revealed by Atomic Layer Deposition of V2O5 and Sulfur-Filled Carbon Nanotubes for Lithium-Sulfur Batteries.

PubMed

Carter, Rachel; Oakes, Landon; Muralidharan, Nitin; Cohn, Adam P; Douglas, Anna; Pint, Cary L

2017-03-01

Despite the promise of surface engineering to address the challenge of polysulfide shuttling in sulfur-carbon composite cathodes, melt infiltration techniques limit mechanistic studies correlating engineered surfaces and polysulfide anchoring. Here, we present a controlled experimental demonstration of polysulfide anchoring using vapor phase isothermal processing to fill the interior of carbon nanotubes (CNTs) after assembly into binder-free electrodes and atomic layer deposition (ALD) coating of polar V 2 O 5 anchoring layers on the CNT surfaces. The ultrathin submonolayer V 2 O 5 coating on the CNT exterior surface balances the adverse effect of polysulfide shuttling with the necessity for high sulfur utilization due to binding sites near the conductive CNT surface. The sulfur loaded into the CNT interior provides a spatially separated control volume enabling high sulfur loading with direct sulfur-CNT electrical contact for efficient sulfur conversion. By controlling ALD coating thickness, high initial discharge capacity of 1209 mAh/g S at 0.1 C and exceptional cycling at 0.2 C with 87% capacity retention after 100 cycles and 73% at 450 cycles is achieved and correlated to an optimal V 2 O 5 anchoring layer thickness. This provides experimental evidence that surface engineering approaches can be effective to overcome polysulfide shuttling by controlled design of molecular-scale building blocks for efficient binder free lithium sulfur battery cathodes.

Sulfur doping of GaAs with (NH4)2Sx solution

NASA Astrophysics Data System (ADS)

Lee, Jong-Lam

1999-01-01

A novel technique for sulfur doping to GaAs was demonstrated. The surface of GaAs was treated with (NH4)2Sx solution, subsequent to annealing using either furnace or rapid thermal processing. Sulfur atoms adsorbed at the surface of GaAs during the (NH4)2Sx treatment diffuse into GaAs during the annealing. The diffusion profiles of sulfur in both types of annealing treatments show a concave shape from the GaAs surface. Diffusion constants of sulfur determined using the Boltzmann-Matano technique increase with the decrease of sulfur concentration via the depth from the surface of GaAs. This suggests that immobile sulfur donor SAs+ forms at the near surface interacts with a Ga divacancy, and results in the production of mobile As interstitials, IAs. The IAs moves fast toward the inside of GaAs and kickout the SAs+ donor, producing a fast diffusing species of interstitial S atoms. The diffusion coefficients of sulfur determined are 2.5×10-14 cm2/s at 840 °C and 5×10-12 cm2/s at 900 °C. The sulfur doping technique is applied to the fabrication of metal-semiconductor field-effect transistors (MESFETs). The MESFETs with 1.0 μm gate length exhibit transconductance of 190 mS/mm, demonstrating the applicability of this technique to the formation of active channel layer of MESFETs.

Effects of Na and secondary phases on physical properties of SnS thin film after sulfurization process

NASA Astrophysics Data System (ADS)

Kawano, Yu; Kodani, Yuto; Chantana, Jakapan; Minemoto, Takashi

2016-09-01

2.48%-efficient SnS thin film solar cell is obtained under thermal evaporation method by optimizing growth temperature. The method to fabricate SnS films is limited by growth temperature, which should not be over 200 °C to prevent re-evaporation of SnS. To further enhance SnS grains, SnS films were annealed in H2S gas from 200 to 500 °C, namely sulfurization process. SnS grain size was increased with sulfurization temperature of above 400 °C however, secondary phase grains on film’s surface were observed owing to the accumulated Na, diffused from soda-lime glass substrate into the film, thus deteriorating film’s quality, implied by Urbach energy.

Interface engineering of Cu(In,Ga)Se2 and atomic layer deposited Zn(O,S) heterojunctions

NASA Astrophysics Data System (ADS)

Schmidt, Sebastian S.; Merdes, Saoussen; Steigert, Alexander; Klenk, Reiner; Kaufmann, Christian A.; Simsek Sanli, Ekin; van Aken, Peter A.; Oertel, Mike; Schneikart, Anja; Dimmler, Bernhard; Schlatmann, Rutger

2017-08-01

Atomic layer deposition of Zn(O,S) is an attractive dry and Cd-free process for the preparation of buffer layers for chalcopyrite solar modules. As we previously reported, excellent cell and module efficiencies were achieved using absorbers from industrial pilot production. These absorbers were grown using a selenization/sulfurization process. In this contribution we report on the interface engineering required to adapt the process to sulfur-free multi source evaporated absorbers. Different approaches to a local sulfur enrichment at the heterojunction have been studied by using surface analysis (XPS) and scanning transmission electron microscopy. We correlate the microstructure and element distribution at the interface with device properties obtained by electronic characterization. The optimized completely dry process yields cell efficiencies >16% and 30 × 30 cm2 minimodule efficiencies of up to 13.9% on industrial substrates. Any degradation observed in the dry heat stress test is fully reversible after light soaking.

Post Retort, Pre Hydro-treat Upgrading of Shale Oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordon, John

Various oil feedstocks, including oil from oil shale, bitumen from tar sands, heavy oil, and refin- ery streams were reacted with the alkali metals lithium or sodium in the presence of hydrogen or methane at elevated temperature and pressure in a reactor. The products were liquids with sub- stantially reduced metals, sulfur and nitrogen content. The API gravity typically increased. Sodi- um was found to be more effective than lithium in effectiveness. The solids formed when sodium was utilized contained sodium sulfide which could be regenerated electrochemically back to so- dium and a sulfur product using a "Nasicon", sodium ionmore » conducting membrane. In addition, the process was found to be effective reducing total acid number (TAN) to zero, dramatically reduc- ing the asphaltene content and vacuum residual fraction in the product liquid. The process has promise as a means of eliminating sulfur oxide and carbon monoxide emissions. The process al- so opens the possibility of eliminating the coking process from upgrading schemes and upgrad- ing without using hydrogen.« less

Study on optimum technological conditions of ore sintering flue gas desulfurization by using poor manganese

NASA Astrophysics Data System (ADS)

Li, H. Y.; Li, S. E.; Long, Z. G.; Wu, F. Z.; Cui, T. M.; Zhou, X. Z.

2017-11-01

Orthogonal experiments were conducted to study the effect of each single factor on the desulfurization rate and leaching rate of Mn2+ to obtain improved process parameters. The results showed that the use of pyrolusite flue gas and the process method of by-product MnSO4 can not only effectively remove the sulfur in the gas, thereby controlling environmental pollution, but can also recover sulfur.

Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

NASA Astrophysics Data System (ADS)

McDermott, Jill M.; Ono, Shuhei; Tivey, Margaret K.; Seewald, Jeffrey S.; Shanks, Wayne C.; Solow, Andrew R.

2015-07-01

Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) δ34S values range from -5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of δ34S for cubic cubanite and H2S range from -1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero Δ33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. Δ33S values indicate that SO2 disproportionation is an additional process that contributes sulfur to a different back-arc system and to acid spring-type hydrothermal fluid circulation. At the sedimented Guaymus Basin, near-zero Δ33S values are also observed, despite negative δ34S values that indicate inputs of biogenic pyrite for some samples. In contrast with previous studies reporting isotope disequilibrium between H2S and chalcopyrite, the δ34S values of chalcopyrite sampled from the inner 1-2 mm of a chimney wall are within ±1‰ of δ34S values for H2S in the paired vent fluid, suggesting equilibrium fluid-mineral sulfur isotope exchange at 300-400 °C. Isotopic equilibrium between hydrothermal fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in the chalcopyrite lining across a chimney wall may accurately record past hydrothermal activity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordon, John Howard; Alvare, Javier

Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution andmore » may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.« less

Trace desulfurization. [DOE patent application

DOEpatents

Chen, H.L.; Stevens, C.G.

A method for reducing a trace concentration of sulfur-containing compounds in a gas stream from about one part in 10/sup 4/ to about one part in 10/sup 7/. The method includes the steps of irradiating the gas stream with an energy source which has a central emission frequency chosen to substantially match a wavelength of energy absorption of the sulfur-containing compounds and of subsequently contacting the gas stream with a reactive surface which includes a reactant selected from elemental metals and metal oxides so that metallic sulfur-containing compounds are formed. The reduction in concentration allows the gas stream to be processed in certain reactions having catalysts which would otherwise be poisoned by the sulfur-containing compounds.

An Aerosol Condensation Model for Sulfur Trioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grant, K E

This document describes a model for condensation of sulfuric acid aerosol given an initial concentration and/or source of gaseous sulfur trioxide (e.g. fuming from oleum). The model includes the thermochemical effects on aerosol condensation and air parcel buoyancy. Condensation is assumed to occur heterogeneously onto a preexisting background aerosol distribution. The model development is both a revisiting of research initially presented at the Fall 2001 American Geophysical Union Meeting [1] and a further extension to provide new capabilities for current atmospheric dispersion modeling efforts [2]. Sulfuric acid is one of the most widely used of all industrial chemicals. In 1992,more » world consumption of sulfuric acid was 145 million metric tons, with 42.4 Mt (mega-tons) consumed in the United States [10]. In 2001, of 37.5 Mt consumed in the U.S., 74% went into producing phosphate fertilizers [11]. Another significant use is in mining industries. Lawuyi and Fingas [7] estimate that, in 1996, 68% of use was for fertilizers and 5.8% was for mining. They note that H{sub 2}SO{sub 4} use has been and should continue to be very stable. In the United States, the elimination of MTBE (methyl tertiary-butyl ether) and the use of ethanol for gasoline production are further increasing the demand for petroleum alkylate. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used today. Concerns, however, over the safety or potential regulation of hydrofluoric acid are likely to result in most of the growth being for the sulfuric acid process, further increasing demand [11]. The implication of sulfuric acid being a pervasive industrial chemical is that transport is also pervasive. Often, this is in the form of oleum tankers, having around 30% free sulfur trioxide. Although sulfuric acid itself is not a volatile substance, fuming sulfuric acid (referred to as oleum) is [7], the volatile product being sulfur trioxide. Sulfate aerosols and mist may form in the atmosphere on tank rupture. From chemical spill data from 1990-1996, Lawuyi02 and Fingas [7] prioritize sulfuric acid as sixth most serious. During this period, they note 155 spills totaling 13 Mt, out of a supply volume of 3700 Mt. Lawuyi and Fingas [7] summarize information on three major sulfuric acid spills. On 12 February 1984, 93 tons of sulfuric acid were spilled when 14 railroad cars derailed near MacTier, Parry Sound, Ontario. On 13 December 1978, 51 railroad cars derailed near Springhill, Nova Scotia. One car, containing 93% sulfuric acid, ruptured, spilling nearly its entire contents. In July 1993, 20 to 50 tons of fuming sulfuric acid spilled at the General Chemical Corp. plant in Richmond, California, a major industrial center near San Francisco. The release occurred when oleum was being loaded into a nonfuming acid railroad tank car that contained only a rupture disk as a safety device. The tank car was overheated and this rupture disk blew. The resulting cloud of sulfuric acid drifted northeast with prevailing winds over a number of populated areas. More than 3,000 people subsequently sought medical attention for burning eyes, coughing, headaches, and nausea. Almost all were treated and released on the day of the spill. By the day after the release, another 5,000 people had sought medical attention. The spill forced the closure of five freeways in the region as well as some Bay Area Rapid Transit System stations. Apart from corrosive toxicity, there is the additional hazard that the reactions of sulfur trioxide and sulfuric acid vapors with water are extremely exothermic [10, 11]. While the vapors are intrinsically denser than air, there is thus the likelihood of strong, warming-induced buoyancy from reactions with ambient water vapor, water-containing aerosol droplets, and wet environmental surface. Nordin [12] relates just such an occurrence following the Richmond, CA spill, with the plume observed to rise to 300 m. For all practical purposes, sulfur trioxide was the constituent released from the heated tank car. The behavior of the resulting plume suggested that initially sulfur trioxide behaved as a dense gas, but the chemical reacted with air humidity, producing sulfuric acid and heat. The heat caused the plume to rise. Eventually the plume cooled, resulting in sulfuric acid descending towards people on the ground. This kind of behavior is not accounted for in the popular gas dispersion models. In the presence of complex terrain, such heat induced buoyancy could enable a sulfur trioxide cloud to leap local drainage boundaries with a single bound. Unless there were insufficient water/humidity to fully react with the SO{sub 3} and H{sub 2}SO{sub 4} on the first ascent, no secondary bounds would be expected, the cloud then behaving as a heavy tracer until sufficiently diluted.« less

Assessment of sulfide production risk in soil during the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification process.

PubMed

Ghorbel, L; Coudert, L; Gilbert, Y; Mercier, G; Blais, J F

2016-10-01

This study aimed to determine the potential of sulfide generation during infiltration through soil of domestic wastewater treated by a sulfur-utilizing denitrification process. Three types of soil with different permeability rates (K s = 0.028, 0.0013, and 0.00015 cm/s) were investigated to evaluate the potential risk of sulfur generation during the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification system. These soils were thoroughly characterized and tested to assess their capacity to be used as drainages for wastewaters. Experiments were conducted under two operating modes (saturated and unsaturated). Sulfate, sulfide, and chemical oxygen demand (COD) levels were determined over a period of 100 days. Despite the high concentration of sulfates (200 mg/L) under anaerobic conditions (ORP = -297 mV), no significant amount of sulfide was generated in the aqueous (<0.2 mg/L) or gaseous (<0.15 ppm) phases. Furthermore, the soil permeability did not have a noticeable effect on the infiltration of domestic wastewater treated by a sulfur-utilizing denitrification system due to low contents of organic matter (i.e., dissolved organic carbon, DOC). The autotrophic denitrification process used to treat the domestic wastewater allowed the reduction of the concentration of biochemical oxygen demand (BOD5) below 5 mg/L, of DOC below 7 mg/L, and of COD below 100 mg/L.

77 FR 1996 - National Organic Program (NOP); Sunset Review (2012)

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-12

... production at Sec. 205.601(g)(1) as follows: Sulfur dioxide--underground rodent control only (smoke bombs). The Environmental Protection Agency (EPA) registers smoke bomb products for underground rodent control...). Smoke bombs are placed into rodent burrows and detonated. The detonation process produces sulfur dioxide...

40 CFR 60.161 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... contained in the concentrate as it passes through an oxidizing atmosphere, or the combustion of a fossil...) Sulfuric acid plant means any facility producing sulfuric acid by the contact process. (i) Fossil fuel means natural gas, petroleum, coal, and any form of solid, liquid, or gaseous fuel derived from such...

40 CFR 60.161 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... contained in the concentrate as it passes through an oxidizing atmosphere, or the combustion of a fossil...) Sulfuric acid plant means any facility producing sulfuric acid by the contact process. (i) Fossil fuel means natural gas, petroleum, coal, and any form of solid, liquid, or gaseous fuel derived from such...

40 CFR 60.161 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... contained in the concentrate as it passes through an oxidizing atmosphere, or the combustion of a fossil...) Sulfuric acid plant means any facility producing sulfuric acid by the contact process. (i) Fossil fuel means natural gas, petroleum, coal, and any form of solid, liquid, or gaseous fuel derived from such...

40 CFR 60.161 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... contained in the concentrate as it passes through an oxidizing atmosphere, or the combustion of a fossil...) Sulfuric acid plant means any facility producing sulfuric acid by the contact process. (i) Fossil fuel means natural gas, petroleum, coal, and any form of solid, liquid, or gaseous fuel derived from such...

40 CFR 60.161 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... contained in the concentrate as it passes through an oxidizing atmosphere, or the combustion of a fossil...) Sulfuric acid plant means any facility producing sulfuric acid by the contact process. (i) Fossil fuel means natural gas, petroleum, coal, and any form of solid, liquid, or gaseous fuel derived from such...

Process for removing sulfur from sulfur-containing gases

DOEpatents

Rochelle, Gary T.; Jozewicz, Wojciech

1990-01-01

The present disclosure relates to i The government may own certain rights in the present invention pursuant to EPA Cooperative Agreement CR 81-1531. This is a continuation of U.S. Ser. No. 928,337, filed Nov. 7, 1986, now U.S. Pat. No. 4,804,521.

40 CFR 62.11610 - Identification of plan.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Reduced Sulfur Emissions from Existing Kraft Pulp Mills § 62.11610 Identification of plan. (a) Title of... Department of Virginia Department of Air Pollution Control, on May 15, 1990. (c) Identification of sources... process (added), Straight kraft recovery furnace (revised), Total reduced sulfur (revised)), 5-40-1690, 5...

Flocculation of high purity wheat straw soda lignin

USDA-ARS?s Scientific Manuscript database

Flocculant action on lignocellulose mixtures has been studied, but flocculant action on purified sulfur-free lignin has not been reported. In the last step of the industrial process, the purified lignin solution is acidified with sulfuric acid which causes the lignin to become insoluble. The feasi...

Anaerobic Copper Toxicity and Iron-Sulfur Cluster Biogenesis in Escherichia coli.

PubMed

Tan, Guoqiang; Yang, Jing; Li, Tang; Zhao, Jin; Sun, Shujuan; Li, Xiaokang; Lin, Chuxian; Li, Jianghui; Zhou, Huaibin; Lyu, Jianxin; Ding, Huangen

2017-08-15

While copper is an essential trace element in biology, pollution of groundwater from copper has become a threat to all living organisms. Cellular mechanisms underlying copper toxicity, however, are still not fully understood. Previous studies have shown that iron-sulfur proteins are among the primary targets of copper toxicity in Escherichia coli under aerobic conditions. Here, we report that, under anaerobic conditions, iron-sulfur proteins in E. coli cells are even more susceptible to copper in medium. Whereas addition of 0.2 mM copper(II) chloride to LB (Luria-Bertani) medium has very little or no effect on iron-sulfur proteins in wild-type E. coli cells under aerobic conditions, the same copper treatment largely inactivates iron-sulfur proteins by blocking iron-sulfur cluster biogenesis in the cells under anaerobic conditions. Importantly, proteins that do not have iron-sulfur clusters (e.g., fumarase C and cysteine desulfurase) in E. coli cells are not significantly affected by copper treatment under aerobic or anaerobic conditions, indicating that copper may specifically target iron-sulfur proteins in cells. Additional studies revealed that E. coli cells accumulate more intracellular copper under anaerobic conditions than under aerobic conditions and that the elevated copper content binds to the iron-sulfur cluster assembly proteins IscU and IscA, which effectively inhibits iron-sulfur cluster biogenesis. The results suggest that the copper-mediated inhibition of iron-sulfur proteins does not require oxygen and that iron-sulfur cluster biogenesis is the primary target of anaerobic copper toxicity in cells. IMPORTANCE Copper contamination in groundwater has become a threat to all living organisms. However, cellular mechanisms underlying copper toxicity have not been fully understood up to now. The work described here reveals that iron-sulfur proteins in Escherichia coli cells are much more susceptible to copper in medium under anaerobic conditions than they are under aerobic conditions. Under anaerobic conditions, E. coli cells accumulate excess intracellular copper, which specifically targets iron-sulfur proteins by blocking iron-sulfur cluster biogenesis. Since iron-sulfur proteins are involved in diverse and vital physiological processes, inhibition of iron-sulfur cluster biogenesis by copper disrupts multiple cellular functions and ultimately inhibits cell growth. The results from this study illustrate a new interplay between intracellular copper toxicity and iron-sulfur cluster biogenesis in bacterial cells under anaerobic conditions. Copyright © 2017 American Society for Microbiology.

Anaerobic Copper Toxicity and Iron-Sulfur Cluster Biogenesis in Escherichia coli

PubMed Central

Tan, Guoqiang; Yang, Jing; Li, Tang; Zhao, Jin; Sun, Shujuan; Li, Xiaokang; Lin, Chuxian; Li, Jianghui; Zhou, Huaibin

2017-01-01

ABSTRACT While copper is an essential trace element in biology, pollution of groundwater from copper has become a threat to all living organisms. Cellular mechanisms underlying copper toxicity, however, are still not fully understood. Previous studies have shown that iron-sulfur proteins are among the primary targets of copper toxicity in Escherichia coli under aerobic conditions. Here, we report that, under anaerobic conditions, iron-sulfur proteins in E. coli cells are even more susceptible to copper in medium. Whereas addition of 0.2 mM copper(II) chloride to LB (Luria-Bertani) medium has very little or no effect on iron-sulfur proteins in wild-type E. coli cells under aerobic conditions, the same copper treatment largely inactivates iron-sulfur proteins by blocking iron-sulfur cluster biogenesis in the cells under anaerobic conditions. Importantly, proteins that do not have iron-sulfur clusters (e.g., fumarase C and cysteine desulfurase) in E. coli cells are not significantly affected by copper treatment under aerobic or anaerobic conditions, indicating that copper may specifically target iron-sulfur proteins in cells. Additional studies revealed that E. coli cells accumulate more intracellular copper under anaerobic conditions than under aerobic conditions and that the elevated copper content binds to the iron-sulfur cluster assembly proteins IscU and IscA, which effectively inhibits iron-sulfur cluster biogenesis. The results suggest that the copper-mediated inhibition of iron-sulfur proteins does not require oxygen and that iron-sulfur cluster biogenesis is the primary target of anaerobic copper toxicity in cells. IMPORTANCE Copper contamination in groundwater has become a threat to all living organisms. However, cellular mechanisms underlying copper toxicity have not been fully understood up to now. The work described here reveals that iron-sulfur proteins in Escherichia coli cells are much more susceptible to copper in medium under anaerobic conditions than they are under aerobic conditions. Under anaerobic conditions, E. coli cells accumulate excess intracellular copper, which specifically targets iron-sulfur proteins by blocking iron-sulfur cluster biogenesis. Since iron-sulfur proteins are involved in diverse and vital physiological processes, inhibition of iron-sulfur cluster biogenesis by copper disrupts multiple cellular functions and ultimately inhibits cell growth. The results from this study illustrate a new interplay between intracellular copper toxicity and iron-sulfur cluster biogenesis in bacterial cells under anaerobic conditions. PMID:28576762

Method of removing sulfur emissions from a fluidized-bed combustion process

DOEpatents

Vogel, Gerhard John; Jonke, Albert A.; Snyder, Robert B.

1978-01-01

Alkali metal or alkaline earth metal oxides are impregnated within refractory support material such as alumina and introduced into a fluidized-bed process for the combustion of coal. Sulfur dioxide produced during combustion reacts with the metal oxide to form metal sulfates within the porous support material. The support material is removed from the process and the metal sulfate regenerated to metal oxide by chemical reduction. Suitable pore sizes are originally developed within the support material by heat-treating to accommodate both the sulfation and regeneration while still maintaining good particle strength.

Final Report - Glass Formulation Testing to Increase Sulfate Volatilization from Melter, VSL-04R4970-1, Rev. 0, dated 2/24/05

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kruger, Albert A.; Matlack, K. A.; Pegg, I. L.

2013-11-13

The principal objectives of the DM100 and DM10 tests were to determine the impact of four different organics and one inorganic feed additive on sulfate volatilization and to determine the sulfur partitioning between the glass and the off-gas system. The tests provided information on melter processing characteristics and off-gas data including sulfur incorporation and partitioning. A series of DM10 and DM100 melter tests were conducted using a LAW Envelope A feed. The testing was divided into three parts. The first part involved a series of DM10 melter tests with four different organic feed additives: sugar, polyethylene glycol (PEG), starch, andmore » urea. The second part involved two confirmatory 50-hour melter tests on the DM100 using the best combination of reductants and conditions based on the DM10 results. The third part was performed on the DM100 with feeds containing vanadium oxide (V{sub 2}O{sub 5}) as an inorganic additive to increase sulfur partitioning to the off-gas. Although vanadium oxide is not a reductant, previous testing has shown that vanadium shows promise for partitioning sulfur to the melter exhaust, presumably through its known catalytic effect on the SO{sub 2}/SO{sub 3} reaction. Crucible-scale tests were conducted prior to the melter tests to confirm that the glasses and feeds would be processable in the melter and that the glasses would meet the waste form (ILAW) performance requirements. Thus, the major objectives of these tests were to: Perform screening tests on the DM10 followed by tests on the DM100-WV system using a LAW -Envelope A feed with four organic additives to assess their impact on sulfur volatilization. Perform tests on the DM100-WV system using a LAW -Envelope A feed containing vanadium oxide to assess its impact on sulfur volatilization. Determine feed processability and product quality with the above additives. Collect melter emissions data to determine the effect of additives on sulfur partitioning and melter emissions. Collect and analyze discharged glass to determine sulfur retention in the glass. Prepare and characterize feeds and glasses with the additives to confirm that the feeds and the glass melts are suitable for processing in the DM100 melter. Prepare and characterize glasses with the additives to confirm that the glasses meet the waste form (ILAW) performance requirements.« less

Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices.

PubMed

Djokic, Marko R; Ristic, Nenad D; Olahova, Natalia; Marin, Guy B; Van Geem, Kevin M

2017-08-04

An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC×GC) equipped with two capillary columns (Rtx ® -1 PONA×SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC×GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H 2 S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC×GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefin-rich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC×GC-FID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75% of the sulfur contained in the feed is converted to hydrogen sulfide, 13% to alkyl homologues of thiophene while the remaining 12% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen evolution, bio-waste pyrolysis, supercritical water treatment, etc. Copyright © 2017 Elsevier B.V. All rights reserved.

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems.

PubMed

Bern, Carleton R; Chadwick, Oliver A; Kendall, Carol; Pribil, Michael J

2015-05-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ(34)S VCDT) of -0.8‰. Bulk deposition on the island of Maui had a δ(34)S VCDT that varied temporally, spanned a range from +8.2 to +19.7‰, and reflected isotopic mixing from three sources: sea-salt (+21.1‰), marine biogenic emissions (+15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to +2.7‰) to relatively high (+17.8 to +19.3‰) soil δ(34)S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from +8.1 to +20.3‰ and generally decreased with increasing elevation (0-2000 m), distance from the coast (0-12 km), and annual rainfall (180-5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur biogeochemistry across relatively small spatial scales. Published by Elsevier B.V.

CONTROL OF SULFUR EMISSIONS FROM OIL SHALE RETORTING USING SPEND SHALE ABSORPTION

EPA Science Inventory

The paper gives results of a detailed engineering evaluation of the potential for using an absorption on spent shale process (ASSP) for controlling sulfur emissions from oil shale plants. The evaluation analyzes the potential effectiveness and cost of absorbing SO2 on combusted s...

40 CFR 80.230 - Who is not eligible for the hardship provisions for small refiners?

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF FUELS AND FUEL ADDITIVES Gasoline Sulfur... reorganization; (3) Importers; and (4) Refiners who produce gasoline other than by processing crude oil through... refineries for which the Administrator has approved an extension of the small refiner gasoline sulfur...

40 CFR 80.230 - Who is not eligible for the hardship provisions for small refiners?

Code of Federal Regulations, 2010 CFR

2010-07-01

... AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF FUELS AND FUEL ADDITIVES Gasoline Sulfur... reorganization; (3) Importers; and (4) Refiners who produce gasoline other than by processing crude oil through... refineries for which the Administrator has approved an extension of the small refiner gasoline sulfur...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wujcik, Kevin H.; Wang, Dunyang Rita; Pascal, Tod A.

Lithium sulfur (Li-S) batteries are well known for their high theoretical specific capacities, but are plagued with scientific obstacles that make practical implementation of the technology impossible. The success of Li-S batteries will likely necessitate the use of thick sulfur cathodes that enable high specific energy densities. However, little is known about the fundamental reaction mechanisms and chemical processes that take place in thick cathodes, as most research has focused on studying thinner cathodes that enable high performance. In this study, in situ X-ray absorption spectroscopy at the sulfur K-edge is used to examine the back of a 115 μmmore » thick Li-S cathode during discharge. Our results show that in such systems, where electrochemical reactions between sulfur and lithium are likely to proceed preferentially toward the front of the cathode, lithium polysulfide dianions formed in this region diffuse to the back of the cathode during discharge. We show that high conversion of elemental sulfur is achieved by chemical reactions between elemental sulfur and polysulfide dianions of intermediate chain length (Li 2S x, 4 ≤ x ≤ 6). Our work suggests that controlling the formation and diffusion of intermediate chain length polysulfide dianions is crucial for insuring full utilization of thick sulfur cathodes.« less

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Development of a tunable Fabry-Perot interferometer UV camera for monitoring sulfur dioxide emissions

NASA Astrophysics Data System (ADS)

Tamminen, J.; Kujanpää, J.; Ojanen, H.; Saari, H.; Näkki, I.; Tukiainen, S.; Kyrölä, E.

2017-12-01

We present a novel UV camera for sulfur dioxide emission monitoring.The camera is equipped with a piezo-actuated Fabry-Perot interferometer allowing thefilter transmission to be tuned to match the differential absorption features ofsulfur dioxide in the wavelength region 305-320 nm. The differential absorption structuresare exploited to reduce the interfering effects of weakly wavelength dependent absorbers, suchas aerosols and black carbon, present in the exhaust gas. A data processing algorithm basedon two air gaps of the filter is presented allowing collection of a sufficient signal-to-noise ratio fordetecting sulfur dioxide in the ship plumes even in the designated emission control areas, such as the Baltic Seawhere the sulfur content limit of fuel oil is 0.1 %. First field tests performed inLänsisatama harbour, Helsinki Finland, indicate that sulfur dioxide can be detectedin ship plumes. The camera is light-weight and can be mounted to a drone.

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

NASA Technical Reports Server (NTRS)

Fielder, W. L.; Singer, J.

1978-01-01

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

PubMed Central

Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

2017-01-01

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid production, and mixed valence state sulfur species generated by the oxidation of the two different substrates suggests a metabolic flexibility in response to sulfur substrate availability. Our results demonstrate that microbial processing of mixed-valence-state sulfur species generates a significant sulfur isotope fractionation in acidic environments and oxidation of mixed-valence state sulfur species may produce sulfate with characteristic sulfur and oxygen isotope signatures. Elemental sulfur and tetrathionate are not only intermediate-valence state sulfur compounds that play a central role in sulfur oxidation pathways, but also key factors in shaping these isotope patterns. PMID:28861071

SOXAL combined SO{sub x}/NO{sub x} flue gas control demonstration. Quarterly report, January--March 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

AQUATECH Systems a business unit of Allied-Signal Inc., proposes to demonstrate the technical viability and cost effectiveness of the SOXAL process a combined SO{sub x}/NO{sub x} control process on a 3 MW equivalent flue gas slip stream from Niagara Mohawk Power Corporation, Dunkirk Steam Station Boiler No. 4, a coal fired boiler. The SOXAL process combines 90+% sulfur dioxide removal from the flue gas using a sodium based scrubbing solution and regeneration of the spent scrubbing liquor using AQUATECH Systems` proprietary bipolar membrane technology. This regeneration step recovers a stream of sulfur dioxide suitable for subsequent processing to salable sulfurmore » or sulfuric acid. Additionally 90+% control of NO{sub x} gases can be achieved in combination with conventional urea/methanol injection of NO{sub 2} gas into the duct. The SOXAL process is applicable to both utility and industrial scale boilers using either high or low sulfur coal. The SOXAL demonstration Program began September 10, 1991 and is approximately 22 months in duration. During the 6 months of scheduled operations period, expected to begin January 1992, data will be collected from the SOXAL system to define: SO{sub 2} and NO{sub x} control efficiencies; Current efficiency for the regeneration unit; Sulfate oxidation in the absorber; Make-up reagent rates; Product quality including concentrations and compositions; System integration and control philosophy; and Membrane stability and performance with respect to foulants.« less

The fate of sulfur in mild gasification liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight, R.A.; Koncar, G.J.; Babu, S.P.

1991-01-01

This investigation addresses the determination of sulfur distribution in mild gasification liquids produced from untreated coal and from modified in two ways to reduce sulfur in the products: (a) physical mixing with a sulfur scavenger (CaO), and (b) pretreatment with aqueous alkali followed by mixing with CaO. Coal pyrolysis in the presence of CaO has previously been investigated, (3,5) showing that CaO can be effective in reducing the sulfur content of the fuel gas, and possibly that of the product liquids. Pretreatment of coals with alkaline chemicals has also been studied,(6,7) showing reduced sulfur and other changes in the liquidmore » products.(8) Data on sulfur distribution in the liquid products could be useful for understanding the chemistry of alkali pretreatment and CaO interaction with coal sulfur during pyrolysis. In this work, a pyrolysis-gas chromatography (Py-GC) technique that simulates mild gasification on a milligram scale was used in conjunction with a carbon-specific flame ionization detector (FID) and a sulfur-specific flame photometric detector (FPD) to determine the sulfur distribution in oils/tars from Illinois No. 6 coal. A low-resolution packed GC column was employed to resolve oils/tars by carbon number, with ranges selected to approximate distillation fractions which might be recovered from a commercial mild gasification process. Oils/tars up to C{sub 18} were also collected from the pyro-probe effluent into dichloromethane for off-line study using a high-resolution GC with atomic emission detector (GC/AED) and with GC-mass spectrometry (GC/MS) to measure specific sulfur compounds. 9 refs., 1 tab.« less

Identification of sulfur fumed Pinelliae Rhizoma using an electronic nose

PubMed Central

Zhou, Xia; Wan, Jun; Chu, Liang; Liu, Wengang; Jing, Yafeng; Wu, Chunjie

2014-01-01

Background: Pinelliae Rhizoma is a commonly used Chinese herb which will change brown during the natural drying process. However, sulfur fumed Pinelliae Rhizoma will get a better appearance than naturally dried one. Sulfur fumed Pinelliae Rhizoma is potentially toxical due to sulfur dioxide and sulfites formed during the fuming procedures. The odor components in sulfur fumed Pinelliae Rhizoma is complex. At present, there is no analytical method available to determine sulfur fumed Pinelliae Rhizoma simply and rapidly. To ensure medication safety, it is highly desirable to have an effective and simple method to identify sulfur fumed Pinelliae Rhizoma. Materials and Methods: This paper presents a novel approach using an electronic nose based on metal oxide sensors to identify whether Pinelliae Rhizoma was fumed with sulfur, and to predict the fuming degree of Pinelliae Rhizoma. Multivariate statistical methods such as principal components analysis (PCA), discriminant factorial analysis (DFA) and partial least squares (PLS) were used for data analyzing and identification. The use of the electronic nose to discriminate between different fuming degrees Pinelliae Rhizoma and naturally dried Pinelliae Rhizoma was demonstrated. Results: The electronic nose was also successfully applied to identify unknown samples including sulfur fumed samples and naturally dried samples, high recognition value was obtained. Quantitative analysis of fuming degree of Pinelliae Rhizoma was also demonstrated. The method developed is simple and fast, which provides a new quality control method of Chinese herbs from the aspect of odor. Conclusion: It has shown that this electronic nose based metal oxide sensor is sensitive to sulfur and sulfides. We suggest that it can serve as a supportive method to detect residual sulfur and sulfides. PMID:24914293

New electrostatic coal cleaning method cuts sulfur content by 40%

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1985-12-01

An emission control system that electrically charges pollutants and coal particles promises to reduce sulfur 40% at half the cost. The dry coal cleaning processes offer superior performance and better economics than conventional flotation cleaning. Advanced Energy Dynamics, Inc. (AED) is developing both fine and ultra fine processes which increase combustion efficiency and boiler reliability and reduced operating costs. The article gives details from the performance tests and comparisons and summarizes the economic analyses. 4 tables.

Effect of Dietary Processed Sulfur Supplementation on Texture Quality, Color and Mineral Status of Dry-cured Ham.

PubMed

Kim, Ji-Han; Ju, Min-Gu; Yeon, Su-Jung; Hong, Go-Eun; Park, WooJoon; Lee, Chi-Ho

2015-01-01

This study was performed to investigate the chemical composition, mineral status, oxidative stability, and texture attributes of dry-cured ham from pigs fed processed sulfur (S, 1 g/kg feed), and from those fed a basal diet (CON), during the period from weaning to slaughter (174 d). Total collagen content and soluble collagen of the S group was significantly higher than that of the control group (p<0.05). The pH of the S group was significantly higher than that of the control group, whereas the S group had a lower expressible drip compared to the control group. The S group also showed the lower lightness compared to the control group (p<0.05). In regard to the mineral status, the S group had significantly lower Fe(2+) and Ca(2+) content than the control group (p<0.05), whereas the proteolysis index of the S group was significantly increased compared to the control group (p<0.05). The feeding of processed sulfur to pigs led to increased oxidative stability, related to lipids and pigments, in the dry-cured ham (p<0.05). Compared to the dry-cured ham from the control group, that from the S group exhibited lower springiness and gumminess; these results suggest that feeding processed sulfur to pigs can improve the quality of the texture and enhance the oxidative stability of dry-cured ham.

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

PubMed Central

Li, Haipeng; Sun, Liancheng; Wang, Zhuo; Zhang, Yongguang; Tan, Taizhe; Wang, Gongkai

2018-01-01

A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S) batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide) aerogel (S/AC/GA) cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO) was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D) interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V. PMID:29373525

DEEP DESULFURIZATION OF DIESEL FUELS BY A NOVEL INTEGRATED APPROACH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiaoliang Ma; Uday Turaga; Shingo Watanabe

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 andmore » 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-through point at 5.0 ppmw sulfur level is 0.35 mg-S/g-A. The spent A-5 can be regenerated by using H2 gas at a flowing rate of 40-50 ml/min, 500 C, and ambient pressure. Adsorption desulfurization of model diesel fuels over metal-sulfide-based adsorbents (A-6-1 and A-6-2) has been conducted at different temperatures to examine the capacity and selectivity of the adsorbents. A regeneration method for the spent metal-sulfide-based adsorbents has been developed. The spent A-6-1 can be easily regenerated by washing the spent adsorbent with a polar solvent followed by heating the adsorbent bed to remove the remainder solvent. Almost all adsorption capacity of the fresh A-6-1 can be recovered after the regeneration. On the other hand, a MCM-41-supported HDS catalyst was developed for deep desulfurization of the refractory sulfur compounds. The results show that the developed MCM-41-supported catalyst demonstrates consistently higher activity for the HDS of the refractory dibenzothiophenic sulfur compounds than the commercial catalyst. On the basis of the fundamental understanding of the adsorptive performance and regeneration natures of the adsorbents, the conceptual design of the novel PSU-SARS process for deep desulfurization of diesel fuel is confirmed and improved further.« less

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions.

PubMed

Lee, Chun W; Serre, Shannon D; Zhao, Yongxin; Lee, Sung Jun; Hastings, Thomas W

2008-04-01

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

NASA Astrophysics Data System (ADS)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Johnston, David T.

2018-02-01

Ultramafic-hosted hydrothermal systems - characterized by ongoing serpentinization reactions - exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20‧N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209). In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of -33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (<120 °C) that permitted microbial activity. The change in temperature regime is locally preserved in individual samples and correlates with the progressive uplift and exposure of mantle rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these systems. Overall, the combined application of in situ and bulk rock multiple sulfur isotope measurements with petrographic observations allows us to resolve the different episodes of sulfur cycling during alteration of the oceanic lithosphere and the temporal changes between abiogenic and biogenic processes that control the sulfur cycling in these systems.

Geochemistry of sulfur in the Florida Everglades; 1994 through 1999

USGS Publications Warehouse

Bates, Anne L.; Orem, W.H.; Harvey, J.W.; Spiker, E. C.

2000-01-01

In this report, we present data on the geochemistry of sulfur in sediments and in surface water, groundwater, and rainwater in the Everglades region in south Florida. The results presented here are part of a larger study intended to determine the roles played by the cycling of carbon, nitrogen, phosphorus, and sulfur in the ecology of the south Florida wetlands. The geochemistry of sulfur in the region is particularly important because of its link to the production of toxic methylmercury through processes mediated by sulfate reducing bacteria. Sediment cores were collected from the Everglades Agricultural Area (EAA), Water Conservation Areas (WCAs) 1A and 2A, from Lake Okeechobee, and from Taylor Slough in the southern Everglades. Water collection was more widespread and includes surface water from WCAs 1A, 2A, 3A, 2B, the EAA, Taylor Slough, Lake Okeechobee, and the Kissimmee River. Groundwater was collected from The Everglades Nutrient Removal Area (ENR) and from WCA 2A. Rainwater was collected at two month intervals over a period of one year from the ENR and from WCA 2A. Water was analyzed for sulfate concentration and sulfate sulfur stable isotopic ratio (34S/32S). Sediment cores were analyzed for total sulfur concentration and/or for concentrations of sulfur species (sulfate, organic sulfur, disulfides, and acid volatile sulfides (AVS)) and for their stable sulfur isotopic ratio. Results show a decrease in total sulfur content (1.57 to 0.61 percent dry weight) with depth in two sediment cores collected in WCA 2A, indicating that there has been an increase in total sulfur content in recent times. A sediment core from the center of Lake Okeechobee shows a decrease in total sulfur content with depth (0.28 to 0.08 percent dry weight). A core from the periphery of the lake (South Bay) likewise shows a decrease in total sulfur content with depth (1.00 to 0.69 percent dry weight), however, the overall sulfur content is greater than that near the center at all depths. This suggests input of sulfur in recent times, especially near the lake margins. Sediments show a general decrease in sulfur concentration with depth, probably because of increases in sulfur input to the marshes in recent times. Regional differences in the concentrations and stable isotopic ratios of sulfate sulfur in surface water show that sulfur contamination to the northern Everglades likely originates from canals draining the EAA.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.