Oxidative Desulfurization of Fuel Oil by Pyridinium-Based Ionic Liquids

OpenAIRE

Erhong Duan; Dishun Zhao; Yanan Wang

2009-01-01

In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF4 was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF4 has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil) /V(H2O2) = 1:1:0.4, temperature 55 °C, the time 30 min. The ...

Metabolic and process engineering for biodesulfurization in Gram-negative bacteria.

Science.gov (United States)

Martínez, I; El-Said Mohamed, M; Santos, V E; García, J L; García-Ochoa, F; Díaz, E

2017-11-20

Microbial desulfurization or biodesulfurization (BDS) is an attractive low-cost and environmentally friendly complementary technology to the hydrotreating chemical process based on the potential of certain bacteria to specifically remove sulfur from S-heterocyclic compounds of crude fuels that are recalcitrant to the chemical treatments. The 4S or Dsz sulfur specific pathway for dibenzothiophene (DBT) and alkyl-substituted DBTs, widely used as model S-heterocyclic compounds, has been extensively studied at the physiological, biochemical and genetic levels mainly in Gram-positive bacteria. Nevertheless, several Gram-negative bacteria have been also used in BDS because they are endowed with some properties, e.g., broad metabolic versatility and easy genetic and genomic manipulation, that make them suitable chassis for systems metabolic engineering strategies. A high number of recombinant bacteria, many of which are Pseudomonas strains, have been constructed to overcome the major bottlenecks of the desulfurization process, i.e., expression of the dsz operon, activity of the Dsz enzymes, retro-inhibition of the Dsz pathway, availability of reducing power, uptake-secretion of substrate and intermediates, tolerance to organic solvents and metals, and other host-specific limitations. However, to attain a BDS process with industrial applicability, it is necessary to apply all the knowledge and advances achieved at the genetic and metabolic levels to the process engineering level, i.e., kinetic modelling, scale-up of biphasic systems, enhancing mass transfer rates, biocatalyst separation, etc. The production of high-added value products derived from the organosulfur material present in oil can be regarded also as an economically viable process that has barely begun to be explored. Copyright © 2017 Elsevier B.V. All rights reserved.

Nano-magnetic particles as multifunctional microreactor for deep desulfurization

Energy Technology Data Exchange (ETDEWEB)

Cui, Xinai; Yao, Dongdong [Engineering Research Center of Historical and Cultural Heritage Protection, Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi' an 710062 (China); Li, Hong [College of Environment and Chemical Engineering, Xi' an Polytechnic University, Xi' an 710048 (China); Yang, Juxiang [Department of Chemistry, Xi' an University of Arts and Science, Xi' an 710065 (China); Hu, Daodao, E-mail: daodaohu@snnu.edu.cn [Engineering Research Center of Historical and Cultural Heritage Protection, Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi' an 710062 (China)

2012-02-29

Highlights: Black-Right-Pointing-Pointer An easy-separated amphiphilic catalyst with small size was prepared for deep desulfurization. Black-Right-Pointing-Pointer The effects of several factors on desulfurization reactivity were systematically investigated. Black-Right-Pointing-Pointer The catalyst demonstrates high performance in the deep desulfurization. Black-Right-Pointing-Pointer The material could make integration of micro-reactor and micro-extractor into one system. - Abstract: Oxidation of dibenzothiophene with hydrogen peroxide using a recyclable amphiphilic catalyst has been studied. The catalyst was synthesized by surfacely covering magnetic silica nanospheres (MSN) with the complexes between 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (AEM) and phosphotungstic acid (PTA). The morphology and components of the composite material were characterized by TEM, EDX, XPS, FT-IR, and VSM, respectively. The effects of several factors on desulfurization reactivity were systematically investigated. The results showed that the composite nanospheres have core/shell structure with the properties of amphiphilicity and superparamagnetism. The composite nanospheres have high catalytic activity in the oxidation of dibenzothiophene to corresponding sulfones by hydrogen peroxide under mild reaction conditions. The sulfur level could be lowered from 487 ppm to less than 0.8 ppm under optimal conditions. Additionally, the amphiphilic catalyst and the oxidized product could be simultaneously separated from medium by external magnetism, and the recovered composite material could be recycled for three times with almost constant activity.

Nano-magnetic particles as multifunctional microreactor for deep desulfurization

International Nuclear Information System (INIS)

Cui, Xinai; Yao, Dongdong; Li, Hong; Yang, Juxiang; Hu, Daodao

2012-01-01

Highlights: ► An easy-separated amphiphilic catalyst with small size was prepared for deep desulfurization. ► The effects of several factors on desulfurization reactivity were systematically investigated. ► The catalyst demonstrates high performance in the deep desulfurization. ► The material could make integration of micro-reactor and micro-extractor into one system. - Abstract: Oxidation of dibenzothiophene with hydrogen peroxide using a recyclable amphiphilic catalyst has been studied. The catalyst was synthesized by surfacely covering magnetic silica nanospheres (MSN) with the complexes between 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (AEM) and phosphotungstic acid (PTA). The morphology and components of the composite material were characterized by TEM, EDX, XPS, FT-IR, and VSM, respectively. The effects of several factors on desulfurization reactivity were systematically investigated. The results showed that the composite nanospheres have core/shell structure with the properties of amphiphilicity and superparamagnetism. The composite nanospheres have high catalytic activity in the oxidation of dibenzothiophene to corresponding sulfones by hydrogen peroxide under mild reaction conditions. The sulfur level could be lowered from 487 ppm to less than 0.8 ppm under optimal conditions. Additionally, the amphiphilic catalyst and the oxidized product could be simultaneously separated from medium by external magnetism, and the recovered composite material could be recycled for three times with almost constant activity.

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

Science.gov (United States)

Zhao, Dishun; Wang, Yanan; Duan, Erhong

2009-10-28

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

Oxidative Desulfurization of Fuel Oil by Pyridinium-Based Ionic Liquids

Directory of Open Access Journals (Sweden)

Erhong Duan

2009-10-01

Full Text Available In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF4 was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT was investigated. Ionic liquids and hydrogen peroxide (30% were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF4 has a better desulfurization effect. The best technological conditions are: V(IL/V(Oil /V(H2O2 = 1:1:0.4, temperature 55 °C, the time 30 min. The ratio of desulfurization to thiophene and DBT reached 78.5% and 84.3% respectively, which is much higher than extraction desulfurization with simple ionic liquids. Under these conditions, the effect of desulfurization on gasoline was also investigated. The used ionic liquids can be recycled up to four times after regeneration.

Oxidative desulfurization of dibenzothiophene with molecular oxygen using emulsion catalysis.

Science.gov (United States)

Lü, Hongying; Gao, Jinbo; Jiang, Zongxuan; Yang, Yongxing; Song, Bo; Li, Can

2007-01-14

Dibenzothiophene (DBT) is oxidized to the corresponding sulfoxide and sulfone in an emulsion system (W/O) composed of polyoxometalate anion [C(18)H(37)N(CH(3))3](5)[PV(2)Mo(10)O(40)] as both the surfactant and catalyst, using molecular oxygen as the oxidant and aldehyde as the sacrificial agent under mild conditions.

Growth and Desulfurization Kinetics of Rhodcoccus Erythropolis IGTS8 on Dibenzothiophen and Petroleum Fraction

International Nuclear Information System (INIS)

El-Temtamy, S.A.; Farahat, L.A.; Mostafa, Y.M.; Al-Shatnawi, D.F.; AI-Sayed, S.

2004-01-01

The growth Kinetics of Rhodococcus erythropolis IGTS8 on dibenzo-thiophene. DBT, of different initial concentrations as well as on two petroleum fractions namely untreated and hydrodesulfurized gasoline and gas oil have been investigated in batch cultures. Using dibenzothiophene as a substrate, the specific growth rates were found to decrease with increasing initial substrate concentration. The removal of dibenzothiophene from culture media was found to follow first order kinetics. The reaction rate constant., k, decreased with increasing substrate concentration. The decrease of both specific growth rate and reaction rate constant with increasing substrate concentration suggested substrate inhibition. The growth rate on untreated gasoline as well as on hydrodesulfurized gasoline gave nearly the same specific growth rates of 0.067 h-I while growth on gas oil gave a higher specific growth rate of 0.1h -1

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

Directory of Open Access Journals (Sweden)

Swapnil A. Dharaskar

2016-07-01

Full Text Available In the present paper the experimental data of extractive desulfurization of liquid fuel using 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM]BF4 have been presented. The data of FTIR, 1H NMR and 13C NMR have been discussed for the molecular confirmation of synthesized [BMIM]BF4. Further, the thermal properties, conductivity, solubility, and viscosity analysis of the [BMIM]BF4 were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of ionic liquid without regeneration on dibenzothiophene removal of liquid fuel were presented. In extractive desulfurization process, the removal of dibenzothiophene in n-dodecane was 73.02% for mass ratio of 1:1 in 30 min at 30 °C under the mild reaction conditions. The ionic liquids could be reused four times without a significant decrease in activity. Also, the desulfurizations of real fuels, multistage extraction were presented. The data and results provided in the present paper explore the significant insights of imidazoled ILs for extractive desulfurization of liquid fuels.

Integrated Mg/TiO2-ionic liquid system for deep desulfurization

Science.gov (United States)

Yin, Yee Cia; Kait, Chong Fai; Fatimah, Hayyiratul; Wilfred, Cecilia

2014-10-01

A series of Mg/TiO2 photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%.

Integrated Mg/TiO2-ionic liquid system for deep desulfurization

International Nuclear Information System (INIS)

Yin, Yee Cia; Kait, Chong Fai; Fatimah, Hayyiratul; Wilfred, Cecilia

2014-01-01

A series of Mg/TiO 2 photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%

Biocatalytic desulfurization of petroleum and middle distillates

International Nuclear Information System (INIS)

Monticello, D.J.

1993-01-01

Biocatalytic Desulfurization (BDS) represents an alternative approach to the reduction of sulfur in fossil fuels. The objective is to use bacteria to selectively remove sulfur from petroleum and middle distillate fractions, without the concomitant release of carbon. Recently, bacteria have been developed which have the ability to desulfurize dibenzothiophene (DBT) and other organosulfur molecules. These bacteria are being developed for use in a biocatalyst-based desulfurization process. Analysis of preliminary conceptual engineering designs has shown that this process has the potential to complement conventional technology as a method to temper the sulfur levels in crude oil, or remove the recalcitrant sulfur in middle distillates to achieve the deep desulfurization mandated by State and Federal regulations. This paper describes the results of initial feasibility studies, sensitivity analyses and conceptual design work. Feasibility studies with various crude oils and middle distillates achieved unoptimized desulfurization levels of 40-80%. Sensitivity analyses indicate that total desulfurization costs of about $3.00 per barrel for crude oil and less than $2.00 per barrel for diesel are possible. Key criteria for commercial success of the process include the cost and half-life of the biocatalyst, residence time in the reactor, oil/water ratios required to extract the sulfur and the disposition of the separated sulfur products. 9 refs., 3 figs

Integrated Mg/TiO{sub 2}-ionic liquid system for deep desulfurization

Energy Technology Data Exchange (ETDEWEB)

Yin, Yee Cia, E-mail: gabrielle.ciayin@gmail.com [Department of Chemical Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak (Malaysia); Kait, Chong Fai, E-mail: chongfaikait@petronas.com.my, E-mail: hayyiratulfatimah@yahoo.com, E-mail: cecili@petronas.com.my; Fatimah, Hayyiratul, E-mail: chongfaikait@petronas.com.my, E-mail: hayyiratulfatimah@yahoo.com, E-mail: cecili@petronas.com.my; Wilfred, Cecilia, E-mail: chongfaikait@petronas.com.my, E-mail: hayyiratulfatimah@yahoo.com, E-mail: cecili@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak (Malaysia)

2014-10-24

A series of Mg/TiO{sub 2} photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%.

DEEP DESULFURIZATION OF DIESEL FUELS BY A NOVEL INTEGRATED APPROACH

Energy Technology Data Exchange (ETDEWEB)

Xiaoliang Ma; Michael Sprague; Lu Sun; Chunshan Song

2002-10-01

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

Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate.

Science.gov (United States)

Hu, Yiwen; He, Qihui; Zhang, Zheng; Ding, Naidong; Hu, Baixing

2011-11-28

With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline.

Enhancement of Oxidative Desulfurization Performance over UiO-66(Zr) by Titanium Ion Exchange.

Science.gov (United States)

Ye, Gan; Qi, Hui; Li, Xiaolin; Leng, Kunyue; Sun, Yinyong; Xu, Wei

2017-07-19

Oxidative desulfurization is considered to be one of the most promising methods for producing ultra-low-sulfur fuels because it can effectively remove refractory sulfur-containing aromatic compounds under mild conditions. In this work, the oxidative desulfurization performance over UiO-66(Zr) is greatly enhanced by Ti ion exchange. This strategy is not only efficient for UiO-66(Zr) with crystal defects but also for UiO-66(Zr) with high crystallinity. In particular, the performance of UiO-66(Zr) with high crystallinity in the oxidative desulfurization of dibenzothiophene can be improved more than 11-fold, which can be mainly attributed to the introduction of active Ti sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

Science.gov (United States)

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

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

Science.gov (United States)

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

2015-05-01

M2(PcAN)2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M2(PcAN)2-W-HZSM-5) or the M2(PcTN)2 doping W-HZSM-5 (M2(PcTN)2/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu2(PcAN)2-W-HZSM-5 and Cu2(PcTN)2/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV-Vis and calcination temperature was obtained by TG-DSC for Cu2(PcTN)2/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. The reaction process of ultra-deep desulfurization.

TiO2-Containing Carbon Derived from a Metal-Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization.

Science.gov (United States)

Bhadra, Biswa Nath; Song, Ji Yoon; Khan, Nazmul Abedin; Jhung, Sung Hwa

2017-09-13

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H 2 N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H 2 N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO 2 nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO 2 nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO 2 , and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO 2 content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO 2 might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.

Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

Science.gov (United States)

Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

2018-01-01

Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

Deep desulfurization by amphiphilic lanthanide-containing polyoxometalates in ionic-liquid emulsion systems under mild conditions.

Science.gov (United States)

Xu, Junhua; Zhao, Shen; Ji, Yuanchun; Song, Yu-Fei

2013-01-07

Amphiphilic lanthanide-containing polyoxometalates (POMs) were prepared by surfactant encapsulation. Investigation of these lanthanide-containing POMs in oxidative desulfurization (ODS) showed that highly efficient deep desulfurization could be achieved in only 14 min with 100% conversion of dibenzothiophene under mild conditions by using (DDA)(9)LaW(10)/[omim]PF(6) (DDA=dimethyldioctadecylammonium, omim=1-octyl-3-methyl-imidazolium) in the presence of H(2) O(2) . Furthermore, deep desulfurization proceeds smoothly in model oil with an S content as low as 50 ppm. A scaled-up experiment in which the volume of model oil was increased from 5 to 1000 mL with S content of 1000 ppm indicated that about 99% sulfur removal can be achieved in 40 mins in an ionic-liquid emulsion system. To the best of our knowledge, the (DDA)(9)LaW(10)/[omim]PF(6) catalyst system with H(2)O(2) as oxidant is one of the most efficient desulfurization systems reported so far. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Preparation and Characterization of MoO3/Al2O3 Catalyst for Oxidative Desulfurization of Diesel using H2O2: Effect of Drying Method and Mo Loading

OpenAIRE

Azam Akbari; Mohammadreza Omidkhah; Jafar Toufighi Darian

2012-01-01

The mesoporous MoO3/γ-Al2O3 catalyst was prepared by incipient wetness impregnation method aiming to investigate the effect of drying method and molybdenum content on the catalyst property and performance towards the oxidation of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyle dibenzothiophene (4,6-DMDBT) with H2O2 for deep oxidative desulfurization of diesel fuel. The catalyst was characterized by XRD, BET, BJH and SEM method. The catalyst with 10wt.% and 1...

Adsorptive on-board desulfurization over multiple cycles for fuel-cell-based auxiliary power units operated by different types of fuels

Science.gov (United States)

Neubauer, Raphael; Weinlaender, Christof; Kienzl, Norbert; Bitschnau, Brigitte; Schroettner, Hartmuth; Hochenauer, Christoph

2018-05-01

On-board desulfurization is essential to operate fuel-cell-based auxiliary power units (APU) with commercial fuels. In this work, both (i) on-board desulfurization and (ii) on-board regeneration performance of Ag-Al2O3 adsorbent is investigated in a comprehensive manner. The herein investigated regeneration strategy uses hot APU off-gas as the regeneration medium and requires no additional reagents, tanks, nor heat exchangers and thus has remarkable advantages in comparison to state-of-the-art regeneration strategies. The results for (i) show high desulfurization performance of Ag-Al2O3 under all relevant operating conditions and specify the influence of individual operation parameters and the combination of them, which have not yet been quantified. The system integrated regeneration strategy (ii) shows excellent regeneration performance recovering 100% of the initial adsorption capacity for all investigated types of fuels and sulfur heterocycles. Even the adsorption capacity of the most challenging dibenzothiophene in terms of regeneration is restored to 100% over 14 cycles of operation. Subsequent material analyses proved the thermal and chemical stability of all relevant adsorption sites under APU off-gas conditions. To the best of our knowledge, this is the first time 100% regeneration after adsorption of dibenzothiophene is reported over 14 cycles of operation for thermal regeneration in oxidizing atmospheres.

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

Energy Technology Data Exchange (ETDEWEB)

Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Gao, Ruimin [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Wang, Junlong [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China)

2015-05-15

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

Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

Energy Technology Data Exchange (ETDEWEB)

Qiu, Jianghua; Wang, Guanghui; Zeng, Danlin; Tang, Yan [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Wang, Meng; Li, Yanjun [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

2009-12-15

Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]{sub 2} in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly. (author)

Preparation of AAO-CeO2 nanotubes and their application in electrochemical oxidation desulfurization of diesel

Science.gov (United States)

Du, Xiaoqing; Yang, Yumeng; Yi, Chenxi; Chen, Yu; Cai, Chao; Zhang, Zhao

2017-02-01

The coaxial arrays of AAO-CeO2 NTs have been successfully galvanostatically deposited on an anode, characterized and adopted as a catalyst for removing organic sulfurs from diesel. The influence of the main electrochemical oxidation factors on the efficiency of desulfurization have also been investigated. The results show that the fabrication process of AAO-CeO2 NTs is accompanied by the formation of a new phase, namely Al3Ce, and the main oxidation products of the diesel are soluble inorganic sulphides, especially Ce2(SO4)3. When compared with dibenzothiophene and 4, 6-dimethyldibenzothiophene, benzothiophene is much more easily removed, with a removal efficiency that reaches 87.2%. Finally, a possible electrochemical oxidation desulfurization pathway for diesel is proposed.

L-proline-based deep eutectic solvents (DESs) for deep catalytic oxidative desulfurization (ODS) of diesel.

Science.gov (United States)

Hao, Lingwan; Wang, Meiri; Shan, Wenjuan; Deng, Changliang; Ren, Wanzhong; Shi, Zhouzhou; Lü, Hongying

2017-10-05

A series of L-proline-based DESs was prepared through an atom economic reaction between L-proline (L-Pro) and four different kinds of organic acids. The DESs were characterized by Fourier transform infrared spectroscopy (FT-IR), H nuclear magnetic resonance ( 1 HNMR), cyclic voltammogram (CV) and the Hammett method. The synthesized DESs were used for the oxidative desulfurization and the L-Pro/p-toluenesultonic acid (L-Pro/p-TsOH) system shows the highest catalytic activity that the removal of dibenzothiophene (DBT) reached 99% at 60°C in 2h, which may involve the dual activation of the L-Pro/p-TsOH. The acidity of four different L-proline-based DESs was measured and the results show that it could not simply conclude that the correlation between the acidity of DESs and desulfurization capability was positive or negative. The electrochemical measurements evidences and recycling experiment indicate a good stability performance of L-Pro/p-TsOH in desulfurization. This work will provide a novel and potential method for the deep oxidation desulfurization. Copyright © 2017 Elsevier B.V. All rights reserved.

Optimization of operating conditions in oxidation of dibenzothiophene in the light hydrocarbon model

Directory of Open Access Journals (Sweden)

Akbari Azam

2014-01-01

Full Text Available In this research, the effects of process variables on the efficiency and mechanism of dibenzothiophene oxidation in formicacid/H2O2 system for deep desulfurization of a light hydrocarbon model were systematically studied by statistical modelling and optimization using response surface methodology and implementing the central composite design. A quadratic regression model was developed to predict the yield of sulfur oxidation as the model response. The model indicated that temperature was the most significant effective factor and suggested an important interaction between temperature and H2O2/sulfur ratio; at temperatures above 56°C, more excess oxidant was necessary because of instability of active peroxo intermediates and loss of H2O2 due to thermal decomposition. In contrast, the water hindrance effect of H2O2 aqueous solution in desulfurization progress was more significant at temperatures bellow 56°C. In the optimization process, minimizing H2O2/sulfur ratio and catalyst consumption for maximum yield of desulfurization was economically considerable. The optimal condition was obtained at temperature of 57 °C, H2O2/sulfur ratio of 2.5 mol/mol and catalyst dosage of 0.82 mL in 50 mL solution of DBT in n-hexane leading to a maximum oxidation yield of 95% after 1 hour reaction. Good agreement between predicted and experimental results (less than 4% error was found.

Enhancement of dibenzothiophene biodesulfurization using {beta}-cyclodextrins in oil-to-water media

Energy Technology Data Exchange (ETDEWEB)

Ainhoa Caro; Pedro Leton; Eloy Garcia-Calvo; Leonardo Setti [Universidad de Alcala, Madrid (Spain). Departamento de Quimica Analitica e Ingeniera Quimica

2007-11-15

It has been reported that biodesulfurization (BDS) of dibenzothiophene (DBT) in oil-to-water emulsions is carried out by growing cells of the aerobic Rhodococcus erythropolis IGTS8 strain and developing the so-called 4S desulfurization pathway. On adding {beta}-cyclodextrins, it is possible to improve the BDS yields, increase the diffusion of DBT into the aqueous phase or avoid the HBP accumulation. Moreover, by using greater biocatalyst initial concentrations and adding 15 ppm of {beta}-cyclodextrin, a very high BDS yield has been observed, but the presence of mass transfer limitations and the inhibition effects were not satisfactorily avoided. The Haldane kinetic model agreed well with the experimental results obtained, and the values of the kinetic parameters were determined. Short communication. 20 refs., 2 figs., 2 tabs.

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

Science.gov (United States)

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

2014-08-30

A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and (1)H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50°C in 3h under conditions of VPIL/Vmodel oil=1:10 and H2O2/DBT (O/S, molar ratio)=5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT>4,6-dimethyldibenzothiophene (4,6-DMDBT)>benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of Influential Parameters in Deep Oxidative Desulfurization of Dibenzothiophene with Hydrogen Peroxide and Formic Acid

OpenAIRE

Haghighat Mamaghani, Alireza; Fatemi, Shohreh; Asgari, Mehrdad

2013-01-01

An effective oxidative system consisting of hydrogen peroxide, formic acid, and sulfuric acid followed by an extractive stage were implemented to remove dibenzothiophene in the simulated fuel oil. The results revealed such a great performance in the case of H2O2 in the presence of formic and sulfuric acids that led to the removal of sulfur compounds. Sulfuric acid was employed to increase the acidity of media as well as catalytic activity together with formic acid. The oxidation reaction was ...

THE BIOCATALYTIC DESULFURIZATION PROJECT

Energy Technology Data Exchange (ETDEWEB)

Steven E. Bonde; David Nunn

2003-04-01

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

Integrated photooxidative-extractive desulfurization system for fuel oil using Cu, Fe and Cu-Fe/TiO2 and eutectic based ionic liquids: Effect of calcination temperature and duration

Science.gov (United States)

Zaid, Hayyiratul Fatimah Mohd; Kait, Chong Fai; Mutalib, Mohamed Ibrahim Abdul

2014-10-01

Photocatalyts TiO2 doped with Cu, Fe and Cu-Fe metal at different calcination temperature and duration were successfully prepared and characterized. Photocatalytic oxidative desulfurization of model oil containing dibenzothiophene as the sulfur compound (100 ppm) using the prepared photocatalyst was investigated. The photocatalyst calcined at 500°C and duration of 1 h showed the best performance.

Oxovanadium(IV)-catalysed oxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene.

Science.gov (United States)

Ogunlaja, Adeniyi S; Chidawanyika, Wadzanai; Antunes, Edith; Fernandes, Manuel A; Nyokong, Tebello; Torto, Nelson; Tshentu, Zenixole R

2012-12-07

The reaction between [V(IV)OSO(4)] and the tetradentate N(2)O(2)-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [V(IV)O(sal-HBPD)]. The molecular structure of [V(IV)O(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N(2)O(2) binding mode of the tetradentate ligand. The formation of the polymer-supported p[V(IV)O(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [V(IV)OSO(4)]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[V(IV)O(sal-AHBPD)] were found to be 6.9 m(2) g(-1) and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [V(IV)O(sal-HBPD)] and p[V(IV)O(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [V(IV)O(sal-HBPD)] and p[V(IV)O(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO(2)) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO(2)) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[V(IV)O(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application

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

Energy Technology Data Exchange (ETDEWEB)

Lü, Hongying, E-mail: hylv@ytu.edu.cn; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

2014-08-30

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Ultrasound-assisted oxidation of dibenzothiophene with phosphotungstic acid supported on activated carbon.

Science.gov (United States)

Liu, Liyan; Zhang, Yu; Tan, Wei

2014-05-01

Phosphotungstic acid (HPW) supported on activated carbon (AC) was applied to catalyze deep oxidation desulfurization of fuel oil with the assist of ultrasound. The sulfur-conversion rate was evaluated by measuring the concentration of dibenzothiophene (DBT) in n-octane before and after the oxidation. Supporting HPW on AC has been verified to play a positive role in UAOD process by a series of contrast tests, where only HPW, AC or a mixture of free HPW and AC was used. The influences of catalyst dose, ultrasound power, reaction temperature, H2O2:oil volume ratio and the reuse of catalyst on the catalytic oxidation desulfurization kinetics were investigated. The DBT conversion rate of the reaction catalyzed by supported HPW under ultrasound irradiation was higher than the summation of the reactions with HPW only and AC only as catalyst. With the increase of loading amount of HPW on AC, ultrasound power, H2O2:oil volume ratio and reaction temperature, the catalytic oxidation reactivity of DBT would be enhanced. The optimum loading amount of HPW was 10%, exceed which DBT conversion would no longer increase obviously. DBT could be completely converted under the optimized conditions (volume ratio of H2O2 to model oil: 1:10, mass ratio of the supported HPW to model oil: 1.25%, temperature: 70°C) after 9 min of ultrasound irradiation. Copyright © 2013 Elsevier B.V. All rights reserved.

Deep Desulfurization of Diesel Fuels with Plasma/Air as Oxidizing Medium, Diperiodatocuprate (III) as Catalyzer and Ionic Liquid as Extraction Solvent

Science.gov (United States)

Ban, Lili; Liu, Ping; Ma, Cunhua; Dai, Bin

2013-12-01

In this paper, the oxidative desulfurization (ODS) system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge (DBD) plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeCl4 (1-butyl-3-methylimidazolium tetrachloroferrate). This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm (S removal rate up to 97.5%) under the following optimal reaction conditions: air flow rate (ν) of 60 mL/min, amplitude of applied voltage (U) on DBD of 16 kV, input frequency (f) of 79 kHz, catalyst amount (ω) of 1.25 wt%, reaction time (t) of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene (BT) or 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system.

Deep Desulfurization of Diesel Fuels with Plasma/Air as Oxidizing Medium, Diperiodatocuprate (III) as Catalyzer and Ionic Liquid as Extraction Solvent

International Nuclear Information System (INIS)

Ban Lili; Liu Ping; Ma Cunhua; Dai Bin

2013-01-01

In this paper, the oxidative desulfurization (ODS) system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge (DBD) plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeCl 4 (1-butyl-3-methylimidazolium tetrachloroferrate). This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm (S removal rate up to 97.5%) under the following optimal reaction conditions: air flow rate (ν) of 60 mL/min, amplitude of applied voltage (U) on DBD of 16 kV, input frequency (f) of 79 kHz, catalyst amount (ω) of 1.25 wt%, reaction time (t) of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene (BT) or 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system. (plasma technology)

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

Science.gov (United States)

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

2015-12-07

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

Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

OpenAIRE

José da Silva, Márcio; Faria dos Santos, Lidiane

2013-01-01

A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by ace...

Biodesulfurization of dibenzothiophene in Escherichia coli is enhanced by expression of a Vibrio harveyi oxidoreductase gene

Energy Technology Data Exchange (ETDEWEB)

Reichmuth, D.S.; Hittle, J.L.; Blanch, H.W.; Keasling, J.D.

2000-01-05

One possible alternative to current fuel hydrodesulfurization methods is the use of microorganisms to remove sulfur compounds. Biodesulfurization requires much milder processing conditions, gives higher specificity, and does not require molecular hydrogen. In the present work the authors have produced two compatible plasmids: pDSR3, which allows Escherichia coli to convert dibenzothiophene (DBT) to hydroxybiphenyl (HBP), and pDSR2, which produces a Vibrio harveyi flavin oxidoreductase. The authors show that the flavin oxidoreductase enhances the rate of DBT removal when co-expressed in vivo with the desulfurization enzymes. The plasmids pDSR2 and pDSR3 were co-expressed in growing cultures. The expression of oxidoreductase caused an increase in the rate of DBT removal but a decrease in the rate of HBP production. The maximum rate of DBT removal was 8 mg/h {center{underscore}dot} g dry cell weight. Experiments were also conducted using resting cells with the addition of various carbon sources. It was found that the addition of glucose or glycerol to cultures with oxidoreductase expression produced the highest DBT removal rate. The culture with acetate and no oxidoreductase expression had the highest level of HBP production. For all carbon sources, the DBT removal rate was faster and the HBP generation rate slower with the expression of the oxidoreductase. Analysis of desulfurization intermediates indicates that the last enzyme in the pathway may be limiting.

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

Science.gov (United States)

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

International Nuclear Information System (INIS)

Muhammad, Yaseen; Lu Yingzhou; Shen Chong; Li Chunxi

2011-01-01

Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 o C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al 2 O 3 , Ni-Mo/Al 2 O 3 , Ru-Co-Mo/Al 2 O 3 and Ru-Ni-Mo/Al 2 O 3 were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N 2 adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al 2 O 3 catalyst at 380 o C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al 2 O 3 > Ni-Mo/Al 2 O 3 > Ru-Co-Mo/Al 2 O 3 > Co-Mo/Al 2 O 3 at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT.

Fabrication of photocatalytic composite of multi-walled carbon nanotubes/TiO2 and its application for desulfurization of diesel

International Nuclear Information System (INIS)

Vu, Thu Ha Thi; Nguyen, Thu Trang Thi; Nguyen, Phuong Hoa Thi; Do, Manh Hung; Au, Hang Thi; Nguyen, Thanh Binh; Nguyen, Dinh Lam; Park, Jun Seo

2012-01-01

Highlights: ► MWNTs and TiO 2 were mixed well, forming uniform microstructure in MWNTs/TiO 2 composites. ► The combination of MWNTs and TiO 2 contribute to improving photocatalytic activity of TiO 2 . ► MWNTs/TiO 2 composite is an effective photo-catalyst for the removal of sulfur from commercial diesel. -- Abstract: Composite of multi-walled carbon nanotubes (MWNTs) and titanium (IV) oxide (TiO 2 ) were prepared by a heterogeneous gelation method. The activities of the MWNTs/TiO 2 composites were evaluated by photocatalytic oxidative desulfurization using dibenzothiophene (DBT), 4,6-dimethyl dibenzothiophene (4,6-DMDBT), n-tetradecane, and commercial diesel under irradiation using a high-pressure Hg lamp. The microstructures of MWNTs/TiO 2 composites were characterized by N 2 adsorption, scanning electron microscopy, transmission electron microscope, and X-ray diffraction. It was found that more than 98% of sulfur compounds in commercial diesel were oxidized and removed by the use of the MWNTs/TiO 2 composite as a photocatalyst.

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

Science.gov (United States)

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

2011-03-21

Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance

International Nuclear Information System (INIS)

Zhang, Shuna; Zhang, Shujuan; Song, Limin; Wu, Xiaoqing; Fang, Sheng

2014-01-01

Graphical abstract: Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance. - Highlights: • Three-dimensional Ni 2 P has been prepared using foam nickel as a template. • The microstructures interconnected and formed sponge-like porous networks. • Three-dimensional Ni 2 P shows superior hydrodesulfurization activity. - Abstract: Three-dimensional microstructured nickel phosphide (Ni 2 P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni 2 P samples, as interconnected networks, maintained the original mesh structure of foamed nickel. The crystal structure and morphology of the as-synthesized Ni 2 P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the three-dimensionally structured Ni 2 P was postulated and discussed in detail. To investigate its catalytic properties, SiO 2 supported three-dimensional Ni 2 P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni 2 P/SiO 2

Desulfurization of Diesel Fuel by Oxidation and Solvent Extraction

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Wadood Taher Mohammed

2015-02-01

Full Text Available This research presents a study in ultra-desulfurization of diesel fuel produced from conventional hydro desulfurization process, using oxidation and solvent extraction techniques. Dibenzothiophene (DBT was the organosulfur compound that had been detected in sulfur removal. The oxidation process used hydrogen peroxide as an oxidant and acetic acid as homogeneous catalyst . The solvent extraction process used acetonitrile (ACN and N-methyl – 2 - pyrrolidone (NMP as extractants . Also the effect of five parameters (stirring speed :150 , 250 , 350 , and 450 rpm, temperature (30 , 40 , 45 , and 50 oC, oxidant/simulated diesel fuel ratio (0.5 , 0.75 , 1 , and 1.5 , catalyst/oxidant ratio(0.125,0.25,0.5,and0.75 , and solvent/simulated diesel fuel ratio(0.5,0.6,0.75,and1 were examined as well as solvent type. The results exhibit that the highest removal of sulfur is 98.5% using NMP solvent while it is 95.8% for ACN solvent. The set of conditions that show the highest sulfur removal is: stirring speed of 350 rpm , temperature 50oC , oxidant/simulated diesel fuel ratio 1 , catalyst/oxidant ratio 0.5 , solvent/simulated diesel fuel ratio 1. These best conditions were applied upon real diesel fuel (produced from Al-Dora refinerywith 1000 ppm sulfur content . It was found that sulfur removal was 64.4% using ACN solvent and 75% using NMP solvent.

Biodesulfurization of dibenzothiophene in Escherichia coli is enhanced by expression of a Vibrio harveyi oxidoreductase gene.

Science.gov (United States)

Reichmuth, D S; Hittle, J L; Blanch, H W; Keasling, J D

2000-01-05

One possible alternative to current fuel hydrodesulfurization methods is the use of microorganisms to remove sulfur compounds. Biodesulfurization requires much milder processing conditions, gives higher specificity, and does not require molecular hydrogen. In the present work we have produced two compatible plasmids: pDSR3, which allows Escherichia coli to convert dibenzothiophene (DBT) to hydroxybiphenyl (HBP), and pDSR2, which produces a Vibrio harveyi flavin oxidoreductase. We show that the flavin oxidoreductase enhances the rate of DBT removal when co-expressed in vivo with the desulfurization enzymes. The plasmids pDSR2 and pDSR3 were co-expressed in growing cultures. The expression of oxidoreductase caused an increase in the rate of DBT removal but a decrease in the rate of HBP production. The maximum rate of DBT removal was 8 mg/h. g dry cell weight. Experiments were also conducted using resting cells with the addition of various carbon sources. It was found that the addition of glucose or glycerol to cultures with oxidoreductase expression produced the highest DBT removal rate (51 mg/h. g dry cell weight). The culture with acetate and no oxidoreductase expression had the highest level of HBP production. For all carbon sources, the DBT removal rate was faster and the HBP generation rate slower with the expression of the oxidoreductase. Analysis of desulfurization intermediates indicates that the last enzyme in the pathway may be limiting. Copyright 2000 John Wiley & Sons, Inc.

Investigation of Influential Parameters in Deep Oxidative Desulfurization of Dibenzothiophene with Hydrogen Peroxide and Formic Acid

Directory of Open Access Journals (Sweden)

Alireza Haghighat Mamaghani

2013-01-01

Full Text Available An effective oxidative system consisting of hydrogen peroxide, formic acid, and sulfuric acid followed by an extractive stage were implemented to remove dibenzothiophene in the simulated fuel oil. The results revealed such a great performance in the case of H2O2 in the presence of formic and sulfuric acids that led to the removal of sulfur compounds. Sulfuric acid was employed to increase the acidity of media as well as catalytic activity together with formic acid. The oxidation reaction was followed by a liquid-liquid extraction stage using acetonitrile as a polar solvent to remove produced sulfones from the model fuel. The impact of operating parameters including the molar ratio of formic acid to sulfur (, hydrogen peroxide to sulfur (, and the time of reaction was investigated using Box-Behnken experimental design for oxidation of the model fuel. A significant quadratic model was introduced for the sulfur removal as a function of effective parameters by the statistic analysis.

A novel [Bmim]PW/HMS catalyst with high catalytic performance for the oxidative desulfurization process

Energy Technology Data Exchange (ETDEWEB)

Tang, Ling; Luo, Guangqing; Kang, Lihua; Zhu, Mingyuan; Dai, Bin [Shihezi University, Shihezi (China)

2013-02-15

To effectively reduce the sulfur content in model fuel, [Bmim]PW/HMS catalyst was synthesized through impregnating the hexagonal mesoporous silica (HMS) support by phosphotungstic acid (HPW) and ionic liquid [Bmim] HSO{sub 4}. Physical structure characterizations of the catalysts showed that HMS retained mesoporous structure, and [Bmim] PW was well dispersed on the support of HMS. The catalytic activity of the [Bmim]PW/HMS was evaluated in the oxidative desulfurization process, and the optimal reaction conditions including loading of the catalysts, reaction temperature, catalyst amount, O/S (H{sub 2}O{sub 2}/sulfur) molar ratio and agitation speed were investigated. Under the optimal reaction conditions, the conversion of benzothiophene (BT), dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) could reach 79%, 98%, 88%, respectively.

A novel [Bmim]PW/HMS catalyst with high catalytic performance for the oxidative desulfurization process

International Nuclear Information System (INIS)

Tang, Ling; Luo, Guangqing; Kang, Lihua; Zhu, Mingyuan; Dai, Bin

2013-01-01

To effectively reduce the sulfur content in model fuel, [Bmim]PW/HMS catalyst was synthesized through impregnating the hexagonal mesoporous silica (HMS) support by phosphotungstic acid (HPW) and ionic liquid [Bmim] HSO 4 . Physical structure characterizations of the catalysts showed that HMS retained mesoporous structure, and [Bmim] PW was well dispersed on the support of HMS. The catalytic activity of the [Bmim]PW/HMS was evaluated in the oxidative desulfurization process, and the optimal reaction conditions including loading of the catalysts, reaction temperature, catalyst amount, O/S (H 2 O 2 /sulfur) molar ratio and agitation speed were investigated. Under the optimal reaction conditions, the conversion of benzothiophene (BT), dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) could reach 79%, 98%, 88%, respectively

Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

Energy Technology Data Exchange (ETDEWEB)

Muhammad, Yaseen; Shen, Chong; Li, Chunxi [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Lu, Yingzhou [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

2011-02-15

Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al{sub 2}O{sub 3}, Ni-Mo/Al{sub 2}O{sub 3}, Ru-Co-Mo/Al{sub 2}O{sub 3} and Ru-Ni-Mo/Al{sub 2}O{sub 3} were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N{sub 2} adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al{sub 2}O{sub 3} catalyst at 380 C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al{sub 2}O{sub 3}> Ni-Mo/Al{sub 2}O{sub 3}> Ru-Co-Mo/Al{sub 2}O{sub 3}> Co-Mo/Al{sub 2}O{sub 3} at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT. (author)

Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

Science.gov (United States)

Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

2012-04-10

Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimized Ultrasound-Assisted Oxidative Desulfurization Process of Simulated Fuels over Activated Carbon-Supported Phosphotungstic Acid

Directory of Open Access Journals (Sweden)

Peniel Jean Gildo

2018-01-01

Full Text Available Recent technological advancements respond to the call to minimize/eliminate emissions to the atmosphere. However, on the average, fuel oils which is one of the major raw materials, is found to increase in sulfur concentration due to a phenomenon called thermal maturation. As such, a deeper desulfurization process is needed to obtain low/ultra-low sulfur fuel oils. In the present study, the ultrasound assisted oxidative desulfurization (UAOD processes using the H2O2 and HPW-AC oxidizing system applied to simulated fuel (~2800 ppm sulfur in the form of dibenzothiophene, benzothiophene, and thiophene dissolved in toluene, were optimized. After the pre-saturation of the HPW-AC with the simulated fuel, H2O2 was added just before the reaction was commenced under ultrasonic irradiation. After the application of both 2k-factorial design of experiment for screening and Face-Centered Design of Experiment for optimization, it was found that 25.52 wt% of H2O2 concentration, 983.9 mg of catalyst dose, 9.52 mL aqueous phase per 10 mL of the organic phase and 76.36 minutes of ultrasonication time would render 94.74% oxidation of the sulfur compounds in the simulated fuel. After the application of the optimized parameters to kerosene and employing a 4-cycle extraction using acetonitrile, 99% of the original sulfur content were removed from the kerosene using the UAOD optimized parameters. The desulfurization process resulted in a low-sulfur kerosene which retained its basic fuel properties such as density, viscosity and calorific value.

Fabrication of photocatalytic composite of multi-walled carbon nanotubes/TiO{sub 2} and its application for desulfurization of diesel

Energy Technology Data Exchange (ETDEWEB)

Vu, Thu Ha Thi, E-mail: ptntd2004@yahoo.fr [Vietnam Institute of Industrial Chemistry, Hanoi (Viet Nam); Nguyen, Thu Trang Thi; Nguyen, Phuong Hoa Thi; Do, Manh Hung; Au, Hang Thi [Vietnam Institute of Industrial Chemistry, Hanoi (Viet Nam); Nguyen, Thanh Binh [Faculty of Chemistry, Hanoi University of Science, Vietnam National University, Hanoi (Viet Nam); Nguyen, Dinh Lam [Faculty of Chemical Engineering, Danang University of Technology, University of Danang (Viet Nam); Park, Jun Seo [Division of Chemical Engineering, Hankyong National University, Ansung 456-749 (Korea, Republic of)

2012-02-15

Highlights: Black-Right-Pointing-Pointer MWNTs and TiO{sub 2} were mixed well, forming uniform microstructure in MWNTs/TiO{sub 2} composites. Black-Right-Pointing-Pointer The combination of MWNTs and TiO{sub 2} contribute to improving photocatalytic activity of TiO{sub 2}. Black-Right-Pointing-Pointer MWNTs/TiO{sub 2} composite is an effective photo-catalyst for the removal of sulfur from commercial diesel. -- Abstract: Composite of multi-walled carbon nanotubes (MWNTs) and titanium (IV) oxide (TiO{sub 2}) were prepared by a heterogeneous gelation method. The activities of the MWNTs/TiO{sub 2} composites were evaluated by photocatalytic oxidative desulfurization using dibenzothiophene (DBT), 4,6-dimethyl dibenzothiophene (4,6-DMDBT), n-tetradecane, and commercial diesel under irradiation using a high-pressure Hg lamp. The microstructures of MWNTs/TiO{sub 2} composites were characterized by N{sub 2} adsorption, scanning electron microscopy, transmission electron microscope, and X-ray diffraction. It was found that more than 98% of sulfur compounds in commercial diesel were oxidized and removed by the use of the MWNTs/TiO{sub 2} composite as a photocatalyst.

Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

International Nuclear Information System (INIS)

Farzin Nejad, N.; Shams, E.; Amini, M.K.

2015-01-01

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm and transmission electron microscopy. Nitrogen adsorption–desorption measurement revealed the high surface area (810 m 2 g −1 ), maxima pore size of 3.3 nm and large pore volume (1.01 cm 3 g −1 ) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g −1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles. - Highlights: • Adsorptive desulfurization of model oil with magnetic ordered mesoporous carbon adsorbent, Fe-OMC, was studied. • Maximum adsorption capacity (q max ) of Fe-OMC for DBT was found to be 111.1 mg g −1 . • Freundlich isotherm best represents the equilibrium adsorption data. • Rate of DBT adsorption process onto Fe-OMC is controlled by at least two steps

Bio desulfurization of a system containing synthetic fuel by rhodococcus erythropolis ATCC 4277; Remocao de compostos sulfurosos de sitema bifasico contendo combustivel sintetico por Rhodococcus erythropolis ATCC 4277

Energy Technology Data Exchange (ETDEWEB)

Maass, Danielle; Souza, Antonio Augusto Ulson de; Souza, Selene Maria de Arruda Guelli Ulson de [Universidade Federal de Santa Catarina (UFSC), SC (Brazil)

2012-07-01

For decades the burning of fossil fuels released a lot of pollutants in the atmosphere. Among the most harmful is sulfur dioxide (SO{sub 2}), which reacts with the moisture in the air and turns into sulfuric acid, being the main cause of acid rain. Acid rain is very harmful to animal and plant kingdoms; accelerates the corrosion's processes of buildings and monuments, and causes serious health problems for humans. As a result, many countries have reformed their legislation to require the sale of fuels with very low sulfur content. The existing processes of desulfurization are not capable of removing sulfur so low. Therefore, there has developed a new process called bio desulfurization. In this process, the degradation of sulfur occurs through the action of microorganisms that act as catalysts. The bacterium Rhodococcus erythropolis has emerged as one of the most promising for bio desulfurization because it removes the sulfur without breaking the benzene rings, thereby maintaining the potential energy of the same. Using dibenzothiophene as a model of sulfur compounds, the products of the bio desulfurization process are 2- hydroxybiphenyl and sulfate. In this study we sought to examine the desulfurizing capacity of national Rhodococcus erythropolis strain ATCC4277 in a batch reactor using concentrations of organic phase (n-dodecane) of 20 and 80% (v/v). Rhodococcus erythropolis ATCC4277 was capable of degrading DBT in 93.3 and 98.0% in the presence of 20 and 80% (v/v) of synthetic fuel, respectively. (author)

Preparation of mesoporous Cs-POM@MOF-199@MCM-41 under two different synthetic methods for a highly oxidesulfurization of dibenzothiophene.

Science.gov (United States)

Li, Si-Wen; Li, Jia-Rong; Jin, Qi-Ping; Yang, Zhi; Zhang, Rong-Lan; Gao, Rui-Min; Zhao, Jian-She

2017-09-05

Two different synthetic methods, the direct method and the substitution method, were used to synthesize the Cs-POM@MOF-199@MCM-41 (Cs-PMM), in which the modified heteropolyacid with cesium salt has been encapsulated into the pores with the mixture of MOF and MCM-41. The structural properties of the as-prepared catalysts were characterized using various analytical techniques: powder X-ray diffraction, FT-IR, SEM, TEM, XPS and BET, confirming that the Cs-POM active species retained its Keggin structure after immobilization. The substitution method of Cs-PMM exhibited more excellent catalytic performance for oxidative desulfurization of dibenzothiophene in the presence of oxygen. Under optimal conditions, the DBT conversion rate reached up to 99.6% and could be recycled 10 times without significant loss of catalytic activity, which is mainly attributed to the slow leaching of the active heteropolyacid species from the strong fixed effect of the mixture porous materials. Copyright © 2017. Published by Elsevier B.V.

Hydrothermal Synthesis of MoO2 and Supported MoO2 Cata-lysts for Oxidative Desulfurization of Dibenzothiophene

Institute of Scientific and Technical Information of China (English)

Wang Danhong; Zhang Jianyong; Liu Ni; Zhao Xin; Zhang Minghui

2014-01-01

A novel method for obtaining spherical MoO2 nanoparticles and SiO2-Al2O3 supported MoO2 by hydrothermal reduction of Mo (VI) species was studied. The obtained MoO2 catalysts show very high catalytic activity in the oxidative desulfurization (ODS) process. The effect of hydrothermal temperature and crystallization temperature on ODS activity was investigated. The ODS activity of supported MoO2 catalysts with various MoO2 contents were also investigated. The mecha-nism for formation of MoO2 involving oxalic acid was proposed.

BIOTRANSFORMATION AND REMOVAL OF SULFUR FROM DIBENZOTHIOPHENE USING IMPROVED BIOCATALYTIC METHODS

OpenAIRE

LAROTTA, C. E; MORA, A. L; MADERO, A; MOGOLLÓN, L. I

1998-01-01

Three methods for the removal of sulfurfrom dibenzothiophene were evaluated using biocatalytic processes. The methods were a microbial, an enzymatic and a combined one that involves a previous enzymatic oxidation followed by microbial degradation. The byconversion was evaluated over the molecular dibenzothiophene model, obtaining higher byconversion percentages through the combined method. The microorganisms used in this study correspond to several Colombian indigenous strains isolated by dir...

Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

Energy Technology Data Exchange (ETDEWEB)

Farzin Nejad, N., E-mail: Farzinnejadn@ripi.ir [Petroleum Refining Technology Development Division, Research Institute of Petroleum Industry, Tehran 14857-33111 (Iran, Islamic Republic of); Shams, E.; Amini, M.K. [Department of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

2015-09-15

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm and transmission electron microscopy. Nitrogen adsorption–desorption measurement revealed the high surface area (810 m{sup 2} g{sup −1}), maxima pore size of 3.3 nm and large pore volume (1.01 cm{sup 3} g{sup −1}) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g{sup −1} of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles. - Highlights: • Adsorptive desulfurization of model oil with magnetic ordered mesoporous carbon adsorbent, Fe-OMC, was studied. • Maximum adsorption capacity (q{sub max}) of Fe-OMC for DBT was found to be 111.1 mg g{sup −1}. • Freundlich isotherm best represents the equilibrium adsorption data. • Rate of DBT adsorption process onto Fe-OMC is controlled by at least two steps.

Preparation of ionic liquid-modified SBA-15 doped with molybdovanadophosphoric acid for oxidative desulfurization

International Nuclear Information System (INIS)

Zhuang, Jiang Zhou; Jin, Xiao Yin; Shen, Xian Lin; Tan, Jun Jun; Nie, Long Hui; Xiang, Jian; Hu, Bing

2015-01-01

A series of catalysts, ionic liquid-modified SBA-15 (denoted ILSBA) doped with H 5 PMo 10 V 2 O 40 (HPMoV 2 ) have been synthesized and characterized by XRD, FT-IR, 1 H NMR, TG-DTA, and TEM. The catalyst was used for the removal of dibenzothiophene (DBT) in model oil combined with hydrogen peroxide (the oxidant) and acetonitrile (the phase-transfer agent). It was observed that the sulfur content of DBT can be reduced from 500 to 2 ppm by adjusting the amount of catalyst, the reaction temperatures and the reaction time. Besides, the catalyst activity for different sulfur compounds showed a huge difference which may be mainly affected by the electron densities of sulfur atom. Moreover, the catalyst can be recycled seven times without a significant loss in activity, which could be ascribed to the strong electrostatic interaction between ILSBA and HPMoV 2 . In addition, a postulated mechanism was proposed to reveal the oxidative desulfurization process

Model description of dibenzothiophene mass transfer in oil/water dispersions with respect to biodesulfurization

NARCIS (Netherlands)

Marcelis, C.L.M.; Leeuwen, van M.; Polderman, H.G.; Janssen, A.J.H.; Lettinga, G.

2003-01-01

A mathematical model was developed in order to describe the mass transfer rate of dibenzothiophene within the oil droplet to the oil/water interface of droplets created in a stirred tank reactor. The mass transfer rate of dibenzothiophene was calculated for various complex hydrocarbon distillates

The Oxidation of Dibenzothiophene using Oxidovanadium(IV ...

African Journals Online (AJOL)

... and EPR also confirmed the presence of oxidovanadium(IV) within the nanofibres. Oxidation of dibenzothiophene (DBT) was investigated by varying the catalyst amount, substrate amount, oxidant and temperature, and the progress of oxidation was followed with a gas chromatograph fitted with a flame ionization detector.

Synthesis of mesoporous TS-1 using a hybrid SiO2–TiO2 xerogel for catalytic oxidative desulfurization

International Nuclear Information System (INIS)

Yang, Seung-Tae; Jeong, Kwang-Eun; Jeong, Soon-Yong; Ahn, Wha-Seung

2012-01-01

Graphical abstract: Display Omitted Highlights: ► Meso-TS-1 catalyst was synthesized using a SiO 2 –TiO 2 xerogel with an organosilane precursor. ► Hierarchical pore structure was confirmed by characterization of the materials. ► Catalytic activity was tested using oxidative desulfurization of the model sulfur compounds. ► Meso-TS-1 demonstrated significantly improved catalytic activity than TS-1. -- Abstract: Mesoporous TS-1 (M-TS-1) was synthesized using a hybrid SiO 2 –TiO 2 xerogel combined with an organosilane precursor. Prepared samples were characterized by XRD, UV–vis spectroscopy, SEM, and N 2 adsorption–desorption measurement. M-TS-1, prepared in 2 days, showed high crystallinity and the best textural properties among the samples. The N 2 adsorption–desorption isotherms of M-TS-1 exhibited a hysteresis loop at pressure higher than P/P 0 = 0.4, clearly indicating the existence of mesopores. M-TS-1 has significantly larger mesopore volume (0.48 cm 3 /g) than that of conventional TS-1 (0.07 cm 3 /g), and showed a narrow peak centered at ca. 6.3 nm. In the oxidative desulfurization reaction, M-TS-1 was more active than conventional TS-1 at the same Ti-loading; M-TS-1 produced a dibenzothiophene (DBT) conversion of 96%, whereas conventional TS-1 produced a final DBT conversion of 5.6% after a reaction time of 180 min. Oxidative desulfurization over TS-1 was influenced both by electron density and steric hindrance in the sulfur compounds tested.

Novel cleavage and oligomerization reactions of nickel (o) complexes. Application to homogeneous deoxygenation and desulfurization

International Nuclear Information System (INIS)

Eisch, J.J.; Im, K.R.

1979-01-01

The ease of interaction of Ni(0) complexes with organic substrates has been shown to depend upon both the ligands on nickel and the solvent. The presence of α,α'-bipyridyl with the Ni(0) complex and the alkyne led to the isolation of a nickelacyclopropene, an observation in accord with the recently proposed metallocyclic pathway for the Ni(0)-catalyzed trimerization of alkynes. Allylic and benzylic ethers and epoxides have been observed to undergo oxidative insertion of Ni(0) into their C-O bonds with solvent (TMEDA > THF (tetrahydrofuran) > Et 2 O > C 6 H 6 ) and ligand (Et 3 P (tripthyl phosphine) > Ph 3 P (triphenyl phosphine); α,α'-bipy > COD) effects consistent with an electron-transfer attack by Ni(0). With such sulfur heterocycles as dibenzothiophene, phenoxathiin, phenothiazine, and thianthrene, a 1:1 admixture of (COD) 2 Ni with α,α'-bipyridyl gave as the principal product the desulfurized, ring-contracted cyclic product

Extractive oxidative desulfurization of model oil/crude oil using KSF montmorillonite-supported 12-tungstophosphoric acid

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Ezzat Rafiee

2016-10-01

Full Text Available Abstract 12-Tungstophosphoric acid (PW supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization (ODS of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide (H2O2 as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-to-sulfur compounds (S-compounds molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene (DBT and mixed thiophenic model oil under atmospheric pressure at 75 °C in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.

Electronic transitions of fluorene, dibenzofuran, carbazole, and dibenzothiophene

DEFF Research Database (Denmark)

Nguyen, Duy Duc; Trunk, John; Nakhimovsky, Lina

2010-01-01

A comparative study of the electronic transitions of fluorene and its hetero-analogues dibenzofuran, carbazole, and dibenzothiophene was performed in a wide energy range. Gas phase, crystal phase, and linear dichroism electronic transmittance spectra were measured with synchrotron radiation...

Attapulgite-CeO2/MoS2 ternary nanocomposite for photocatalytic oxidative desulfurization

Science.gov (United States)

Li, Xiazhang; Zhang, Zuosong; Yao, Chao; Lu, Xiaowang; Zhao, Xiaobing; Ni, Chaoying

2016-02-01

Novel attapulgite(ATP)-CeO2/MoS2 ternary nanocomposites were synthesized by microwave assisted assembly method. The structures of the nanocomposites were characterized by XRD, FT-IR, UV-vis, XPS and in situ TEM. The photocatalytic activities of ATP-CeO2/MoS2 composites were investigated by degradating dibenzothiophene (DBT) in gasoline under visible light irradiation. The effect of the mass ratio of CeO2 to MoS2 on photocatalytic activity was investigated. The results indicate that the three-dimensional network structure is firmly constructed by ATP skeleton, CeO2 particles and MoS2 nanosheet which effectively increase the surface area of the composites and promote the separation of electrons and holes by resulting electronic transmission channels of multi-channel in space. The degradation rate of DBT can reach 95% under 3 h irradiation when the mass ratio of CeO2/MoS2 is 4/10. A plausible mechanism for the photocatalytic oxidative desulfurization of this nanocomposite is put forward.

Bicarbonate-induced activation of H₂O₂ for metal-free oxidative desulfurization.

Science.gov (United States)

Bokare, Alok D; Choi, Wonyong

2016-03-05

Efficient oxidative desulfurization (ODS) of model oil containing dibenzothiophene (DBT) and aromatic thiophenic derivatives has been achieved at room temperature using hydrogen peroxide activation by inorganic bicarbonate (HCO3(-)). Using in-situ formation of peroxymonocarbonate as oxidant, the transformation of main model substrate DBT to corresponding DBT-sulfone was easily accomplished in biphasic reaction conditions. In the presence of water-acetonitrile polar phase, increasing the water content upto 50% decreased the extraction capacity more than 3 times, but ∼ 90% DBT oxidation was still achieved. The oxidizing capacity of bicarbonate catalyst was maintained during repeated ODS cycles, but DBT removal efficiency was critically dependent on the extraction capacity of the polar phase. Under heterogeneous reaction conditions, bicarbonate-modified ion-exchange resin achieved similar ODS activity compared to the homogeneous catalytic system. Additionally, the efficient formation of peroxymonocarbonate using gaseous CO2 precursor in alkaline conditions was also utilized for DBT oxidation. The present study proposes the NaHCO3/H2O2 catalytic system as an efficient and cheap metal-free alternative for the oxidative removal of aromatic sulfur compounds from fuel oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Removal of Dibenzothiophene Using Activated Carbon/γ-Fe2O3 Nano-Composite: Kinetic and Thermodynamic Investigation of the Removal Process

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Maryam Fayazi

2015-12-01

Full Text Available In the present study, removal of dibenzothiophene (DBT from model oil (n-hexane was investigated using magnetic activated carbon (MAC nano-composite adsorbent. The synthesized nano-composite was characterized by FT-IR, FE-SEM, BET and VSM techniques. The MAC nano-composite exhibited a nearly superparamagnetic property with a saturation magnetization (Ms of 29.2 emu g-1, which made it desirable for separation under an external magnetic field. The magnetic adsorbent afforded a maximum adsorption capacity of 38.0 mg DBT g-1 at the optimized conditions (adsorbent dose, 8 g l-1; contact time, 1 h; temperature, 25 °C. Langmuir, Freundlich and Temkin isotherm models were used to fit equilibrium data for MAC nano-composite. Adsorption process could be well described by the Langmuir model. Kinetic studies were carried out and showed the sorption kinetics of DBT was best described by a pseudo-second-order kinetic model. In addition, the MAC nano-composite exhibited good capability of recycling to adsorb DBT in gasoline deep desulfurization.

Adsorption isotherms and kinetics for dibenzothiophene on activated

Indian Academy of Sciences (India)

Adsorption isotherms were obtained and desulphurization kinetics were carried out on solutions of dibenzothiophene (DBT) and thiophene in a model fuel. The efficiencies of DBT and thiophene removal were reported. The adsorption isotherms fitted the Langmuir and Freundlich models. The highest adsorption capacity for ...

Preparation of ionic liquid-modified SBA-15 doped with molybdovanadophosphoric acid for oxidative desulfurization

Energy Technology Data Exchange (ETDEWEB)

Zhuang, Jiang Zhou; Jin, Xiao Yin; Shen, Xian Lin; Tan, Jun Jun; Nie, Long Hui; Xiang, Jian; Hu, Bing [Dept. of chool of Chemistry and Chemical Engineering, Hubei University of Technology, Wuhan (China)

2015-07-15

A series of catalysts, ionic liquid-modified SBA-15 (denoted ILSBA) doped with H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} (HPMoV{sub 2}) have been synthesized and characterized by XRD, FT-IR, {sup 1}H NMR, TG-DTA, and TEM. The catalyst was used for the removal of dibenzothiophene (DBT) in model oil combined with hydrogen peroxide (the oxidant) and acetonitrile (the phase-transfer agent). It was observed that the sulfur content of DBT can be reduced from 500 to 2 ppm by adjusting the amount of catalyst, the reaction temperatures and the reaction time. Besides, the catalyst activity for different sulfur compounds showed a huge difference which may be mainly affected by the electron densities of sulfur atom. Moreover, the catalyst can be recycled seven times without a significant loss in activity, which could be ascribed to the strong electrostatic interaction between ILSBA and HPMoV{sub 2}. In addition, a postulated mechanism was proposed to reveal the oxidative desulfurization process.

Attapulgite-CeO{sub 2}/MoS{sub 2} ternary nanocomposite for photocatalytic oxidative desulfurization

Energy Technology Data Exchange (ETDEWEB)

Li, Xiazhang, E-mail: lixiazhang509@163.com [Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164 (China); Jiangsu Key Laboratory for Environment Functional Materials, Suzhou University of Science and Technology, Suzhou 215009 (China); W.M.Keck Center for Advanced Microscopy and Microanalysis, University of Delaware, Newark, DE 19716 (United States); Zhang, Zuosong [School of Materials Science and Engineering, Changzhou University, Changzhou 213164 (China); Yao, Chao [Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164 (China); Lu, Xiaowang [School of Materials Science and Engineering, Changzhou University, Changzhou 213164 (China); Zhao, Xiaobing [School of Materials Science and Engineering, Changzhou University, Changzhou 213164 (China); Jiangsu Key Laboratory for Environment Functional Materials, Suzhou University of Science and Technology, Suzhou 215009 (China); Ni, Chaoying [W.M.Keck Center for Advanced Microscopy and Microanalysis, University of Delaware, Newark, DE 19716 (United States)

2016-02-28

Graphical abstract: - Highlights: • Novel attapulgite(ATP)-CeO{sub 2}/MoS{sub 2} ternary nanocomposites were fabricated. • ATP possessed outstanding adsorption property and enhanced the stability of the network structure. • CeO{sub 2}/MoS{sub 2} couples facilitated the separation of photo-induced electrons and holes. • Mass ratio of CeO{sub 2}/MoS{sub 2} influenced the photocatalytic oxidation desulfurization. - Abstract: Novel attapulgite(ATP)-CeO{sub 2}/MoS{sub 2} ternary nanocomposites were synthesized by microwave assisted assembly method. The structures of the nanocomposites were characterized by XRD, FT-IR, UV–vis, XPS and in situ TEM. The photocatalytic activities of ATP-CeO{sub 2}/MoS{sub 2} composites were investigated by degradating dibenzothiophene (DBT) in gasoline under visible light irradiation. The effect of the mass ratio of CeO{sub 2} to MoS{sub 2} on photocatalytic activity was investigated. The results indicate that the three-dimensional network structure is firmly constructed by ATP skeleton, CeO{sub 2} particles and MoS{sub 2} nanosheet which effectively increase the surface area of the composites and promote the separation of electrons and holes by resulting electronic transmission channels of multi-channel in space. The degradation rate of DBT can reach 95% under 3 h irradiation when the mass ratio of CeO{sub 2}/MoS{sub 2} is 4/10. A plausible mechanism for the photocatalytic oxidative desulfurization of this nanocomposite is put forward.

Ultra-deep desulfurization via reactive adsorption on peroxophosphomolybdate/agarose hybrids.

Science.gov (United States)

Xu, Jian; Li, Huacheng; Wang, Shengtian; Luo, Fang; Liu, Yunyu; Wang, Xiaohong; Jiang, Zijiang

2014-09-01

A catalyst system composed of peroxophosphomolybdates as catalytic center and agarose as matrix material had been designed. The [C16H33N(CH3)3]3[PO4{MoO(O2)2}4]/agarose (C16PMo(O2)2/agarose) hybrid was found to be active for oxidation desulfurization (ODS) of dibenzothiophene (DBT) or real fuel into corresponding sulfone by H2O2 as an oxidant, while the sulfur content could be reduced to 5ppm. The higher activity comes from its components including [PO4{MoO(O2)2}4] catalytic sites, the hydrophobic quaternary ammonium cation affinity to low polarity substrates, and agarose matrix affinity to H2O2 and sulfone. During the oxidative reaction, the mass transfer resistance between H2O2 and organic sulfurs could be decreased and the reaction rate could increase by the assistance of agarose and hydrophobic tails of [C16H33N(CH3)3]3[PO4{MoO(O2)2}4]. Meanwhile, the oxidative products could be adsorbed by agarose matrix to give clean fuel avoiding the post-treatment. In addition, the hybrid was easily regenerated to be reused. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preparation and characterization of nanocomposite of graphitic carbon nitride and TiO2 as a porous support for nano catalyst for desulfurization process

Directory of Open Access Journals (Sweden)

Ezzat Rafiee

2017-12-01

Full Text Available A novel heterogeneous nanocatalyst H3PW12O40/TiO2/g-C3N4 (PW/TiO2/CN was successfully synthesized by immobilization of PW on TiO2/CN nanocomposite, and characterized by SEM, BET, FT-IR, XRD, EDX, TEM and ICP. Catalytic performance of the as-prepared catalyst was investigated for the selective oxidation of sulfides to sulfoxides and sulfones in the presence of H2O2 as oxidant with good conversion and high selectivity. The main factors influencing the ability for selective oxidation of sulfides were studied, including reaction temperature, amounts of the catalyst, H2O2 and type of the reaction solvent. Catalytic oxidation of the different model oils containing dibenzothiophene (DBT, benzothiophene (BT and thiophene (T into corresponding sulfone was also studied. Effects of different extractive solvents, aromatics, alkenes and nitrogen compounds on the oxidative desulfurization processes (ODS were also studied. In addition, reducing the level of sulfur content in real oil was investigated. The recyclability of the PW/TiO2/CN nanocatalyst for various cycles without a significant loss of activity was proved. The heterogeneity of the as-prepared catalyst was confirmed by leaching tests. Keywords: Graphitic carbon nitride, Extraction, Tetrabutyl titanate, Heteropoly acid, Oxidative desulfurization, Oil

Benzo[b]naphthothiophenes and alkyl dibenzothiophenes: molecular tracers for oil migration distances

Science.gov (United States)

Li, Meijun; Wang, T.-G.; Shi, Shengbao; Liu, Keyu; Ellis, Geoffrey S.

2014-01-01

The secondary migration of petroleum is one of the most critical geological processes responsible for the accumulation of hydrocarbons in a sedimentary basin. Pyrrolic nitrogen compounds such as carbazoles and benzocarbazoles are thought to be practical molecular indicators for estimating relative migration distances of oil. In light oils or condensates, however, considerable analytical errors are usually caused by low concentrations of NSO-compounds. Here we show that polycyclic sulfur aromatic hydrocarbons such as dibenzothiophene, C1∼C3 alkylated dibenzothiophenes and benzo[b]naphthothiophenes, which are present in relatively higher concentrations than the pyrrolic nitrogen compounds, exhibit changes in both absolute and relative concentrations that correlate with migration distances. The polycyclic sulfur aromatic hydrocarbons related parameters — benzo[b]naphtho[2,1-d]thiophene/{benzo[b]naphtho[2,1-d]thiophene + benzo[b]naphtho[1,2-d]thiophene} (abbreviated as [2,1]BNT/([2,1]BNT+[1,2]BNT) and the concentration of total dibenzothiophenes plus benzo[b]naphthothiophenes — are proposed by this paper to trace the oil migration distances.

A novel Bacillus pumilus-related strain from tropical landfarm soil is capable of rapid dibenzothiophene degradation and biodesulfurization.

Science.gov (United States)

Buzanello, Elizandra Bruschi; Rezende, Rachel Passos; Sousa, Fernanda Maria Oliveira; Marques, Eric de Lima Silva; Loguercio, Leandro Lopes

2014-10-08

The presence of organic sulfur-containing compounds in the environment is harmful to animals and human health. The combustion of these compounds in fossil fuels tends to release sulfur dioxide in the atmosphere, which leads to acid rain, corrosion, damage to crops, and an array of other problems. The process of biodesulfurization rationally exploits the ability of certain microorganisms in the removal of sulfur prior to fuel burning, without loss of calorific value. In this sense, we hypothesized that bacterial isolates from tropical landfarm soils can demonstrate the ability to degrade dibenzothiophene (DBT), the major sulfur-containing compound present in fuels. Nine bacterial isolates previously obtained from a tropical landfarm soil were tested for their ability to degrade dibenzothiophene (DBT). An isolate labeled as RR-3 has shown the best performance and was further characterized in the present study. Based on physiological aspects and 16 s rDNA sequencing, this isolate was found to be very closely related to the Bacillus pumillus species. During its growth, high levels of DBT were removed in the first 24 hours, and a rapid DBT degradation within the first hour of incubation was observed when resting cells were used. Detection of 2-hydroxybiphenyl (HBP), a marker for the 4S pathway, suggests this strain has metabolical capability for DBT desulfurization. The presence of MgSO4 in growth medium as an additional sulfur source has interfered with DBT degradation. To our knowledge, this is the first study showing that a Bacillus strain can metabolize DBT via the 4S pathway. However, further evidences suggest RR-3 can also use DBT (and/or its derivative metabolites) as carbon/sulfur source through another type of metabolism. Compared to other reported DBT-degrading strains, the RR-3 isolate showed the highest capacity for DBT degradation ever described in quantitative terms. The potential application of this isolate for the biodesulfurization of this sulfur

Nano clay Ni/NiO nanocomposite new sorbent for separation and preconcentration dibenzothiophene from crude prior to UV–vis spectrophotometery determination

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Amineh Mashkuri

2017-06-01

Full Text Available In this work, Ni/Ni nanoparticles were immobilized on modified nanoclay then, the resultant nanocomposite was used as a sorbent for separation of dibenzothiophene. The concentration of dibenzothiophene was determined with UV–vis spectrophotometry at 287 nm. Different parameters affecting the separation of dibenzothiophene such as: the ratio of Ni/NiO nanoparticles to nanoclay, amounts of Ni/NiO nanoparticles and nanoclay, stirring time of dibenzothiophene solution on the sorbent, type of eluent, eluent volume, elution time, stirring time for preparing the sorbent were optimized. The obtained results were shown quantitative desorption of dibenzothiophene performed using ethanol as eluent. A linear concentration range of 0.5–15 mg/L was obtained with a detection limit of 0.047 mg/mL. The sorbent capacity was found to be 32 mg/g. Relative standard deviation was ±1.4 for six replicated determination of 5 mg/g of dibenzothiophene. The optimized procedure was successfully used for a crude oil sample.

Preparation And Characterization of Cu-Fe/ TiO2 Photocatalyst for Visible Light Deep Desulfurization

International Nuclear Information System (INIS)

Hayyiratul Fatimah Mohd Zaid; Kait, C.F.; Mohamed Ibrahim Abdul Mutalib

2016-01-01

A photooxidative system for deep desulfurization of model diesel fuel was explored. Nanoparticles of anatase titania (TiO 2 ) were synthesized via sol-gel hydrothermal method. The TiO 2 was further modified with bimetallic Cu-Fe using wet-impregnation method followed by calcination process in order to extend the activity region of the photocatalyst to visible-light. A series of bimetallic 2.2 wt % Cu-Fe/ TiO 2 photocatalysts with different Cu:Fe mass compositions were characterized for their physical, chemical and optical properties using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), diffuse reflectance UV-visible spectroscopy (DR-UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR) and Brunauer-Emmet-Teller (BET) surface area analysis. The performance of the photocatalysts was evaluated for photooxidation of dibenzothiophene (DBT) as the sulfur species from model oil in the presence of hydrogen peroxide, H 2 O 2 under 500 W visible light illumination. The highest sulfur conversion of 82.36 % was observed for photocatalyst with 10:1Cu:Fe mass composition. (author)

Oxidative desulfurization of tire pyrolysis oil

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Ahmad Shahzad

2016-01-01

Full Text Available This paper presents a low cost method for the purification of oils obtained from the pyrolysis of used tires. Oxidative desulfurization is a promising route for purification of tire pyrolysis oils as hydro-desulfurization may not be affordable for small scale industries. Different additives and acids have been employed for the enhancement of properties of pyrolytic oils. The experimental conditions were kept identical throughout, i.e. atmospheric pressure and 50°C temperature for comparison of performance of various additives. The use of hydrogen peroxide-acetic acid mixture (10 wt.% was found more economical and effective in desulfurization and improvement of fuel properties of sample oils. The contribution of sulfuric acid in desulfurization and decreasing viscosity was also satisfactory but due to high price of concentrated sulfuric acid its use may not be economical. Calcium oxide and Fuller’s earth was not found to be effective in desulfurization. Results indicate that oxidative desulfurization could render tire pyrolysis oils suitable for blending as heating fuel.

Synthesis of mesoporous TS-1 using a hybrid SiO{sub 2}–TiO{sub 2} xerogel for catalytic oxidative desulfurization

Energy Technology Data Exchange (ETDEWEB)

Yang, Seung-Tae [Department of Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of); Jeong, Kwang-Eun; Jeong, Soon-Yong [Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology, P.O. Box 107, 141 Gajeong-ro, Yuseong, Daejeon 305-600 (Korea, Republic of); Ahn, Wha-Seung, E-mail: whasahn@inha.ac.kr [Department of Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► Meso-TS-1 catalyst was synthesized using a SiO{sub 2}–TiO{sub 2} xerogel with an organosilane precursor. ► Hierarchical pore structure was confirmed by characterization of the materials. ► Catalytic activity was tested using oxidative desulfurization of the model sulfur compounds. ► Meso-TS-1 demonstrated significantly improved catalytic activity than TS-1. -- Abstract: Mesoporous TS-1 (M-TS-1) was synthesized using a hybrid SiO{sub 2}–TiO{sub 2} xerogel combined with an organosilane precursor. Prepared samples were characterized by XRD, UV–vis spectroscopy, SEM, and N{sub 2} adsorption–desorption measurement. M-TS-1, prepared in 2 days, showed high crystallinity and the best textural properties among the samples. The N{sub 2} adsorption–desorption isotherms of M-TS-1 exhibited a hysteresis loop at pressure higher than P/P{sub 0} = 0.4, clearly indicating the existence of mesopores. M-TS-1 has significantly larger mesopore volume (0.48 cm{sup 3}/g) than that of conventional TS-1 (0.07 cm{sup 3}/g), and showed a narrow peak centered at ca. 6.3 nm. In the oxidative desulfurization reaction, M-TS-1 was more active than conventional TS-1 at the same Ti-loading; M-TS-1 produced a dibenzothiophene (DBT) conversion of 96%, whereas conventional TS-1 produced a final DBT conversion of 5.6% after a reaction time of 180 min. Oxidative desulfurization over TS-1 was influenced both by electron density and steric hindrance in the sulfur compounds tested.

Ultra-Deep Adsorptive Desulfurization of Light-Irradiated Diesel Fuel over Supported TiO₂-CeO₂ Adsorbents

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jing; Wang, Xiaoxing; Chen, Yongsheng; Fujii, Mamoru; Song, Chunshan [SCUT-China; (Penn)

2014-02-13

This study investigates ultra-deep adsorptive desulfurization (ADS) from light-irradiated diesel fuel over supported TiO₂–CeO₂ adsorbents. A 30-fold higher desulfurization capacity of 95 mL of fuel per gram of adsorbent (mL-F/g-sorb) or 1.143 mg of sulfur per gram of adsorbent (mg-S/g-sorb) was achieved from light-irradiated fuel over the original low-sulfur fuel containing about 15 ppm by weight (ppmw) of sulfur. The sulfur species on spent TiO₂–CeO₂/MCM-48 adsorbent was identified by sulfur K-edge XANES as sulfones and the adsorption selectivity to different compounds tested in a model fuel decreases in the order of indole > dibenzothiophenesulfone → dibenzothiophene > 4-methyldibenzothiophene > benzothiophene > 4,6-dimethyldibenzothiophene > phenanthrene > 2-methylnaphthalene ~ fluorene > naphthalene. The results suggest that during ADS of light-irradiated fuel, the original sulfur species were chemically transformed to sulfones, resulting in the significant increase in desulfurization capacity. For different supports for TiO2–CeO2 oxides, the ADS capacity increases with a decrease in the point of zero charge (PZC) value; for silica-supported TiO₂–CeO₂ oxides (the lowest PZC value of 2–4) with different surface areas, the ADS capacity increases monotonically with increasing surface area. The supported TiO₂–CeO₂/MCM-48 adsorbent can be regenerated using oxidative air treatment. The present study provides an attractive new path to achieve ultraclean fuel more effectively.

Degradation of carbazole, dibenzothiophene, and dibenzofuran at low temperature by Pseudomonas sp. strain C3211.

Science.gov (United States)

Jensen, Anne-Mette; Finster, Kai Waldemar; Karlson, Ulrich

2003-04-01

Pseudomonas sp. strain C3211 was isolated from a temperate climate soil contaminated with creosote. This strain was able to degrade carbazole, dibenzothiophene and dibenzofuran at 10 degrees C with acetone as a co-substrate. When dibenzothiophene was degraded by strain C3211, an orange compound, which absorbed at 472 nm, accumulated in the medium. Degradation of dibenzofuran was followed by accumulation of a yellowish compound, absorbing at 462 nm. The temperature optimum of strain C3211 for degradation of dibenzothiophene and dibenzofuran was at 20 to 21 degrees C, while the maximum temperature for degradation was at 27 degrees C. Both compounds were degraded at 4 degrees C. Degradation at 10 degrees C was faster than degradation at 25 degrees C. This indicates that strain C3211 is adapted to life at low temperatures.

Rare earth oxides in gaseous desulfurization

International Nuclear Information System (INIS)

Kay, D.A.R.; Wilson, W.G.

1988-01-01

Phase stability diagrams are used to predict the abilities of lanthanum and cerium oxides to desulfurize coal gasification products in the temperature range 800-1000 C. Results of desulfurization studies in laboratory fixed bed reactors illustrate the effects of sorbent preparation, input gas quality and temperature, on the desulfurization reaction: 2CeO( 2 - x )(s) + H 2 S(g) + (1-2x)H 2 = Ce 2 O 2 S(s) + 2(1 - x)H 2 O(g). The results of desulfurization/oxidation regeneration cycles are also reported

Biotransformation and removal of sulfur from dibenzothiophene using improved bio catalytic methods

International Nuclear Information System (INIS)

La Rotta, C. E; Mora, A.L; Madero, A; Mogollon, L.I

1998-01-01

Three methods for the removal of sulfur from dibenzothiophene were evaluated using bio catalytic processes. The methods were a microbial, an enzymatic and a combined one that involves a previous enzymatic oxidation followed by microbial degradation. The bioconversion was evaluated over the molecular dibenzothiophene model, obtaining higher bioconversion percentages through the combined method. The microorganisms used in this study correspond to several Colombian indigenous strains isolated by direct methods from natural sources, and using a standard strain as positive control. All strains have shown sulfur removal capacity, and organic solvent tolerance. The enzyme used was a hemo protein with peroxidase activity, Cytochrome C, obtained from equine heart

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

International Nuclear Information System (INIS)

González, J.; Chen, L.F.; Wang, J.A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J.L.

2016-01-01

Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V 2 O 5 /Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H 2 O 2 as oxidant. ODS activity was found to be proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts, indicating that the surface vanadium pentoxide (V 2 O 5 ) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V 2 O 5 ) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V 2 O 5 /Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Preparation of WO3/g-C3N4 composites and their application in oxidative desulfurization

Science.gov (United States)

Zhao, Rongxiang; Li, Xiuping; Su, Jianxun; Gao, Xiaohan

2017-01-01

WO3/graphitic carbon nitride (g-C3N4) composites were successfully synthesized through direct calcining of a mixture of WO3 and g-C3N4 at 400 °C for 2 h. The WO3 was prepared by calcination of phosphotungstic acid at 550 °C for 4 h, and the g-C3N4 was obtained by calcination of melamine at 520 °C for 4 h. The WO3/g-C3N4 composites were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), and Brunner-Emmett-Teller analysis (BET). The WO3/g-C3N4 composites exhibited stronger XRD peaks of WO3 and g-C3N4 than the WO3 and pure g-C3N4. In addition, two WO3 peaks at 25.7° and 26.6° emerged for the 36% -WO3/g-C3N4 composite. This finding indicated that WO3 was highly dispersed on the surface of the g-C3N4 nanosheets and interacted with the nanosheets, which resulted in the appearance of (012) and (022) planes of WO3. The WO3/g-C3N4 composite also exhibited a larger specific surface area and higher degree of crystallization than WO3 or pure g-C3N4, which resulted in high catalytic activity of the catalyst. Desulfurization experiments demonstrated that the desulfurization rate of dibenzothiophene (DBT) in model oil reached 91.2% under optimal conditions. Moreover, the activity of the catalyst was not significantly decreased after five recycles.

Influence of surface phenomena in oxidative desulfurization with WOx/ZrO2 catalysts

Science.gov (United States)

Torres-García, E.; Canizal, G.; Velumani, S.; Ramírez-Verduzco, L. F.; Murrieta-Guevara, F.; Ascencio, J. A.

2004-12-01

Oil refinery related catalysis, particularly hydro desulfurization is viewed as a mature technology, but still we view that more efforts have to be made to boost the efficiency of the existing catalysts. So in this article we report the use of WOx/ZrO2 catalysts for the oxidation of dibenzothiophene (DBT) as a more effective material in nanometer scales. The WOx/ZrO2 samples were prepared by solid impregnation of ZrO2-x(OH)2x with ammonium metatungstate solution maintaining the pH at 10. Detailed structural and surface morphological analyses were carried out using Raman spectroscopy and Atomic force microscopy. In order to understand the catalytic activity which is largely influenced by the surface morphology, an interpretation based on the experimental results is given. The results showed an important correlation between the catalytic efficiency with the morphology of the surface which is identified as arrays of planes with steps of around 10 nm with the structures showing faceting with a preferential angle of 90°. It was established that when the number of W atoms in the surface increase the catalytic efficiency also increases. Thus we conclude that the material efficiency as a catalyst is directly related with the surface structure.

Heterogeneous oxidative desulfurization of diesel fuel catalyzed by mesoporous polyoxometallate-based polymeric hybrid.

Science.gov (United States)

Yang, Huawei; Jiang, Bin; Sun, Yongli; Zhang, Luhong; Huang, Zhaohe; Sun, Zhaoning; Yang, Na

2017-07-05

In this work, the simple preparation of novel polymer supported polyoxometallates (POMs) catalysts has been reported. Soluble task-specific cross-linked poly (ionic liquid) (PIL) was prepared with N,​N-​dimethyl-​dodecyl-​(4-​vinylbenzyl) ammonium chloride and divinylbenzene as co-monomers. The as-prepared cationic PILs were assembled with different commercial POMs to form the interlinked mesoporous catalysts, and the formation mechanism was provided. The catalytic oxidation activities of the catalysts were closely related to the formation pathway of their corresponding peroxide active species. The catalyst with H 2 W 12 O 42 10- as counterion, which exhibited the best activity in the oxidation of benzothiophene (BT) and dibenzothiophene (DBT) to sulfones in model oil with hydrogen peroxide (H 2 O 2 , 30wt%) as oxidant, was characterized by different techniques and systematically studied for its sulfur removal performance. As for the oxidative desulfurization of a real diesel, it was observed that almost all of the original sulfur compounds could be completely converted, and the catalyst could be reused for at least eight cycles without noticeable changes in both catalytic activity and chemical structure. In the end, a catalytic mechanism was put forward with the assistant of Raman analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Desulfurization of Jordanian oil shale

International Nuclear Information System (INIS)

Abu-Jdayil, B. M.

1990-01-01

Oxy desulfurization process and caustic treatment were applied in this work to remove sulfur from Jordanian oil shale. The oxy desulfurization process has been studied in a batch process using a high pressure autoclave, with constant stirring speed, and oxygen and water were used as desulfurizing reagents. Temperature, oxygen pressure, batch time, and particle size were found to be important process variables, while solid/liquid ratio was found to have no significant effect on the desulfurization process. The response of different types of oil shale to this process varied, and the effect of the process variables on the removal of total sulfur, pyritic sulfur, organic sulfur, total carbon, and organic carbon were studied. An optimum condition for oxy desulfurization of El-Lajjun oil shale, which gave maximum sulfur removal with low loss of carbon, was determined from the results of this work. The continuous reaction model was found to be valid, and the rate of oxidation for El-Lajjun oil shale was of the first order with respect to total sulfur, organic sulfur, total carbon, and organic carbon. For pyritic sulfur oxidation, the shrinking core model was found to hold and the rate of reaction controlled by diffusion through product ash layer. An activation energy of total sulfur, organic sulfur, pyritic sulfur, total carbon, and organic carbon oxidation was calculated for the temperature range of 130 -190 degrees celsius. In caustic treatment process, aqueous sodium hydroxide at 160 degrees celsius was used to remove the sulfur from El-Lajjun oil shale. The variables tested (sodium hydroxide concentration and treatment time) were found to have a significant effect. The carbon losses in this process were less than in the oxy desulfurization process. 51 refs., 64 figs., 121 tabs. (A.M.H.)

Magnesite base desulfurizer of metallurgical physical chemistry research

Directory of Open Access Journals (Sweden)

G. D. Liu

2017-01-01

Full Text Available This topic put carbon thermal vacuum method in combination with magnesium based desulfurization technology with magnesite reduction of magnesium vapor directly on hot metal desulphurization. This is a new type of desulfurization technology, the retrieval related literature at home and abroad was not reported in the recent ten years, according to the relationship between heat of desulfurizer preparation MgO style content can reach 50 %.It was found that the desulfurizer sample with 50 % MgO content was in accordance with the requirements, without adding flux, but its viscosity did not meet the requirements; adding 1 % flux (CaF2, the sample viscosity was significantly reduced, and about 1 400 °C sample viscosity suitable for hot metal pretreatment desulfurization.

Adsorptive desulfurization of model oil using untreated, acid activated and magnetite nanoparticle loaded bentonite as adsorbent

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Muhammad Ishaq

2017-02-01

Full Text Available The present research work focuses on a novel ultraclean desulfurization process of model oil by the adsorption method using untreated, acid activated and magnetite nanoparticle loaded bentonite as adsorbent. The parameters investigated are effect of contact time, adsorbent dose, initial dibenzothiophene (DBT concentration and temperature. Experimental tests were conducted in batch process. Pseudo first and second order kinetic equations were used to examine the experimental data. It was found that pseudo second order kinetic equation described the data of the DBT adsorption onto all types of adsorbents very well. The isotherm data were analyzed using Langmuir and Freundlich isotherm models. The Langmuir isotherm model fits the data very well for the adsorption of DBT onto all three forms of adsorbents. The adsorption of DBT was also investigated at different adsorbent doses and was found that the percentage adsorption of DBT was increased with increasing the adsorbent dose, while the adsorption in mg/g was decreased with increasing the adsorbent dose. The prepared adsorbents were analyzed by scanning electron microscopy (SEM, energy dispersive X-ray spectrometry (EDX and X-ray diffraction (XRD.

Surface chemistry and catalytic properties of VO{sub X}/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

Energy Technology Data Exchange (ETDEWEB)

González, J. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Chen, L.F., E-mail: lchen@ipn.mx [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Wang, J.A.; Manríquez, Ma.; Limas, R. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Schachat, P.; Navarrete, J. [Dirección de Investigación, Instituto Mexicano del Petróleo, Eje Lázaro Cárdenas 152, 07730 México D.F. (Mexico); Contreras, J.L. [Laboratorio de Catálisis y Polímeros, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-A, Av. San Pablo No. 180, 02200 México D.F. (Mexico)

2016-08-30

Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V{sub 2}O{sub 5}/Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H{sub 2}O{sub 2} as oxidant. ODS activity was found to be proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts, indicating that the surface vanadium pentoxide (V{sub 2}O{sub 5}) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V{sub 2}O{sub 5}) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V{sub 2}O{sub 5}/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Effects of the surfactant Tween 80 on the growth and dibenzothiophene utilization by Exophiala spinifera isolated from oil- contaminated soil

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Fatemeh Elmi

2016-06-01

Full Text Available Introduction: Oil is one of the most important energy sources that contain variety of organosulfur compounds that are combustible and can produce sulfur dioxide which will cause pollution over the atmosphere and the soil. Dibenzothiophene (DBT is often used as a model for biodesulfurization studies and surfactant Tween80 increases the solubility of DBT in water that leads to higher consumption by microorganisms. Materials and methods: DBT specific UV spectrophotometry at a wavelength of 323 nm was used to evaluate the ability of isolated Exophiala spinifera fungus in removal of DBT. The effect of various concentrations of surfactant Tween80 on the growth of the fungus and DBT utilization was studied. Results: Exophiala spinifera was able to remove 100% DBT after 7 days of incubation at 30 ° C and 180 rpm shaking. The effect of different concentrations of surfactant Tween80 on growth and DBT utilization by this fungus was examined and it was observed that the presence of surfactant in the culture medium increased the growth and removal of DBT, therefore the amount of DBT utilized with 0.4% concentration of the surfactant was about 30% more than that utilized without surfactant. However, higher concentrations of surfactant Tween80 decreased the growth and consumption of DBT by fungi. Discussion and conclusion: Exophiala spinifera was isolated from oil contaminated soil and able to utilize toxic compound DBT as a sulfur source in the presence of other carbon sources such as glucose. So this isolated strain could be a good candidate for the petroleum desulfurization and it is the first report about desulfurization of DBT by fungus Exophiala spinifera. Growth and removal of DBT by fungus increased in the presence of surfactant Tween80. It can be concluded that the surfactant increases the total DBT transfer between the organic and aqueous phases and has a potential application in DBT bioremediation system by the studied fungus biocatalyst.

Desulfurization performance of azole-based ionic liquids

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Liubei CHENG

2017-10-01

Full Text Available In order to study the addition of functional groups in ionic liquid anion and cation to achieve better absorbing of SO2, the 1,1,3,3-tetramethylguanidine triazole ( is synthesized using 1,1,3,3-tetramethylguanidine and triazole as raw materials. The desulfurization performance of the synthesized is systematically studied. The desulfurization performance and desulfurization mechanism of the are discussed. The results show that the has good performance of desulfurization and regeneration. At the atmospheric pressure, 1 mol of the absorbs 2.964 mol of SO2 at 20 ℃. With the increase of temperature, the desulfurization capacity of the decreases gradually. The molar absorption ratio increases with the increase of SO2 partial pressure, and under the conditions of 130 ℃, the desorption rate of the ionic liquid after saturated adsorption reaches over 95%. The mechanism investigation results show that the interaction of SO2 and is the combination of chemical absorption and physical absorption. The results have a certain reference value to improve the efficiency of flue gas treatment.

Revisiting dibenzothiophene thermochemical data: Experimental and computational studies

International Nuclear Information System (INIS)

Freitas, Vera L.S.; Gomes, Jose R.B.; Ribeiro da Silva, Maria D.M.C.

2009-01-01

Thermochemical data of dibenzothiophene were studied in the present work by experimental techniques and computational calculations. The standard (p 0 =0.1MPa) molar enthalpy of formation, at T = 298.15 K, in the gaseous phase, was determined from the enthalpy of combustion and sublimation, obtained by rotating bomb calorimetry in oxygen, and by Calvet microcalorimetry, respectively. This value was compared with estimated data from G3(MP2)//B3LYP computations and also with the other results available in the literature.

Method of treating final products from flue gas desulfurization

International Nuclear Information System (INIS)

Bloss, W.; Mohn, U.

1984-01-01

A method of treating final products from a flue gas desulfurization. The flue gas desulfurization is carried out by the absorption of sulfur oxide in a spray dryer with a suspension which contains lime, or in a reactor with a dry, fine-grained, absorbent which contains lime. Prior to desulfurization, the fly ash carried along by the flue gas which is to be desulfurized is separated entirely, partially, or not at all from the flue gas, and the final products from the flue gas desulfurization, prior to any further treatment thereof, amount to 1-99% by weight, preferably 1-70% by weight, of fly ash, and 1-99% by weight, preferably 30-99% by weight, of the sum of the desulfurization products, preferably calcium sulfite hemihydrate, and/or calcium sulfite, and/or calcium sulfate dyhydrate, and/or calcium sulfate hemihydrate, and/or calcium sulfate, as well as residue of the absorbent. The reduction of the amount of calcium sulfite is implemented by a dry oxidation with air

Review of desulfurization process for biogas purification

Science.gov (United States)

Xiao, Cong; Ma, Yunqian; Ji, Dandan; Zang, Lihua

2017-12-01

Hydrogen sulfide (H2S) is a toxic and odorous compound present in biogas produced by the anaerobic digestion of biosolids and other organic materials. Elimination of H2S is necessary as it is extremely hazardous to human health, poisonous to process catalysts and corrosive to equipment. The desulfurization technology is an important part for efficient utilization of biogas. In this paper, the traditional wet and dry desulfurization technology for biogas was reviewed, and the new research progress of biological desulfurization technologies are also introduced.

Boosting the IGCLC process efficiency by optimizing the desulfurization step

International Nuclear Information System (INIS)

Hamers, H.P.; Romano, M.C.; Spallina, V.; Chiesa, P.; Gallucci, F.; Sint Annaland, M. van

2015-01-01

Highlights: • Pre-CLC hot gas desulfurization and post-CLC desulfurization are assessed. • Process efficiency increases by 0.5–1% points with alternative desulfurization methods. • Alternative desulfurization methods are more beneficial for CFB configurations. - Abstract: In this paper the influence of the desulfurization method on the process efficiency of an integrated gasification chemical-looping combustion (IGCLC) systems is investigated for both packed beds and circulating fluidized bed CLC systems. Both reactor types have been integrated in an IGCLC power plant, in which three desulfurization methods have been compared: conventional cold gas desulfurization with Selexol (CGD), hot gas desulfurization with ZnO (HGD) and flue gas desulfurization after the CLC reactors (post-CLC). For CLC with packed bed reactors, the efficiency gain of the alternative desulfurization methods is about 0.5–0.7% points. This is relatively small, because of the relatively large amount of steam that has to be mixed with the fuel to avoid carbon deposition on the oxygen carrier. The HGD and post-CLC configurations do not contain a saturator and therefore more steam has to be mixed with a negative influence on the process efficiency. Carbon deposition is not an issue for circulating fluidized bed systems and therefore a somewhat higher efficiency gain of 0.8–1.0% point can be reached for this reactor system, assuming that complete fuel conversion can be reached and no sulfur species are formed on the solid, which is however thermodynamically possible for iron and manganese based oxygen carriers. From this study, it can be concluded that the adaptation of the desulfurization method results in higher process efficiencies, especially for the circulating fluidized bed system, while the number of operating units is reduced.

Desulfurization of AL-Ahdab Crude Oil using Oxidative Processes

Directory of Open Access Journals (Sweden)

Neran Khalel Ibrahim

2015-07-01

Full Text Available Two different oxidative desulfurization strategies based on oxidation/adsorption or oxidation/extraction were evaluated for the desulfurization of AL-Ahdab (AHD sour crude oil (3.9wt% sulfur content. In the oxidation process, a homogenous oxidizing agent comprising of hydrogen peroxide and formic acid was used. Activated carbons were used as sorbent/catalyst in the oxidation/adsorption process while acetonitrile was used as an extraction solvent in the oxidation/extraction process. For the oxidation/adsorption scheme, the experimental results indicated that the oxidation desulfurization efficiency was enhanced on using activated carbon as catalyst/sorbent. The effects of the operating conditions (contact time, temperature, mixing speed and sorbent dose on the desulfurization efficiency were examined. The desulfurization efficiency measured at the best operating conditions(optimum conditions: 60 , 500rpm, 60min contact time and sorbent dose of 0.7g AC/100 ml AHD crude, was 32.8% corresponding to a sulfur content of 2.6 wt%. Applying the same optimum operating conditions and at 3:1 solvent/oil ratio, the oxidation/extraction method gave comparable desulfurization efficiency of 31.5%.

Oxidative desulfurization of tire pyrolysis oil

OpenAIRE

Ahmad Shahzad; Ahmad Muhammad Imran; Naeem Khawar; Humayun Muhammad; Sebt-E-Zaeem; Faheem Farrukh

2016-01-01

This paper presents a low cost method for the purification of oils obtained from the pyrolysis of used tires. Oxidative desulfurization is a promising route for purification of tire pyrolysis oils as hydro-desulfurization may not be affordable for small scale industries. Different additives and acids have been employed for the enhancement of properties of pyrolytic oils. The experimental conditions were kept identical throughout, i.e. atmospheric pressure a...

SULFUR REDUCTION IN GASOLINE AND DIESEL FUELS BY EXTRACTION/ADSORPTION OF REFRACTORY DIBENZOTHIOPHENES

Energy Technology Data Exchange (ETDEWEB)

Scott G. McKinley; Celedonio M. Alvarez

2003-03-01

The purpose of this study was to remove thiophene, benzothiophene and dibenzothiophene from a simulated gasoline feedstock. We found that Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} reacts with a variety of thiophenes (Th*), affording Ru(NH{sub 3}){sub 5}(Th*){sup 2+}. We used this reactivity to design a biphasic extraction process that removes more than 50% of the dibenzothiophene in the simulated feedstock. This extraction system consists of a hydrocarbon phase (simulated petroleum feedstock) and extractant Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} in an aqueous phase (70% dimethylformamide, 30% H{sub 2}O). The DBT is removed in situ from the newly formed Ru(NH{sub 3}){sub 5}(DBT){sup 2+} by either an oxidation process or addition of H{sub 2}O, to regenerate Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+}.

Ultrasound-Assisted Oxidative Desulfurization of Diesel

OpenAIRE

Niran K. Ibrahim; Walla A. Noori; Jaffar M. Khasbag

2016-01-01

Due to the dramatic environmental impact of sulfur emissions associated with the exhaust of diesel engines, last environmental regulations for ultra-low-sulfur diesel require a very deep desulfurization (up to 15 ppm), which cannot be met by the conventional hydrodesulfurization units alone. The proposed method involves a batch ultrasound-assisted oxidative desulfurization (UAODS) of a previously hydrotreated diesel (containing 480 ppm sulfur) so as to convert the residual sulfur-bearing comp...

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

Science.gov (United States)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Liquefaction and desulfurization of coal using synthesis gas

Science.gov (United States)

Fu, Yuan C.

1977-03-08

A process for desulfurizing and liquefying coal by heating said coal at a temperature of 375.degree.-475.degree. C in the presence of a slurry liquid, hydrogen, carbon monoxide, steam, and a catalyst comprising a desulfurization catalyst and an alkali metal salt.

Experimental study on desulfurization efficiency and gas-liquid mass transfer in a new liquid-screen desulfurization system

International Nuclear Information System (INIS)

Sun, Zhongwei; Wang, Shengwei; Zhou, Qulan; Hui, Shi'en

2010-01-01

This paper presents a new liquid-screen gas-liquid two-phase flow pattern with discarded carbide slag as the liquid sorbent of sulfur dioxide (SO 2 ) in a wet flue gas desulfurization (WFGD) system. On the basis of experimental data, the correlations of the desulfurization efficiency with flue gas flow rate, slurry flow rate, pH value of slurry and liquid-gas ratio were investigated. A non-dimensional empirical model was developed which correlates the mass transfer coefficient with the liquid Reynolds number, gas Reynolds number and liquid-gas ratio (L/G) based on the available experimental data. The kinetic reaction between the SO 2 and the carbide slag depends on the pressure distribution in this desulfurizing tower, gas liquid flow field, flue gas component, pH value of slurry and liquid-gas ratio mainly. The transient gas-liquid mass transfer involving with chemical reaction was quantified by measuring the inlet and outlet SO 2 concentrations of flue gas as well as the characteristics of the liquid-screen two-phase flow. The mass transfer model provides a necessary quantitative understanding of the hydration kinetics of sulfur dioxide in the liquid-screen flue gas desulfurization system using discarded carbide slag which is essential for the practical application. (author)

Application of wasted sea-shell to desulfurizer in fluidized bed coal combustion

Energy Technology Data Exchange (ETDEWEB)

Naruse, Ichiro; Saito, Katsuhiro; Murakami, Takahiro

1999-07-01

Almost all wasted seashells consist of CaCo{sub 3}, and are similar to limestone. It would be proposed that the seashell could be applied as a desulfurizer. In this study, desulfurization characteristics of the seashell are fundamentally studied by using a thermobalance and a bubbling fluidized coal combustor with comparing the results obtained by limestone as a reference. Under the constant calcination temperature, the desulfurization efficiency for the seashells attains more than about 70% after the desulfurization period of 30 h. For the limestones, on the other hand, the desulfurization efficiency becomes only 38%. Under practical conditions of fluidized bed coal combustion, the desulfurization efficiency for the seashells also indicates higher value than that for the limestones. The desulfurization efficiency depends on the pore size distribution of CaO rather than its specific surface area. The mean pore size of the calcined seashell is about 10 times as large as that of the calcined limestones. from Scanning Electro-Microscope (SEM) photos of the surface of CaCO{sub 3}, CaO and the sulfurized particles of the seashells the large pores can be observed. In measuring cross-sectional distribution of sulfur inside the particles by using an Energy Dispersed X-ray (EDX) system, the sulfur in the sulfurized particle of limestone is only trapped near the particle surface. For the seashells, whereas, the sulfur is distributed over the whole body of particle. Desulfurization efficiency for the limestone, into which some alkali metal compounds are added, increases with increasing the concentration of alkali metal compounds added. In order of increasing effect the key elemental species to enhance the desulfurization activities are Cl, Na and K. Alkali metal compounds can enhance the desulfurization activities, due to solution of CaO in molten NaCl. This is one of the reasons why the desulfurization efficiency for the seashells improves.

Enzymatic desulfurization of coal

Energy Technology Data Exchange (ETDEWEB)

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

1991-05-16

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

Desulfurization of organic sulfur from lignite by an electron transfer process

Energy Technology Data Exchange (ETDEWEB)

Demirbas, A. [Selcuk University, Konya (Turkey). Dept. for Chemical Engineering

2006-10-15

This study is an attempt to desulfurize organic sulfur from lignite samples with ferrocyanide ion as the electron transferring agent. Effect of temperature, particle size and concentration of ferrocyanide ion on desulfurization from the lignite samples has been investigated. The desulfurization process has been found to be continuous and gradually increases with increase of temperature from 298 to 368 K. The particle size has no significant impact on sulfur removal from the lignite samples. Particle size has no profound impact on the amount of sulfur removal. The desulfurization reaction has been found to be dependent on the concentration of potassium ferrocyanide. Gradual increase in the concentration of potassium ferrocyanide raised the magnitude of desulfurization, but at a higher concentration, the variation is not significant.

ABB wet flue gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Niijhawan, P.

1994-12-31

The wet limestone process for flue gas desulfurization (FGD) is outlined. The following topics are discussed: wet flue gas desulfurization, wet FGD characteristics, wet scrubbers, ABB wet FGD experience, wet FGD forced oxidation, advanced limestone FGD systems, key design elements, open spray tower design, spray tower vs. packed tower, important performance parameters, SO{sub 2} removal efficiency, influence by L/G, limestone utilization, wet FGD commercial database, particulate removal efficiencies, materials of construction, nozzle layout, spray nozzles, recycle pumps, mist elimination, horizontal flow demister, mist eliminator washing, reagent preparation system, spray tower FGDS power consumption, flue gas reheat options, byproduct conditioning system, and wet limestone system.

Effect of Silicon on Desulfurization of Aluminum-killed Steels

Science.gov (United States)

Roy, Debdutta

Recent reports have suggested that silicon has a beneficial effect on the rate of desulfurization of Al-killed steel. This effect is difficult to understand looking at the overall desulfurization reaction which does not include silicon. However an explanation is proposed by taking into account the (SiO2)/[Si] equilibrium in which some Al reaching the slag-metal interface is used in reducing the SiO2 in the slag. This reaction can be suppressed to some extent if the silicon content of the metal is increased and in doing so, more Al will be available at the slag-metal interface for the desulfurization reaction and this would increase the rate of the desulfurization reaction. A model was developed, assuming the rates are controlled by mass transfer, taking into account the coupled reactions of the reduction of silica, and other unstable oxides, namely iron oxide and manganese oxide, in the slag and desulfurization reaction in the steel by aluminum. The model predicts that increasing silicon increases the rate and extent of desulfurization. Plant data was analyzed to obtain rough estimates of ladle desulfurization rates and also used to validate the model predictions. Experiments have been conducted on a kilogram scale of material in an induction furnace to test the hypothesis. The major conclusions of the study are as follows: The rate and extent of desulfurization improve with increasing initial silicon content in the steel; the effect diminishes at silicon contents higher than approximately 0.2% and with increasing slag basicity. This was confirmed with kilogram-scale laboratory experiments. The effects of the silicon content in the steel (and of initial FeO and MnO in the slag) largely arise from the dominant effects of these reactions on the equilibrium aluminum content of the steel: as far as aluminum consumption or pick-up is concerned, the Si/SiO2 reaction dominates, and desulfurization has only a minor effect on aluminum consumption. The rate is primarily

Studies On An Aerobic Oxidation Of Dibenzothiophene And Related Compounds Using Ruthenium Catalyst

Directory of Open Access Journals (Sweden)

Morishita Y.

2015-06-01

Full Text Available An aerobic oxidation of dibenzothiophene and related compounds using a catalytic amount of ruthenium chloride in hydrocarbon solvents at 80°C for 20 h gave the corresponding sulfones in almost quantitative yields. The reaction might proceed via autoxidation of solvents to hydroperoxides and the reaction of sulfur compounds with the resulting hydroperoxides.

Oxidative desulfurization of synthetic diesel using supported catalysts. Part 3. Support effect on vanadium-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Cedeno-Caero, Luis; Gomez-Bernal, Hilda; Fraustro-Cuevas, Adriana; Guerra-Gomez, Hector D.; Cuevas-Garcia, Rogelio [UNICAT, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria 04510, Mexico D.F. (Mexico)

2008-04-15

Oxidesulfurization (ODS) of benzothiophenic compounds prevailing in diesel was conducted with hydrogen peroxide in presence of various catalysts, using a model diesel and actual diesel fuel. ODS activities of dibenzothiophenes (DBTs) in hexadecane for a series of V{sub 2}O{sub 5} catalysts supported on alumina, titania, ceria, niobia and silica, were evaluated. Results show that the oxidation activity of DBTs depends on the support used. It was observed that the sulfone yield is not proportional to textural properties or V content. For all catalysts, ODS of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) decreased in the following order: DBT > 4-MDBT > 4,6-DMDBT > BT. This trend does not depend on the catalyst used or the textural properties of the catalysts and supports. In presence of indole ODS activities diminish, except with catalysts supported on alumina-titania mixed oxide, whereas with V{sub 2}O{sub 5}/TiO{sub 2} catalyst the performance is the highest. ODS of Mexican diesel fuel was carried out in presence of this catalyst and S level was diminished in about 99%. (author)

Radiation methods for demercaptanization and desulfurization of oil products

International Nuclear Information System (INIS)

Zaykina, R.F.; Zaykin, Yu.A.; Mamonova, T.B.; Nadirov, N.K.

2002-01-01

A two-stage method for the desulfurization of oil is presented. The first stage strongly oxidizes sulfuric material to do away with its chemical aggressiveness and promote its removal. Desulfurization of the overall product is reached at the second stage by means of conventional methods

Radiation methods for demercaptanization and desulfurization of oil products

Science.gov (United States)

Zaykina, R. F.; Zaykin, Yu. A.; Mamonova, T. B.; Nadirov, N. K.

2002-03-01

A two-stage method for the desulfurization of oil is presented. The first stage strongly oxidizes sulfuric material to do away with its chemical aggressiveness and promote its removal. Desulfurization of the overall product is reached at the second stage by means of conventional methods.

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

International Nuclear Information System (INIS)

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

2011-01-01

Radiation-induced desulfurization of four types of Arabian crude oils (heavy, medium, light and extra light) and straight-run diesel (SRD) was investigated over the range of 10-200 kGy. Results show that gamma radiation processing at absorbed doses up to 200 kGy without further treatment is not sufficient for desulfurization. However, the combination of gamma-irradiation with other physical/chemical processes (i.e. L/L extraction, adsorption and oxidation) may be capable of removing considerable levels of sulfur compounds in the investigated products. Currently, this approach of combined radiation/physical/chemical processes is under investigation. The findings of these attempts will be reported in the future. - Highlights: → Irradiation effect on desulfurization in Arabian crude oils and straight-run diesel was investigated. → No noticeable changes in sulfur content after irradiation up to 200 kGy were observed. → Stricter regulations on sulfur levels in fuels motivate search for improved desulfurization processes. → Limited investigations on radiation-induced desulfurization of oil products are conducted.

Practical use of dry desulfurization equipment using coal ash and effective use of used desulfurizer. Sekitanbai riyo kanshiki datsuryu sochi no jitsuyoka to shiyozumi datsuryuzai no yukoriyo ni tsuite

Energy Technology Data Exchange (ETDEWEB)

Suzuki, T.; Ueno, T. (The Hokkaido Electric Power CO. Inc., Hokkaido (Japan))

1992-01-30

Practical use of dry desulfurization equipment using coal ash installed in Atsuma power plant no.1 is explained. Outline of dry desulferization process is consisted of basic principles and structure of the process which includes desulfurizer production equipment and absorption equipment. When compared with conventional wet process, equipments for waste water and for reheating of exhaust gas are not necessary, and operation maintenance has been more convenient with the simplification of the system and absorber has graded up the elimination function. Advantages of simplification of treatment of used desulfurizer, and absorption of sulfurdioxide by desulfurizer together with characteristics of desulfurizer production are given. As far as practical macineries are concerned, outline of instrument facilities, construction technology and results of experimental operation are reported. Effective Use of desulfurizer using deodorant and hedro treatment has been verified from ammonium absorption experiment and practical investigation results. However use of hedro material has required, conformity of surface caking technology, under water caking technology, under water covering technology and effect on under water living environment. 13 figs., 4 tabs.

Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

Science.gov (United States)

Sundararaman, Ramanathan

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

Desulfurization of chalcopyrite and molybdenite by atomic hydrogen

International Nuclear Information System (INIS)

Bagdasaryan, V.R.; Kosoyan, A.Zh.; Niazyan, O.M.

1989-01-01

Molybdenite (MoS 2 ) desulfurization by monatomic hydrogen in 625-800 K range was studied using helium as diluent gas. Desulfurization degree at 680 K equals 9%. Temperature growth elevates sulfur content in molybdenite. The effect of initial molybdenite enrichment with temperature growth up to 800 K is probably caused by removal of reduced molybdenum capable to form oxide in the presence of traces of oxygen contained in inert diluent gas

Ultrasound-assisted oxidative desulfurization of bitumen

Science.gov (United States)

Kamal, Wan Mohamad Ikhwan bin Wan; Okawa, Hirokazu; Kato, Takahiro; Sugawara, Katsuyasu

2017-07-01

Bitumen contains a high percentage of sulfur (about 4.6 wt %). A hydrodesulfurization method is used to remove sulfur from bitumen. The drawback of this method is the requirement for a high temperature of >300 °C. Most of the sulfur in bitumen exists as thiophene. Oxidative desulfurization (ODS), involving oxidizing sulfur using H2O2, then removing it using NaOH, allows the removal of sulfur in thiophene at low temperatures. We removed sulfur from bitumen using ODS treatment under ultrasound irradiation, and 52% of sulfur was successfully removed. Additionally, the physical action of ultrasound assisted the desulfurization of bitumen, even at low H2O2 concentrations.

Preparation of WO3/g-C3N4 composites and their application in oxidative desulfurization

International Nuclear Information System (INIS)

Zhao, Rongxiang; Li, Xiuping; Su, Jianxun; Gao, Xiaohan

2017-01-01

Highlights: • The WO 3 /g-C 3 N 4 was successfully synthesized through simple calcination. • The process is simple and the cost raw materials is cheap. • The WO 3 /g-C 3 N 4 firstly applied to ODS. • The desulpurization rate of WO 3 /g-C 3 N 4 may attach to 91.2%. • Five recycles of WO 3 /g-C 3 N 4 still attach to 89.5% due to heterogeneous catalysis. - Abstract: WO 3 /graphitic carbon nitride (g-C 3 N 4 ) composites were successfully synthesized through direct calcining of a mixture of WO 3 and g-C 3 N 4 at 400 °C for 2 h. The WO 3 was prepared by calcination of phosphotungstic acid at 550 °C for 4 h, and the g-C 3 N 4 was obtained by calcination of melamine at 520 °C for 4 h. The WO 3 /g-C 3 N 4 composites were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), and Brunner−Emmett−Teller analysis (BET). The WO 3 /g-C 3 N 4 composites exhibited stronger XRD peaks of WO 3 and g-C 3 N 4 than the WO 3 and pure g-C 3 N 4 . In addition, two WO 3 peaks at 25.7° and 26.6° emerged for the 36% −WO 3 /g-C 3 N 4 composite. This finding indicated that WO 3 was highly dispersed on the surface of the g-C 3 N 4 nanosheets and interacted with the nanosheets, which resulted in the appearance of (012) and (022) planes of WO 3 . The WO 3 /g-C 3 N 4 composite also exhibited a larger specific surface area and higher degree of crystallization than WO 3 or pure g-C 3 N 4 , which resulted in high catalytic activity of the catalyst. Desulfurization experiments demonstrated that the desulfurization rate of dibenzothiophene (DBT) in model oil reached 91.2% under optimal conditions. Moreover, the activity of the catalyst was not significantly decreased after five recycles.

Biodesulfurization techniques: Application of selected microorganisms for organic sulfur removal from coals. Final report

Energy Technology Data Exchange (ETDEWEB)

Elmore, B.B.

1993-08-01

As an alternative to post-combustion desulfurization of coal and pre-combustion desulfurization using physicochemical techniques, the microbial desulfurization of coal may be accomplished through the use of microbial cultures that, in an application of various microbial species, may remove both the pyritic and organic fractions of sulfur found in coal. Organisms have been isolated that readily depyritize coal but often at prohibitively low rates of desulfurization. Microbes have also been isolated that may potentially remove the organic-sulfur fraction present in coal (showing promise when acting on organic sulfur model compounds such as dibenzothiophene). The isolation and study of microorganisms demonstrating a potential for removing organic sulfur from coal has been undertaken in this project. Additionally, the organisms and mechanisms by which coal is microbially depyritized has been investigated. Three cultures were isolated that grew on dibenzothiophene (DBT), a model organic-sulfur compound, as the sole sulfur source. These cultures (UMX3, UMX9, and IGTS8) also grew on coal samples as the sole sulfur source. Numerous techniques for pretreating and ``cotreating`` coal for depyritization were also evaluated for the ability to improve the rate or extent of microbial depyritization. These include prewashing the coal with various solvents and adding surfactants to the culture broth. Using a bituminous coal containing 0.61% (w/w) pyrite washed with organic solvents at low slurry concentrations (2% w/v), the extent of depyritization was increased approximately 25% in two weeks as compared to controls. At slurry concentrations of 20% w/v, a tetrachloroethylene treatment of the coal followed by depyritization with Thiobacillus ferrooxidans increased both the rate and extent of depyritization by approximately 10%.

A novel semidry flue gas desulfurization process with the magnetically fluidized bed reactor

International Nuclear Information System (INIS)

Zhang Qi; Gui Keting

2009-01-01

The magnetically fluidized bed (MFB) was used as the reactor in a novel semidry flue gas desulfurization (FGD) process to achieve high desulfurization efficiency. Experiments in a laboratory-scale apparatus were conducted to reveal the effects of approach to adiabatic saturation temperature, Ca/S molar ratio and applied magnetic field intensity on SO 2 removal. Results showed that SO 2 removal efficiency can be obviously enhanced by decreasing approach to adiabatic saturation temperature, increasing Ca/S molar ratio, or increasing applied magnetic field intensity. At a magnetic field intensity of 300 Oe and a Ca/S molar ratio of 1.0, the desulfurization efficiency (excluding desulfurization efficiency in the fabric filter) was over 80%, while spent sorbent appeared in the form of dry powder. With the SEM, XRD and EDX research, it can be found that the increase of DC magnetic field intensity can make the surface morphology on the surface of the ferromagnetic particles loose and enhance the oxidation of S(IV), hence reducing the liquid phase mass transfer resistance of the slurry droplets and increasing desulfurization reaction rate, respectively. Therefore, the desulfurization efficiency increased obviously with the increase of DC field intensity.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

Results of the desulfurization programme at coal-fired power plants operated by CEZ a.s

International Nuclear Information System (INIS)

Anon.

1996-01-01

The Czech utility CEZ, which is the major power plant operator in the Czech Republic, is running an extensive coal-fired power plant desulfurization programme to improve the environmental situation in the region. Flue gas desulfurization is achieved in 2 ways: by augmenting the existing units with desulfurization equipment, and by replacing old boilers with new, fluidized-bed combustion facilities. Both wet limestone scrubbing and the dry limestone method are applied. A survey of the power plants, desulfurized power, desulfurization equipment suppliers, and contract prices is presented in a tabular form. Plots showing the contribution of CEZ's power plants to sulfur dioxide emissions in the Czech Republic are reproduced. (P.A.). 1 tab., 3 figs

Desulfurization kinetics of molten copper by gas bubbling

Science.gov (United States)

Fukunaka, Y.; Nishikawa, K.; Sohn, H. S.; Asaki, Z.

1991-02-01

Molten copper with 0.74 wt pct sulfur content was desulfurized at 1523 K by bubbling Ar-O2 gas through a submerged nozzle. The reaction rate was significantly influenced not only by the oxygen partial pressure but also by the gas flow rate. Little evolution of SO2 gas was observed in the initial 10 seconds of the oxidation; however, this was followed by a period of high evolution rate of SO2 gas. The partial pressure of SO2 gas decreased with further progress of the desulfurization. The effect of the immersion depth of the submerged nozzle was negligible. The overall reaction is decomposed to two elementary reactions: the desulfurization and the dissolution rate of oxygen. The assumptions were made that these reactions are at equilibrium and that the reaction rates are controlled by mass transfer rates within and around the gas bubble. The time variations of sulfur and oxygen contents in the melt and the SO2 partial pressure in the off-gas under various bubbling conditions were well explained by the mathematical model combined with the reported thermodynamic data of these reactions. Based on the present model, it was anticipated that the oxidation rate around a single gas bubble was mainly determined by the rate of gas-phase mass transfer, but all oxygen gas blown into the melt was virtually consumed to the desulfurization and dissolution reactions before it escaped from the melt surface.

Desulfurization of AL-Ahdab Crude Oil using Oxidative Processes

OpenAIRE

Neran Khalel Ibrahim; Saja Mohsen Jabbar

2015-01-01

Two different oxidative desulfurization strategies based on oxidation/adsorption or oxidation/extraction were evaluated for the desulfurization of AL-Ahdab (AHD) sour crude oil (3.9wt% sulfur content). In the oxidation process, a homogenous oxidizing agent comprising of hydrogen peroxide and formic acid was used. Activated carbons were used as sorbent/catalyst in the oxidation/adsorption process while acetonitrile was used as an extraction solvent in the oxidation/extraction process. For the ...

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

Science.gov (United States)

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.

Oxidative Desulfurization of Gasoline by Ionic Liquids Coupled with Extraction by Organic Solvents

OpenAIRE

Abro, Rashid; Gao, Shurong; Chen, Xiaochun; Yu, Guangren; Abdeltawab, Ahmed A.; Al-Deyab, Salem S.

2016-01-01

In this work, desulfurization of real fluidized catalytic cracking (FCC) gasoline was investigated in dual steps; first in oxidative desulfurization (ODS) using imidazolium and pyrrolidonium based Brønsted acidic ionic liquids (ILs) as solvent and catalyst and hydrogen peroxide as oxidant. In second step, extractive desulfurization took place using organic solvents of furfural, furfural alcohol and ethylene glycol. Variety of factors such as temperature, time, mass ratio of oil/ILs and regene...

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

Energy Technology Data Exchange (ETDEWEB)

Wei Zaishan [School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275 (China)], E-mail: weizaishan98@163.com; Lin Zhehang; Niu Hejingying; He Haiming; Ji Yongfeng [School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275 (China)

2009-03-15

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

Multi-objective optimization of oxidative desulfurization in a sono-photochemical airlift reactor.

Science.gov (United States)

Behin, Jamshid; Farhadian, Negin

2017-09-01

Response surface methodology (RSM) was employed to optimize ultrasound/ultraviolet-assisted oxidative desulfurization in an airlift reactor. Ultrasonic waves were incorporated in a novel-geometry reactor to investigate the synergistic effects of sono-chemistry and enhanced gas-liquid mass transfer. Non-hydrotreated kerosene containing sulfur and aromatic compounds was chosen as a case study. Experimental runs were conducted based on a face-centered central composite design and analyzed using RSM. The effects of two categorical factors, i.e., ultrasound and ultraviolet irradiation and two numerical factors, i.e., superficial gas velocity and oxidation time were investigated on two responses, i.e., desulfurization and de-aromatization yields. Two-factor interaction (2FI) polynomial model was developed for the responses and the desirability function associate with overlay graphs was applied to find optimum conditions. The results showed enhancement in desulfurization ability corresponds to more reduction in aromatic content of kerosene in each combination. Based on desirability approach and certain criteria considered for desulfurization/de-aromatization, the optimal desulfurization and de-aromatization yields of 91.7% and 48% were obtained in US/UV/O 3 /H 2 O 2 combination, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Inhibition of carbon disulfide on bio-desulfurization in the process of ...

African Journals Online (AJOL)

Biological desulfurization is a novel technology for the removal of hydrogen sulfide from some biogas or sour gas, in which there are always a certain amounts of carbon disulfide together with much hydrogen sulfide. Nowadays, carbon disulfide is found to have negative effect on the biological desulfurization, but seldom ...

Experimental study of desulfurization of Zhong Liang Shau high sulfur coal by flotation

Energy Technology Data Exchange (ETDEWEB)

Jiang, Z.; Huang, B.; Cao, J. [China University of Mining and Technology (China). Beijing Graduate School

1994-12-01

Emission of large amount of SO{sub 2} from combustion of high sulfur coal causes serious environmental pollution. Pre-combustion desulfurization of high sulfur coal has become a necessity. This paper reports test results of fine coal desulfurization with different flotation technology and the effect of pyrite depressant. Test work showed that when the coal sample from Zhong Liang Shau was processed with a Free Jet Flotation Column its pyritic sulfur content was reduced from 3.08% to 0.84%, with 72.22% recovery of combustible matter in clean coal. The concept of Desulfurization Efficiency Index E{sub ds} for comprehensive evaluation of desulfurization process is proposed, which is defined as the product of the ratio of sulfur content reduction of clean coal and the recovery of combustible matters. 6 refs., 4 figs., 3 tabs.

Process for desulfurizing shale oil, etc

Energy Technology Data Exchange (ETDEWEB)

Escherich, F

1922-12-17

A process is described for the desulfurizing of shale oil or tar, with recovery of valuable oils and hydrocarbons, characterized in that the raw material is heated in an autoclave to a pressure of 100 atmospheres or more.

Desulfurization technology in the blast furnace raceway by MgO-SiO{sub 2} flux injection

Energy Technology Data Exchange (ETDEWEB)

Orimoto, T.; Noda, T.; Ichida, M.; Nagasaka, T. [Hokkai Iron & Coke Corporation, Hokkaido (Japan)

2008-07-01

This paper presents a study on desulfurization technology in the steel industry, with attention focused on the removal of sulfur that forms acid rain, which has been creating various global problems. The study was confined to the technology that injects a mixture of serpentine and pulverized coals. Thermodynamically, a magnesium gas producing reaction occurs when magnesium oxide is turned into a hot strongly reducing atmosphere and the resulting magnesium gas forms magnesium sulfide by reaction with the sulfur in the molten iron. By dividing this desulfurization process into a magnesium gas producing reaction and a desulfurization reaction by the magnesium gas, the desulfurization effect of the magnesium oxide flux was confirmed through laboratory experiment. A thermodynamic study on the desulfurization reaction in which SiO gas resulting from the reduction of SiO{sub 2} produces a silicon sulfide gas by reaction with the sulfur in the molten iron revealed that the possibility of desulfurization of the molten iron by the silicon sulfide gas is not negligible.

Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

Science.gov (United States)

Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

2015-03-01

Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

Desulfurization technologies for flue gases from power stations, technological and financial characteristics

International Nuclear Information System (INIS)

Naumoski, Koce

1997-01-01

Harms on life environment, caused by aero pollution, for the last decades enforced fast development of technologies for filtration of gases that come from thermal power plants and other objects. SO 2 , that appear as one of outputs of fossil fuels combustion, and also processing of sulphide ore, is a main component of acid rains. Acid rains represent one of the most risky factors, responsible for dryne of woods and changing of flora and fauna on land and in water. Starting from 1931 year when on the thermal power plant BATTERSEA STATION, property of London Power, first scrubbers were monnted for filtration of flue gases of SO 2 , and up till today, many procedures are developed for desulfurization of flue gases. For easier coping with numerous technologies for desulfurization , various classifications were made. By state of aggregation of the absorption agent , the technologies for desulfurization of gases are divided in wet , semidry and dry procedures. Wet procedures are technologies with highness rate of desulfurization of 90-95 % and most flexible of the quality of fuel whose flue gases are filtered. Presently they have high price of 90-220 $/kw installed power. According to American sources, their price at the world market is forecasted that till 2000 year will reach price of 100 $/kw. Dry technologies for desulfurization of flue gases are last technologies. The rate of desulfurization is 50-60 % and its prise is 76 -113 $/kw. Their negative side is high variable costs 250 - 388 $/ ton SO 2 (at wet procedures variable costs 76 - 157 $/ton SO 2 ). Semidry technologies by financial and technological characteristics are wet and dry procedures. (Author)

SULFUR REDUCTION IN GASOLINE AND DIESEL FUELS BY EXTRACTION/ADSORPTION OF REFRACTORY DIBENZOTHIOPHENES

Energy Technology Data Exchange (ETDEWEB)

Robert J. Angelici

2003-06-01

Refractory 4,6-dimethyldibenzothiophene, which is difficult to remove from petroleum feedstocks, binds to the Ru in Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} by displacing the H{sub 2}O ligand. Thiophene, benzothiophene and dibenzothiophene (DBT) also react with Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} similarly. This binding ability of Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} has been used to remove over 50% of the DBT in simulated petroleum feedstocks by a biphasic extraction process. The extraction phase is readily regenerated by air-oxidation thereby completing a cyclic process that removes DBT from petroleum feedstocks. Solid phase extractants consisting of Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+}, CpRu(CO){sub 2}(BF{sub 4}), CpFe(CO){sub 2}(C{sub 4}H{sub 8}){sup +} and AgX (where X = BF{sub 4}{sup -}, PF{sub 6}{sup -} or NO{sub 3}{sup -}) adsorbed on silica have also been used to remove DBT and 4,6-Me{sub 2}DBT from simulated petroleum feedstocks. The AgX/silica adsorbents remove 90% of the DBT and 4,6-Me{sub 2}DBT and can be regenerated and re-used for multiple extractions, which makes these adsorbents of potential industrial use for the removal of refractory dibenzothiophenes from petroleum feedstocks.

Desulfurization and denitrogenation in copyrolysis of coal with hydrogen-rich gases

Energy Technology Data Exchange (ETDEWEB)

Liao, H.; Li, B.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). Institute of Coal Chemistry

1999-06-01

Desulfurization and denitrogenation were systematically investigated by analyzing the chars and tars from copyrolysis of Yanzhou high sulfur bituminous coal with coke-oven gas (COG), synthesis gas (SG) and hydrogen. The results indicated that under the conditions of 3MPa, up to 650{degree}C with a heating rate of 10{degree}C/min, the desulfurization of coal pyrolysis with COG, SG and hydrogen were almost equal (about 80%, w%, ad), the order of denitrogenation were: hydrogen (41%) {gt} SG(35%) {gt} COG(30%). The distributions of sulfur in char, oil and gas was very similar under the three reactive gases, i.e., about 205 in char, 105 in tar and 70% (diff.) in gas, respectively. Compared with hydropyrolysis at the same hydrogen partial pressure, the desulfurization of coal pyrolysis with coke oven gas was increased by about 4.5%, while the denitrogenation was decreased by about 3.5%. There is an important desulfurization advantage for hydropyrolysis using COG and SG instead of pure hydrogen. Compared with the copyrolysis of coal with COG, Yanzhou coal pyrolysis under SG can achieve the same level of desufurization but higher denitrogenation. 11 refs., 3 figs., 4 tabs.

Mercury isotope fractionation during transfer from post-desulfurized seawater to air.

Science.gov (United States)

Huang, Shuyuan; Lin, Kunning; Yuan, Dongxing; Gao, Yaqin; Sun, Lumin

2016-12-15

Samples of dissolved gaseous mercury (DGM) in the post-desulfurized seawater discharged from a coal-fired power plant together with samples of gaseous elemental mercury (GEM) over the post-desulfurized seawater surface were collected and analyzed to study the mercury isotope fractionation during transfer from post-desulfurized seawater to air. Experimental results showed that when DGM in the seawater was converted to GEM in the air, the δ 202 Hg and Δ 199 Hg values were changed, ranging from -2.98 to -0.04‰ and from -0.31 to 0.64‰, respectively. Aeration played a key role in accelerating the transformation of DGM to GEM, and resulted in light mercury isotopes being more likely to be enriched in the GEM. The ratio Δ 199 Hg/Δ 201 Hg was 1.626 in all samples, suggesting that mercury mass independent fractionation occurred owing to the nuclear volume effect during the transformation. In addition, mass independent fractionation of mercury even isotopes was found in the GEM above the post-desulfurized seawater surface in the aeration pool. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultrasound-Assisted Oxidative Desulfurization of Diesel

Directory of Open Access Journals (Sweden)

Niran K. Ibrahim

2016-11-01

Full Text Available Due to the dramatic environmental impact of sulfur emissions associated with the exhaust of diesel engines, last environmental regulations for ultra-low-sulfur diesel require a very deep desulfurization (up to 15 ppm, which cannot be met by the conventional hydrodesulfurization units alone. The proposed method involves a batch ultrasound-assisted oxidative desulfurization (UAODS of a previously hydrotreated diesel (containing 480 ppm sulfur so as to convert the residual sulfur-bearing compounds into their corresponding highly polar oxides, which can be eliminated easily by extraction with a certain highly polar solvent. The oxidizing system utilized was H2O2 as an oxidant, CH3COOH as a promoter, with FeSO4 as a catalyst; whereas acetonitrile was used as extractant. The major influential parameters related to UAODS process have been investigated, namely: ratio of oxidant/fuel, ratio of the promoter/oxidant, dose of catalyst, reaction temperature, and intensity of ultrasonic waves. Kinetics of the reaction has been also studied; it was observed that the UAODS of diesel fuels fitted pseudo-first-order kinetics under the best experimental conditions, whereas values of the apparent rate constant and activation energy were 0.373 min-1 and 24 KJ/mol, respectively. The oxidation treatment, in combination with ultrasonic irradiation, revealed a synergistic effect for diesel desulfurization. The experimental results showed that sulfur removal efficiency could amount to 98% at mild operating conditions (70 ○C and 1 bar. This indicates that the process is efficient and promising for the production of ultra-low-sulfur diesel fuels.

Numerical Investigation of Desulfurization Kinetics in Gas-Stirred Ladles by a Quick Modeling Analysis Approach

Science.gov (United States)

Cao, Qing; Nastac, Laurentiu; Pitts-Baggett, April; Yu, Qiulin

2018-03-01

A quick modeling analysis approach for predicting the slag-steel reaction and desulfurization kinetics in argon gas-stirred ladles has been developed in this study. The model consists of two uncoupled components: (i) a computational fluid dynamics (CFD) model for predicting the fluid flow and the characteristics of slag-steel interface, and (ii) a multicomponent reaction kinetics model for calculating the desulfurization evolution. The steel-slag interfacial area and mass transfer coefficients predicted by the CFD simulation are used as the processing data for the reaction model. Since the desulfurization predictions are uncoupled from the CFD simulation, the computational time of this uncoupled predictive approach is decreased by at least 100 times for each case study when compared with the CFD-reaction kinetics fully coupled model. The uncoupled modeling approach was validated by comparing the evolution of steel and slag compositions with the experimentally measured data during ladle metallurgical furnace (LMF) processing at Nucor Steel Tuscaloosa, Inc. Then, the validated approach was applied to investigate the effects of the initial steel and slag compositions, as well as different types of additions during the refining process on the desulfurization efficiency. The results revealed that the sulfur distribution ratio and the desulfurization reaction can be promoted by making Al and CaO additions during the refining process. It was also shown that by increasing the initial Al content in liquid steel, both Al oxidation and desulfurization rates rapidly increase. In addition, it was found that the variation of the initial Si content in steel has no significant influence on the desulfurization rate. Lastly, if the initial CaO content in slag is increased or the initial Al2O3 content is decreased in the fluid-slag compositional range, the desulfurization rate can be improved significantly during the LMF process.

Numerical Investigation of Desulfurization Kinetics in Gas-Stirred Ladles by a Quick Modeling Analysis Approach

Science.gov (United States)

Cao, Qing; Nastac, Laurentiu; Pitts-Baggett, April; Yu, Qiulin

2018-06-01

A quick modeling analysis approach for predicting the slag-steel reaction and desulfurization kinetics in argon gas-stirred ladles has been developed in this study. The model consists of two uncoupled components: (i) a computational fluid dynamics (CFD) model for predicting the fluid flow and the characteristics of slag-steel interface, and (ii) a multicomponent reaction kinetics model for calculating the desulfurization evolution. The steel-slag interfacial area and mass transfer coefficients predicted by the CFD simulation are used as the processing data for the reaction model. Since the desulfurization predictions are uncoupled from the CFD simulation, the computational time of this uncoupled predictive approach is decreased by at least 100 times for each case study when compared with the CFD-reaction kinetics fully coupled model. The uncoupled modeling approach was validated by comparing the evolution of steel and slag compositions with the experimentally measured data during ladle metallurgical furnace (LMF) processing at Nucor Steel Tuscaloosa, Inc. Then, the validated approach was applied to investigate the effects of the initial steel and slag compositions, as well as different types of additions during the refining process on the desulfurization efficiency. The results revealed that the sulfur distribution ratio and the desulfurization reaction can be promoted by making Al and CaO additions during the refining process. It was also shown that by increasing the initial Al content in liquid steel, both Al oxidation and desulfurization rates rapidly increase. In addition, it was found that the variation of the initial Si content in steel has no significant influence on the desulfurization rate. Lastly, if the initial CaO content in slag is increased or the initial Al2O3 content is decreased in the fluid-slag compositional range, the desulfurization rate can be improved significantly during the LMF process.

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

Science.gov (United States)

Sun, Tonghua; Shen, Yafei; Jia, Jinping

2014-02-18

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

Peroxide-mediated desulfurization of phosphorothioate oligonucleotides and its prevention.

Science.gov (United States)

Krotz, Achim H; Mehta, Rahul C; Hardee, Gregory E

2005-02-01

Desulfurization at the internucleotide phosphorothioate linkage of antisense oligonucleotides (ASOs) in dermatological formulations has been investigated using strong ion exchange chromatography and mass spectroscopy. The formation of phosphate diester linkages appeared to arise from a reaction between the phosphorothioate oligonucleotide and a potent oxidizing agent. Screening of excipients used in the formulation indicated that the cause of desulfurization was related to the presence of polyethylene glycol-derived nonionic surfactants MYRJ 52 or BRIJ 58. Autoxidation of the polyethylene glycol chain is suggested as the probable origin for the observed incompatibility. The ability of various antioxidants to prevent oxidative degradation of ASO-1 in simple test systems and in oil-in-water emulsions is described. It is found that in test systems both lipophilic and hydrophilic antioxidants are effective. However, in cream formulation (oil-in-water emulsions) of ASO-1 the addition of hydrophilic antioxidants L-cysteine or DL-alpha-lipoic acid has been shown to be superior in protecting the oligonucleotide from desulfurization upon storage. Copyright 2004 Wiley-Liss, Inc.

The effect of annealing and desulfurization on oxide spallation of turbine airfoil material

International Nuclear Information System (INIS)

Briant, C.L.; Murphy, W.H.; Schaeffer, J.C.

1995-01-01

In this paper the authors report a study that addresses the sulfur-induced spallation theory. Previous work has shown that a high temperature anneal in hydrogen desulfurizes nickel-base alloys and greatly improves their resistance to oxide spallation. The authors will show that such an anneal can be applied successfully to a Ni-base airfoil material. Both Auger segregation experiments and chemical analyses show that this anneal desulfurizes the material, at least in the absence of yttrium. However, the results suggest that factors other than desulfurization may be contributing to the improvement in spallation resistance produced by the anneal

Oxidation of dibenzothiophene as a model substrate for the removal of organic sulphur from fossil fuels by iron(III ions generated from pyrite by Acidithiobacillus ferrooxidans

Directory of Open Access Journals (Sweden)

VLADIMIR P. BESKOSKI

2007-06-01

Full Text Available Within this paper a new idea for the removal of organically bonded sulphur from fossil fuels is discussed. Dibenzothiophene (DBT was used as a model compound of organicmolecules containing sulphur. This form of (biodesulphurization was performed by an indirect mechanism in which iron(III ions generated from pyrite by Acidithiobacillus ferrooxidans performed the abiotic oxidation. The obtained reaction products, dibenzothiopene sulfoxide and dibenzothiophene sulfone, are more soluble in water than the basic substrate and the obtained results confirmed the basic hypothesis and give the posibility of continuing the experiments related to application of this (biodesulphurization process.

湿法脱硫运行情况总结%Operation Summary of Wet Desulfurization Unit

Institute of Scientific and Technical Information of China (English)

杨文斌

2013-01-01

因栲胶法脱硫效果差，采用添加NDC脱硫剂进行改进，改进后，脱硫效果好，但存在变脱效果差，副盐高等问题。针对这些问题，提出改进方法。%The tanin extract desulfurization unit runs poorly in our company , after dosing NDC desulfurization agent , the desulfurization effects are good . But the problems of the shift gas poor desulfurization and the high secondary salt content have not been solved , some improving methods are put forward .

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

Science.gov (United States)

Chan, Ngo Yeung

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

Subsequent flue gas desulfurization of coal-fired power plant units

International Nuclear Information System (INIS)

Willibal, U.; Braun, Gy.

1998-01-01

The presently operating coal-fired power plant in Hungary do not satisfy the pollution criteria prescribed by the European Union norms. The main polluting agent is the sulfur dioxide emitted by some of the power plants in Hungary in quantities over the limit standards. The power plant units that are in good operating state could be made competitive by using subsequent desulfurization measures. Various flue gas desulfurization technologies are presented through examples that can be applied to existing coal-fired power plants. (R.P.)

Use of Green Mussel Shell as a Desulfurizer in the Blending of Low Rank Coal-Biomass Briquette Combustion

Directory of Open Access Journals (Sweden)

Mahidin Mahidin

2016-08-01

Full Text Available Calcium oxide-based material is available abundantly and naturally. A potential resource of that material comes from marine mollusk shell such as clams, scallops, mussels, oysters, winkles and nerites. The CaO-based material has exhibited a good performance as the desulfurizer oradsorbent in coal combustion in order to reduce SO2 emission. In this study, pulverized green mussel shell, without calcination, was utilized as the desulfurizer in the briquette produced from a mixture of low rank coal and palm kernel shell (PKS, also known as bio-briquette. The ratio ofcoal to PKS in the briquette was 90:10 (wt/wt. The influence of green mussel shell contents and combustion temperature were examined to prove the possible use of that materialas a desulfurizer. The ratio of Ca to S (Ca = calcium content in desulfurizer; S = sulfur content in briquette werefixed at 1:1, 1.25:1, 1.5:1, 1.75:1, and 2:1 (mole/mole. The burning (or desulfurization temperature range was 300-500 °C; the reaction time was 720 seconds and the air flow rate was 1.2 L/min. The results showed that green mussel shell can be introduced as a desulfurizer in coal briquette or bio-briquette combustions. The desulfurization process using that desulfurizer exhibited the first order reaction and the highest average efficiency of 84.5%.

Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

Energy Technology Data Exchange (ETDEWEB)

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

1989-05-02

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

Thermodynamic assessment of IGCC power plants with hot fuel gas desulfurization

International Nuclear Information System (INIS)

Giuffrida, Antonio; Romano, Matteo C.; Lozza, Giovanni G.

2010-01-01

In IGCC power plants, hot gas desulfurization (HGD) represents an attractive solution to simplify syngas treatments and to improve the efficiency, potentially reducing the final cost of electricity. In the present study, the various consequences of the introduction of a HGD station in the power plant are discussed and evaluated, in comparison with conventional near-ambient temperature clean-up. Attention is paid to the potential improvements of the overall energy balance of the complete power station, along with the requirements of the sorbent regeneration process, to the influence of the desulfurization temperature and to the different solutions needed to control the NO x emissions (altered by the presence of HGD). The net performance of complete IGCC power plants (with HGD or with conventional desulfurization) were predicted, with reference to status-of-the-art solutions based on an entrained flow, dry-feed, oxygen-blown gasifier and on an advanced, FB-class combined cycle. The net efficiency experiences about 2.5% point improvement with HGD, even if a small reduction in the power output was predicted, when using the same combustion turbine. An exhaustive sensitivity analysis was carried out to evaluate the effects of different working conditions at the HGD station, e.g. desulfurization temperature and oxygen content in the gaseous stream for sorbent regeneration. According to the obtained results, these parameters have a weak influence on the efficiency. In particular, a very elevated desulfurization temperature (above 400-500 o C) does not provide decisive thermodynamic advantages. Therefore, the HGD unit optimization can be driven by technical and economical aspects and by emission abatement requirements. For instance, utilization of nitrogen for HGD sorbent regeneration (rather than for syngas dilution) and higher fuel temperature may improve the NO formation. Hence, different strategies to achieve acceptable NO x emissions (e.g. steam dilution) and their

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

Science.gov (United States)

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

2013-09-01

This work investigated the ultrasonic assisted oxidative desulfurization of bunker-C oil with TBHP/MoO3 system. The operational parameters for the desulfurization procedure such as ultrasonic irradiation time, ultrasonic wave amplitude, catalyst initial concentration and oxidation agent initial concentration were studied. The experimental results show that the present oxidation system was very efficient for the desulfurization of bunker-C oil and ~35% sulfur was removed which was dependent on operational parameters. The application of ultrasonic irradiation allowed sulfur removal in a shorter time. The stronger the solvent polarity is, the higher the sulfur removal rate, but the recovery rate of oil is lower. The sulfur compounds in bunker-C oil reacted with TBHP to produce corresponding sulfoxide, and further oxidation produced the corresponding sulfone. Copyright © 2013 Elsevier B.V. All rights reserved.

Experimental Study on Hot Metal Desulfurization Using Sintered Red Mud-Based Flux

Science.gov (United States)

Li, Fengshan; Zhang, Yanling; Guo, Zhancheng

2017-09-01

This research presents the results of laboratory and pilot-scale tests conducted on the use of sintered red mud (RM)-based flux in the hot metal desulfurization (HMD) process. Al2O3/Na2O in RM can decrease the melting point of lime-based slag and can work as a flux in the HMD process. Good slag fluidity was observed throughout the process, and high desulfurization rates ( 80%) with a low final S content (pilot-scale test results indicated that a desulfurization rate as high as 91% and a S content <0.0099% could be acquired when RM:lime = 1:1, verifying the feasibility of using sintered RM-based flux in HMD. The data obtained provide important information for promoting the large-scale application of sintered RM in steelmaking.

Progress on flue gas desulfurization and denitration with electron beam irradiation in CAEP

International Nuclear Information System (INIS)

Ren Min; Wang Baojian; Yang Ruizhuang; Huang Wenfeng; He Xiaohai; Mao Benjiang

2005-01-01

The first pilot plant with electron beam irradiation for desulfurization and denitration of flue gas in China and the experimental results based on the pilot plant are briefly introduced in this paper. The FGD (flue gas desulfurization) demonstration installation designed by CAEP (China Academy of Engineering Physics) in Beijing Jingfeng Thermal Powe Co., Ltd. is recommended. (author)

Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

International Nuclear Information System (INIS)

Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

2014-01-01

Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

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

Science.gov (United States)

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

Preparation of WO{sub 3}/g-C{sub 3}N{sub 4} composites and their application in oxidative desulfurization

Energy Technology Data Exchange (ETDEWEB)

Zhao, Rongxiang, E-mail: zylhzrx@126.com; Li, Xiuping, E-mail: lilili_171717@126.com; Su, Jianxun; Gao, Xiaohan

2017-01-15

Highlights: • The WO{sub 3}/g-C{sub 3}N{sub 4} was successfully synthesized through simple calcination. • The process is simple and the cost raw materials is cheap. • The WO{sub 3}/g-C{sub 3}N{sub 4} firstly applied to ODS. • The desulpurization rate of WO{sub 3}/g-C{sub 3}N{sub 4} may attach to 91.2%. • Five recycles of WO{sub 3}/g-C{sub 3}N{sub 4} still attach to 89.5% due to heterogeneous catalysis. - Abstract: WO{sub 3}/graphitic carbon nitride (g-C{sub 3}N{sub 4}) composites were successfully synthesized through direct calcining of a mixture of WO{sub 3} and g-C{sub 3}N{sub 4} at 400 °C for 2 h. The WO{sub 3} was prepared by calcination of phosphotungstic acid at 550 °C for 4 h, and the g-C{sub 3}N{sub 4} was obtained by calcination of melamine at 520 °C for 4 h. The WO{sub 3}/g-C{sub 3}N{sub 4} composites were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), and Brunner−Emmett−Teller analysis (BET). The WO{sub 3}/g-C{sub 3}N{sub 4} composites exhibited stronger XRD peaks of WO{sub 3} and g-C{sub 3}N{sub 4} than the WO{sub 3} and pure g-C{sub 3}N{sub 4}. In addition, two WO{sub 3} peaks at 25.7° and 26.6° emerged for the 36% −WO{sub 3}/g-C{sub 3}N{sub 4} composite. This finding indicated that WO{sub 3} was highly dispersed on the surface of the g-C{sub 3}N{sub 4} nanosheets and interacted with the nanosheets, which resulted in the appearance of (012) and (022) planes of WO{sub 3}. The WO{sub 3}/g-C{sub 3}N{sub 4} composite also exhibited a larger specific surface area and higher degree of crystallization than WO{sub 3} or pure g-C{sub 3}N{sub 4}, which resulted in high catalytic activity of the catalyst. Desulfurization experiments demonstrated that the desulfurization rate of dibenzothiophene (DBT) in model oil reached 91.2% under optimal conditions. Moreover, the activity of the catalyst was not significantly decreased after five recycles.

The desulfurization mechanism of iron-manganese compound oxide desulfurizer for removal of COS from coal gas

Energy Technology Data Exchange (ETDEWEB)

Wang Fang-fang; Zhao Hai; Zhang De-xiang; Gao Jin-sheng [East China University of Science and Technology. Shanghai (China). School of Resource and Environmental Engineering

2008-02-15

The sorbent, atmospheric and components of outlet gas were analyzed by mass spectra, XRD, SEM, EDS etc. Desulfurisation performance of sorbents is good at 240 - 400 {sup o}C, atmospheric pressure and space speed of 500 - 2,000 h {sup -1}. The possible mechanism of desulfurisation reactions was obtained by analyzing the reduction- adsorption-sulfidation process. Carbon oxysulfide (COS) was converted to H{sub 2}S by hydrogen in strongly reducing atmosphere firstly. Then H{sub 2}S was adsorbed on the surface of desulfurizers, reacted with active component and transformed metal sulfides and water. Efficiency of removal of carbonyl sulfur is better in an atmosphere without carbonaceous oxide than in one with it, under test conditions. The existence of carbonaceous oxide restrains hydrogenation and the hydrolytic process of COS, which leads to a higher concentration of COS in the outlet. It is shown that chemical conversion is the main pathway in the reaction system of COS. Hydrogenation is the main process in the removal of COS from syngas. COS is preferentially catalyzed with active components n desulfurization sorbents, and generates H{sub 2}S which is subsequently absorbed. 13 refs., 4 figs., 2 tabs.

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

Science.gov (United States)

Grindley, Thomas

1989-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

2006-02-01

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

Simple biogas desulfurization by microaeration - Full scale experience.

Science.gov (United States)

Jeníček, P; Horejš, J; Pokorná-Krayzelová, L; Bindzar, J; Bartáček, J

2017-08-01

Hydrogen sulfide in biogas is common problem during anaerobic treatment of wastewater with high sulfate concentration (breweries, distilleries, etc.) and needs to be removed before biogas utilization. Physico-chemical desulfurization methods are energetically demanding and expensive compare to biochemical methods. Microaeration, i.e. dosing of small amount of air, is suitable and cost effective biochemical method of sulfide oxidation to elemental sulfur. It has been widely used in biogas plants, but its application in anaerobic reactors for wastewater treatment has been rarely studied or tested. The lack of full-scale experience with microaeration in wastewater treatment plants has been overcome by evaluating the results of seven microaerobic digesters in central Europe. The desulfurization efficiency has been more than 90% in most of the cases. Moreover, microaeration improved the degradability of COD and volatile suspended solids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Design considerations for wet flue gas desulfurization systems - wet scrubber hardware issues

Energy Technology Data Exchange (ETDEWEB)

Hurwitz, H.

1994-12-31

About 20 years ago the first wet flue gas desulfurization systems installed on coal fired utility boilers in the United States were experiencing extreme operating problems. In addition to their failure to achieve the necessary SO{sub 2} removal efficiencies, these FGD systems required a major investment in maintenance, both material and labor, just to remain operational. These first generation systems demonstrated that a lack of understanding of the chemistry and operating conditions of wet flue gas desulfurization can lead to diastrous results. As the air pollution control industry developed, both in the United States and in Japan, a second generation of FGD systems was introduced. These designs incorporated major improvements in both system chemistry control and in the equipment utilized in the process. Indeed, the successful introduction of utility gas desulfurization systems in Germany was possible only through the transfer of the technology improvements developed in the US and in Japan. Today, technology has evolved to a third generation of wet flue gas desulfurication systems and these systems are now offered worldwide through a series of international licensing agreements. The rapid economic growth and development in Asia and the Pacific Rim combined with existing problems in ambient air quality in these same geographic areas, has resulted in the use of advanced air pollution control systems; including flue gas desulfurization both for new utility units and for many retrofit projects. To meet the requirements of the utility industry, FGD systems must meet high standards of reliability, operability and performance. Key components in achieving these objectives are: FGD System reliability/operability/performance; FGD system supplier qualifications; process design; equipment selection. This paper will discuss each of the essential factors with a concentration on the equipment selection and wet scrubber hardware issues.

Comments on "Ceria-Zirconia High-Temperature Desulfurization Sorbents".

Czech Academy of Sciences Publication Activity Database

Hartman, Miloslav; Trnka, Otakar

2006-01-01

Roč. 45, č. 4 (2006), s. 1548-1549 ISSN 0888-5885 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrogen sulfide * desulfurization * cerium sorbent Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.518, year: 2006

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

Science.gov (United States)

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.

Advanced sulfur control concepts for hot gas desulfurization technology

International Nuclear Information System (INIS)

1998-01-01

The objective of this project is to develop a hot-gas desulfurization process scheme for control of H 2 S in HTHP coal gas that can be more simply and economically integrated with known regenerable sorbents in DOE/METC-sponsored work than current leading hot-gas desulfurization technologies. In addition to being more economical, the process scheme to be developed must yield an elemental sulfur byproduct. The Direct Sulfur Recovery Process (DSRP), a leading process for producing an elemental sulfur byproduct in hot-gas desulfurization systems, incurs a coal gas use penalty, because coal gas is required to reduce the SO 2 in regeneration off-gas to elemental sulfur. Alternative regeneration schemes, which avoid coal gas use and produce elemental sulfur, will be evaluated. These include (i) regeneration of sulfided sorbent using SO 2 ; (ii) partial oxidation of sulfided sorbent in an O 2 starved environment; and (iii) regeneration of sulfided sorbent using steam to produce H 2 S followed by direct oxidation of H 2 S to elemental sulfur. Known regenerable sorbents will be modified to improve the feasibility of the above alternative regeneration approaches. Performance characteristics of the modified sorbents and processes will be obtained through lab- and bench-scale testing. Technical and economic evaluation of the most promising processes concept(s) will be carried out

HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

Energy Technology Data Exchange (ETDEWEB)

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

2001-11-01

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

Effect of Rhodococcus sp. on desulfurization, swelling and extraction of coal

Energy Technology Data Exchange (ETDEWEB)

Wang De-qiang; Shui Heng-fu [University of Technology of Anhui, Maanshang (China). School of Chemical Engineering

2006-08-15

Bio-desulfurization of coal by rhodococcus sp. was studied. Some kinds of coal were swelled with different organic solvents, and then the swelled coals were treated by rhodococcus sp. The results show that the ratios of desulfurization of coals increase after they are swelled, especially swelled with NMP, the ratio is more than 80%. The swelling and extraction of coal were also studied after the coal had been treated by rhodococcus sp. The results show that the ratios of swelling increase more than 65%, but the extraction yield decreases for the coal treated by rhodococcus sp. 11 refs., 5 tabs.

Production and performance of desulfurized rubber asphalt binder

Directory of Open Access Journals (Sweden)

Yanping Sheng

2017-05-01

Full Text Available Asphalt rubber binder typically exhibits disadvantages like segregation and high viscosity; however, this can be improved by the incorporation of desulfurized rubber powder. This study examined the swelling principle of desulfurized rubber asphalt (DRA. In addition, it evaluated the performance of DRA fabricated with various rubber powder contents under different shear conditions and development time. Superpave binders tests, including Brookfield viscosity, dynamic shear rheometer (DSR and bending beam rheometer (BBR tests, were applied on three control binders (i.e., neat, 20 mesh asphalt rubber binder, 40 mesh asphalt rubber binder and a DRA binder. Binder testing results indicated that rubber powder swelled into the base binder and resulted in enhanced stability. Optimum performance of the DRA binder was achieved by adding 20% (by weight of rubber powder into the base binder at shear rate, shear temperature, shear time and development time of 7000 r/min, 170 °C, 60 min and 45 min, respectively. Modified ranges of production conditions were also provided to widen the application of DRA in field construction. It appeared that DRA binder benefited from the recovered plasticity and viscosity of the rubber and consequently, exhibited superior performance over the neat and conventional asphalt rubber binders. Preliminary mixture evaluation was also conducted and the DRA binder was found to significantly improve the mixture resistance to permanent deformation and water damage. Overall, the DAR binder is encouraged to be used as a modified binder for flexible pavements. Keywords: Desulfurized rubber asphalt, Swelling model, Production process, Asphalt performance, Rubber asphalt

A modeling and experimental study of flue gas desulfurization in a dense phase tower

International Nuclear Information System (INIS)

Chang, Guanqin; Song, Cunyi; Wang, Li

2011-01-01

We used a dense phase tower as the reactor in a novel semi-dry flue gas desulfurization process to achieve a high desulfurization efficiency of over 95% when the Ca/S molar ratio reaches 1.3. Pilot-scale experiments were conducted for choosing the parameters of the full-scale reactor. Results show that with an increase in the flue gas flow rate the rate of the pressure drop in the dense phase tower also increases, however, the rate of the temperature drop decreases in the non-load hot gas. We chose a water flow rate of 0.6 kg/min to minimize the approach to adiabatic saturation temperature difference and maximize the desulfurization efficiency. To study the flue gas characteristics under different processing parameters, we simulated the desulfurization process in the reactor. The simulated data matched very well with the experimental data. We also found that with an increase in the Ca/S molar ratio, the differences between the simulation and experimental data tend to decrease; conversely, an increase in the flue gas flow rate increases the difference; this may be associated with the surface reactions caused by collision, coalescence and fragmentation between the dispersed phases.

Experimental research on bypass evaporation tower technology for zero liquid discharge of desulfurization wastewater.

Science.gov (United States)

Ma, Shuangchen; Chai, Jin; Wu, Kai; Xiang, Yajun; Jia, Shaoguang; Li, Qingsong

2018-03-20

Zero liquid discharge (ZLD) of wastewater has become the trend of environmental governance after the implementation of 'The Action Plan for Prevention and Treatment of Water Pollution' in China, desulfurization wastewater has gained more attention due to its complex composition and heavy metals. However, current technologies for ZLD have some shortcomings such as high cost and insufficient processing capacity, ZLD cannot be achieved actually. This paper proposes a new evaporation drying technology. An independent bypass evaporation tower was built, part of the hot flue gas before the air preheater was introduced into the evaporation tower for desulfurization wastewater evaporation, and the generated dust after evaporation was discharged back to the flue duct before electrostatic precipitator. This paper reports on the performance of desulfurization wastewater evaporation and the characteristics of evaporation products in depth and makes a comprehensive discussion of the impact on the existing equipment based on the self-designed evaporation tower. Research suggests that this technology has high system reliability and little effect on subsequent equipment and provides theoretical and practical data. Due to environmental policies and huge market demand for ZLD of desulfurization wastewater, bypass evaporation tower technology has a great application prospect in the future.

MARKETING OF BYPRODUCT GYPSUM FROM FLUE GAS DESULFURIZATION

Science.gov (United States)

The report gives results of an evaluation of the 1985 marketing potential of byproduct gypsum from utility flue gas desulfurization (FGD), for the area east of the Rocky Mountains, using the calculated gypsum production rates of 14 selected power plants. The 114 cement plants and...

SULFUR REDUCTION IN GASOLINE AND DIESEL FUELS BY EXTRACTION/ADSORPTION OF REFRACTORY DIBENZOTHIOPHENES; A

International Nuclear Information System (INIS)

Robert J. Angelici; Scott G. McKinley; Celedonio Alvarez

2001-01-01

Using the classical coordination compound, Ru(NH(sub 3))(sub 5)(H(sub 2)O)(sup 2+), they have prepared a metal complex with a 4,6-dimenthyldibenzothiophene ligand. The compound Ru(NH(sub 3))(sub 5)(H(sub 2)O)(sup 2+) also reacts with thiophene, benzothiophene and dibenzothiophene (DBT) at room temperature. They have found that Ru(NH(sub 3))(sub 5)(H(sub 2)O)(sup 2+) removes over 50% of the DBT in simulated petroleum feedstocks by a biphasic extraction process. The extraction phase is readily generated by air-oxidation thereby completing a cyclic process that removes DBT from petroleum feedstocks

A three-phase comprehensive mathematical model of desulfurization in electroslag remelting process

International Nuclear Information System (INIS)

Wang, Qiang; Li, Guangqiang; He, Zhu; Li, Baokuan

2017-01-01

Highlights: • First developed a three-phase coupled model of desulfurization in ESR process. • The MHD thermal flow in the reactor was clarified. • Distributions of sulfur concentration in the three phases were demonstrated. • An experiment was carried out to validate the simulation. - Abstract: A three-phase comprehensive mathematical model has been established to study the desulfurization behavior in electroslag remelting (ESR) process. The solutions of the mass, momentum, energy, and species conservation equations were simultaneously calculated by the finite volume method. The Joule heating and Lorentz force were fully coupled through solving the Maxwell’s equations with the assistance of the magnetic potential vector. The movements of the air-slag and slag-metal interfaces were described by the volume of fluid (VOF) approach. In order to include the influences of the air, the slag and the electric current on the desulfurization, a thermodynamic and kinetic module was introduced. An experiment was conducted to validate the model. The completely comparison between the measured and simulated data indicates that the model can describe the desulfurization behavior in the ESR process with an acceptable accuracy. The sulfur in the metal would be transferred into the slag under the combined effect of the slag treatment and the electrochemical reaction, and is primarily achieved in the period of the droplet formation. The sulfur in the slag then could be transferred into the air because of the oxidation. The maximum calculated removal ratio in the whole process is around 88%.

Left nucleus accumbens atrophy in deficit schizophrenia: A preliminary study.

Science.gov (United States)

De Rossi, Pietro; Dacquino, Claudia; Piras, Fabrizio; Caltagirone, Carlo; Spalletta, Gianfranco

2016-08-30

A question that remains to be answered is whether schizophrenia can be characterized by a single etiopathophysiology or whether separate sub-syndromes should be differentiated to define specific mechanisms for each sub-type. Individuals affected by the deficit subtype of schizophrenia (DSZ) display avolitional/amotivational features that respond poorly to conventional treatments. Characterizing DSZ from a neuroanatomical point of view may help clarify this issue and develop new treatment strategies. To determine if DSZ is associated with structural alterations in specific deep grey matter structures linked to its key clinical features, 22 DSZ patients, 22 non-deficit schizophrenia (NDSZ) patients and 22 healthy controls (HC) were recruited for a case-control cross-sectional study. High-resolution magnetic resonance imaging was performed in all subjects and volumes of deep grey matter structures were measured using FreeSurfer. DSZ patients displayed smaller left accumbens volumes compared to both NDSZ patients and HC. Moreover, age and duration of illness were significantly associated with lower volume of the left accumbens in DSZ but not in NDSZ. Findings indicate that DSZ is associated with lower volume of the nucleus accumbens in the dominant hemisphere. This is consistent with the psychopathological features and functional impairments present in DSZ and thus indicates a potential mechanism. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

Science.gov (United States)

Farzin Nejad, N.; Shams, E.; Amini, M. K.

2015-09-01

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption-desorption isotherm and transmission electron microscopy. Nitrogen adsorption-desorption measurement revealed the high surface area (810 m2 g-1), maxima pore size of 3.3 nm and large pore volume (1.01 cm3 g-1) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g-1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles.

Improving the desulfurization performance of CaCO3 with sodium humate

Science.gov (United States)

Feng, Run; Sun, Zhiguo; Zhang, Wenqing; Huang, Hao; Hu, Haihang; Zhang, Li; Xie, Hongyong

2018-02-01

The influence of these factors on desulphurization efficiency was studied by changing the amount of calcium carbonate, the concentration of sulfur dioxide, the liquid flow rate of absorbent and the air flow rate, the optimum working condition was determined by the research of limestone-gypsum desulphurization process commonly used in industry. By changing the amount of calcium carbonate, we conclude that the volume of water in the desulfurization efficiency does not increase with the adding amount of calcium carbonate. The optimum conditions were determined : at the condicion of the concentration of 500ppm of sulfur dioxide, 10g calcium carbonate, 150L/h liquid flow and the minimum air flow rate of 6.75m3/h, the highest desulfurization efficiency was close to 100% when sodium humate was not added, but the holding time was only about 5 minutes. After adding 3g of humic acid, the desulfurization efficiency was improved obviously, and the instantaneous efficiency of 100% lasting for about 40 minutes. It can be seen that, calcium carbonate in the addition of humic acid sodium can significantly improve the absorption of calcium carbonate performance of SO2.

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

Science.gov (United States)

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

2011-11-01

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

Workshop on sulfur chemistry in flue gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Wallace, W.E. Jr.

1980-05-01

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

Enrichment and cultivation of a sulfide-oxidizing bacteria consortium for its deploying in full-scale biogas desulfurization

International Nuclear Information System (INIS)

González Sánchez, Armando; Flores Márquez, Trinidad Eliseo; Revah, Sergio; Morgan Sagastume, Juan Manuel

2014-01-01

Operational experiences and strategies to get suitable chemolithoautotrophic sulfide-oxidizing biomass from activated sludge wastewater treatment plant for its deploying in a full-scale biogas desulfurization plant are described. An economic nutrient source was applied to foster microbial selection and rapid growth. Respirometry was implemented on full-scale installations to monitor the ability of the specialized bacteria consortium to oxidize reduced sulfur i.e. H 2 S. During the deployment in the full-scale desulfurization reactor, intermittent sulfide feed from biogas scrubbing was performed to accelerate the startup the desulfurization process. - Highlights: • A simple method for reaching high amounts of specialized sulfide-oxidizing bacterial consortium from activated sludge was developed. • The full-scale desulfurization process can be continuously monitored by respirometry allowing fast decision making if problems arise. • The dissolved sulfide concentration was estimated with an empirical correlation between measurements of ORP, dissolved oxygen and pH

HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

Energy Technology Data Exchange (ETDEWEB)

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

2004-03-01

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

3D CFD Modeling of the LMF System: Desulfurization Kinetics

Science.gov (United States)

Cao, Qing; Pitts, April; Zhang, Daojie; Nastac, Laurentiu; Williams, Robert

A fully transient 3D CFD modeling approach capable of predicting the three phase (gas, slag and steel) fluid flow characteristics and behavior of the slag/steel interface in the argon gas bottom stirred ladle with two off-centered porous plugs (Ladle Metallurgical Furnace or LMF) has been recently developed. The model predicts reasonably well the fluid flow characteristics in the LMF system and the observed size of the slag eyes for both the high-stirring and low-stirring conditions. A desulfurization reaction kinetics model considering metal/slag interface characteristics is developed in conjunction with the CFD modeling approach. The model is applied in this study to determine the effects of processing time, and gas flow rate on the efficiency of desulfurization in the studied LMF system.

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

Science.gov (United States)

Lou, Wentao; Zhu, Miaoyong

2014-10-01

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

A complementary and synergistic effect of Fe-Zn binary metal oxide in the process of high-temperature fuel gas desulfurization

Institute of Scientific and Technical Information of China (English)

翁斯灏; 吴幼青

1996-01-01

57Fe Mossbauer spectroscopy was used to investigate the evolution of Fe-Zn binary metal oxide sorbent in the process of high-temperature fuel gas desulfurization. The results of phase analyses show that Fe-Zn binary metal oxide sorbent is rapidly reduced in hot fuel gas and decomposed to new phases of highly dispersed microcrystalline elemental iron and zinc oxide, both of which become the active desulfurization constituents. A complementary and synergistic effect between active iron acting as a high sulfur capacity constituent and active zinc oxide acting as a deep refining desulfurization constituent exists in this type of sorbent for hot fuel gas desulfurization.

Methods for dry desulfurization of flue gas

International Nuclear Information System (INIS)

Bjondahl, F.

2002-01-01

In this report different types of dry desulfurization processes are de-scribed. These processes are utilized for the removal of SO 2 from flue gases. Basic process descriptions, information on different sorbent types and their properties and some comments based on the authors own experience are included. Information on disposal or use of the end product from these processes is also provided. (orig.)

Ultrasonic coal-wash for de-ashing and de-sulfurization. Experimental investigation and mechanistic modeling

Energy Technology Data Exchange (ETDEWEB)

Ambedkar, B. [Indian Institute of Technology Madras, Chennai (India). Dept. of Chemical Engineering

2012-07-01

This study focuses on the physical aspects of ultrasonic de-ashing and de-sulfurization, such as cavitation, streaming and their combined effects. Ambedkar Balraj proposes an ultrasound-assisted coal particle breakage mechanism and explores aqueous and solvent-based ultrasonic techniques for de-ashing and de-sulfurization. Ambedkar designs a Taguchi L-27 fractional-factorial matrix to assess the individual effects of key process variables. In this volume he also describes process optimization and scale-up strategies. The author provides a mechanism-based model for ultrasonic reagent-based coal de-sulfurization, proposes a flow diagram for ultrasonic methods of high-throughput coal-wash and discusses the benefits of ultrasonic coal-wash. Coal will continue to be a major fuel source for the foreseeable future and this study helps improve its use by minimising ash and sulfur impurities.

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

Science.gov (United States)

Grindley, T.

1988-04-05

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

[Effects of desulfurization waste on calcium distribution, Ca(2+)-ATPase activity, and antioxidant characteristics of rice leaf under alkali stress].

Science.gov (United States)

Mao, Gui-Lian; Xu, Xing; Zeng, Jin; Yue, Zi-Hui; Yang, Shu-Juan

2012-02-01

To approach the action mechanisms of desulfurization waste on alleviating alkali stress-induced injury of rice, a pot experiment was conducted to study the variations of leaf total calcium content, calcium distribution, plasma membrane Ca(2+)-ATPase activity, and reactive oxygen content of rice seedlings under alkali stress after the application of desulfurization waste. In the control, a few calcium particulates scattered in the cell wall and chloroplasts, while applying desulfurization waste or CaSO4 increased the calcium particulates in the plasma membrane, intercellular space, cell wall, and vacuole significantly. With the increasing application rate of desulfurization waste or CaSO4, the leaf total calcium content increased, Ca(2+)-ATPase activity in plasma membrane and tonoplast presented an increasing trend, plasma membrane relative permeability, MDA content, and O2 production rate decreased, and SOD and POD activities increased. The desulfurization waste could relieve the alkali stress to rice in some extent, and the main reactive compound in the waste could be CaSO4.

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

Science.gov (United States)

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

2016-10-14

The oxidative desulfurization of model and real diesel has been studied using the complex [MoO2Cl2(4,4'-di-tert-butyl-2,2'-bipyridine)] as (pre)catalyst, aq. H2O2 as oxidant, and an ionic liquid as extraction solvent. Under moderate conditions (50 °C) and short reaction times (desulfurization and ECODS steps, 76% sulfur removal was achieved for a real diesel (Sinitial = 2300 ppm). For both the model and real diesels, the catalyst/IL phase could be easily recycled and reused with no loss of desulfurization efficiency.

Natural desulfurization in coal-fired units using Greek lignite.

Science.gov (United States)

Konidaris, Dimitrios N

2010-10-01

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

Development of economical and high efficient desulfurization process using low rank coal; Teitankadotan wo mochiita ankana kokoritsu datsuryuho no kaihatsu

Energy Technology Data Exchange (ETDEWEB)

Takarada, Y; Kato, K; Kuroda, M; Nakagawa, N [Gunma University, Gunma (Japan). Faculty of Engineering; Roman, M [New Energy and Industrial Technology Development Organization, Tokyo, (Japan)

1997-02-01

Experiment reveals the characteristics of low rank coal serving as a desulfurizing material in fluidized coal bed reactor with oxygen-containing functional groups exchanged with Ca ions. This effort aims at identifying inexpensive Ca materials and determining the desulfurizing characteristics of Ca-carrying brown coal. A slurry of cement sludge serving as a Ca source and low rank coal is agitated for the exchange of functional groups and Ca ions, and the desulfurizing characteristics of the Ca-carrying brown coal is determined. The Ca-carrying brown coal and high-sulfur coal char is mixed and incinerated in a fluidized bed reactor, and it is found that a desulfurization rate of 75% is achieved when the Ca/S ratio is 1 in the desulfurization of SO2. This rate is far higher than the rate obtained when limestone or cement sludge without preliminary treatment is used as a desulfurizer. Next, Ca-carrying brown coal and H2S are caused to react upon each other in a fixed bed reactor, and then it is found that desulfurization characteristics are not dependent on the diameter of the Ca-carrying brown coal grain, that the coal is different from limestone in that it stays quite active against H2S for long 40 minutes after the start of the reaction, and that CaO small in crystal diameter is dispersed in quantities into the char upon thermal disintegration of Ca-carrying brown coal to cause the coal to say quite active. 5 figs.

Bench-Scale Demonstration of Hot-Gas Desulfurization Technology

International Nuclear Information System (INIS)

Portzer, Jeffrey W.; Gangwal, Santosh K.

1997-01-01

Prior to the current project, development of the DSRP was done in a laboratory setting, using synthetic gas mixtures to simulate the regeneration off-gas and coal gas feeds. The objective of the current work is to further the development of zinc titanate fluidized-bed desulfurization (ZTFBD) and the DSRP for hot-gas cleanup by testing with actual coal gas. The objectives of this project are to: (1) Develop and test an integrated, skid-mounted, bench-scale ZTFBD/DSRP reactor system with a slipstream of actual coal gas; (2) Test the bench-scale DSRP over an extended period with a slipstream of actual coal gas to quantify the degradation in performance, if any, caused by the trace contaminants present in coal gas (including heavy metals, chlorides, fluorides, and ammonia); (3) Expose the DSRP catalyst to actual coal gas for extended periods and then test its activity in a laboratory reactor to quantify the degradation in performance, if any, caused by static exposure to the trace contaminants in coal gas; (4) Design and fabricate a six-fold larger-scale DSRP reactor system for future slipstream testing; (5) Further develop the fluidized-bed DSRP to handle high concentrations (up to 14 percent) of SO 2 that are likely to be encountered when pure air is used for regeneration of desulfurization sorbents; and (6) Conduct extended field testing of the 6X DSRP reactor with actual coal gas and high concentrations of SO 2 . The accomplishment of the first three objectives--testing the DSRP with actual coal gas, integration with hot-gas desulfurization, and catalyst exposure testing--was described previously (Portzer and Gangwal, 1994, 1995; Portzer et al., 1996). This paper summarizes the results of previous work and describes the current activities and plans to accomplish the remaining objectives

Shell launches its Claus off-gas desulfurization process

Energy Technology Data Exchange (ETDEWEB)

Groenendaal, W; van Meurs, H C.A.

1972-01-01

The Shell Flue Gas Desulfurization (SFGD) Process was developed for removal of sulfur oxides from flue gases originating from oil-fired boilers or furnaces. It can also be used to remove sulfur dioxide from Claus sulfur recovery tail gases if they are combined with boiler/furnace flue gases. For Claus tail gas only, the Shell Claus off-gas desulfurization process was developed. Claus unit operation and desulfurization by low temperature Claus processes and conversion/concentration processes are discussed. The new Shell process consists of a conversion/concentration process involving a reduction section and an amine absorption section. In the reduction section, all sulfur compounds and free sulfur are completely reduced to hydrogen sulfide with hydrogen, or hydrogen plus carbon monoxide, over a cobalt/molybdenum-on-alumina catalyst at a temperature of about 300/sup 0/C. Extensive bench scale studies on the reduction system have been carried out. A life test of more than 4000 hr showed a stable activity of the reduction catalyst, which means that in commercial units, very long catalyst lives can be expected. The commercial feasibility of the reduction section was further demonstrated in the Godorf refinery of Deutsche Shell AG. More than 80 absorption units using alkanolamine (AIDP) solutions have been installed. Bench scale studies of the ADIP absorption units were compared to commercial experience.The total capital investment of the new Shell process is 0.7, 2.0, and 3.2 $ times 10 to the 6th power for 100, 500, and 1000 tons of sulfur/sd capacity Claus units, respectively. The total operating costs for these units are, respectively, 610, 1930 and 3310 $/stream day. The capital investment corresponds to about 75% of the capital investment of the preceding Claus unit.

Effect of potassium hydroxide activation in the desulfurization process of activated carbon prepared by sewage sludge and corn straw.

Science.gov (United States)

Zeng, Fan; Liao, Xiaofeng; Hu, Hui; Liao, Li

2018-03-01

Series sludge straw-based activated carbons were prepared by sewage sludge and corn straw with potassium hydroxide (KOH) activation, and the desulfurization performance of activated carbons was studied. To obtain the best desulfurization performance, the optimum ratio between the raw materials and the activator was investigated. The results showed that when the mass ratio of sewage sludge, corn straw, and KOH was 3:7:2, the activated carbon obtained the best breakthrough and saturation sulfur sorption capacities, which were 12.38 and 5.74 times, respectively, those of samples prepared by the nonactivated raw materials. The appropriate KOH could improve the microporosity and alkaline groups, meanwhile reducing the lactone groups, which were all beneficial to desulfurization performance. The chemical adsorption process of desulfurization can be simplified to four main steps, and the main desulfurization products are elemental sulfur and sulfate. Sewage sludge (SS) and corn straw (CS) both have great production and wide distribution and are readily available in China. Much attention has been paid on how to deal with them effectively. Based on the environment protection idea of waste treatment with waste and resource recycling, low-cost adsorbents were prepared by these processes. The proposed method can be expanded to the municipal solid waste recycling programs and renewable energy plan. Thus, proceeding with the study of preparing activated carbon by SS and straw as a carbon-based dry desulfurization agent could obtain huge social, economic, and environmental benefits.

The Study of the Desulfurization Process of Oil and Oil Products of "Zhanazhol" Oil Field Using the Approaches of Green Chemistry

OpenAIRE

Zhaksyntay K. Kairbekov; Zhannur K. Myltykbaeva; Nazym T. Smagulova; Dariya K. Kanseitova

2015-01-01

In this paper we studied sono catalytic oxidative desulfurization of oil and diesel fraction from “Zhanazhol” oil deposits. We have established that the combined effect of the ultrasonic field and oxidant (ozone-air mixture) in the presence of the catalyst on the oil is potentially very effective method of desulfurization of oil and oil products. This method allows increasing the degree of desulfurization of oil by 62%.

Economic analysis of ultrasound-assisted oxidative desulfurization

OpenAIRE

Anderson, K.; Atkins, M.P.; Borges, P; Chan, Z.P.; Rafeen, M.S.; Sebran, N.H.; van der Pool, E; Vleeming, J.H.

2017-01-01

Oxidative desulfurization is a method of removing sulfur from diesel fuel that has the potential to compete with conventional hydrodesulfurization processes in refineries. Ultrasound has been shown to greatly increase peroxide oxidation rates of sulfur compounds and can thereby enhance the technology. Through the use of conceptual design modeling, this article critically assesses a range of novel process options. Calculations show that the rate enhancement achieved by ultrasound can translate...

Effects of nano-TiO2 on combustion and desulfurization

International Nuclear Information System (INIS)

Zhao, Yi; Wang, Shuqin; Shen, Yanmei; Lu, Xiaojuan

2013-01-01

Nanosized titanium oxide powder was prepared via the sol–gel process and characterized by transmission electron microscope. The effects of nano-TiO 2 on combustion characteristics of lignite, desulfurization in combustion and the properties of ashes were investigated. The calorific value of coals and the fusion point of the coal ashes were measured by calorimeter and ash fusion point determination meter; the components of coal ashes and the contents of combustible matters in ash were determined by chemical methods; the pore-size distribution and specific surface area of the coal ash were analyzed by surface area analyzer. A thermogravimetric analyzer was used to investigate the effect of nano-TiO 2 on combustion. The results showed that the calorific value of the coal and the fusion temperature of the coal ash were lowered by adding CaO, while on the other hand adding nano-TiO 2 to coal increased the calorific value and the melting temperature effectively. Meanwhile, the coal combustion efficiency and desulfurization in combustion could be effectively improved by the co-action of TiO 2 . - Highlights: • The burn-off rate of coals was raised and the combustible contents were reduced by adding nano-TiO 2 . • The desulfurization in combustion can be achieved by adding CaO, but the combustion efficiency was inhibited. • Nano-TiO 2 can promote the transfer rate of oxygen from gas phase to the surface of char

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

Energy Technology Data Exchange (ETDEWEB)

Sachdeva, T.O.; Pant, K.K. [Department of Chemical Engineering, Indian Institute of Technology, Delhi, New Delhi, 110016 (India)

2010-09-15

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO{sub x}) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

International Nuclear Information System (INIS)

Sachdeva, T.O.; Pant, K.K.

2010-01-01

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO x ) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

THERMODYNAMIC AND KINETIC PARAMETERS OF MIXTURES DESULFURIZING THE MADE WITH CaO, MgO, SiO2 AND CaF2

Directory of Open Access Journals (Sweden)

Felipe Nylo de Aguiar

2012-09-01

Full Text Available This paper presents an analysis of the kinetics and thermodynamics of marble residue mixtures utilisation on desulfurization of pig iron. The desulfurization was carried out using lime, marble residue, fluorite and pig iron. Different mixtures of these materials were added into a bath of pig iron at 1,450°C. Metal samples were collected via vacuum samplers at times of 5, 10, 15, 20 and 30 minutes, in order to check the variation of sulfur content. Based on the results of chemical analysis of the metal and the desulfurizer mixture, the sulfide capacity of mixtures, the sulfur partition coefficient and the sulfur mass transport coefficient values were calculated.The results show the technical feasibility of using marble waste as desulfurizer agent.

Gas-exfoliated porous monolayer boron nitride for enhanced aerobic oxidative desulfurization performance

Science.gov (United States)

Wu, Yingcheng; Wu, Peiwen; Chao, Yanhong; He, Jing; Li, Hongping; Lu, Linjie; Jiang, Wei; Zhang, Beibei; Li, Huaming; Zhu, Wenshuai

2018-01-01

Hexagonal boron nitride has been regarded to be an efficient catalyst in aerobic oxidation fields, but limited by the less-exposed active sites. In this contribution, we proposed a simple green liquid nitrogen gas exfoliation strategy for preparation of porous monolayer nanosheets (BN-1). Owing to the reduced layer numbers, decreased lateral sizes and artificially-constructed pores, increased exposure of active sites was expected, further contributed to an enhanced aerobic oxidative desulfurization (ODS) performance up to ˜98% of sulfur removal, achieving ultra-deep desulfurization. This work not only introduced an excellent catalyst for aerobic ODS, but also provided a strategy for construction of some other highly-efficient monolayer two-dimensional materials for enhanced catalytic performance.

Microbiological desulfurization and conversion of coal

International Nuclear Information System (INIS)

Quigley, D.R.; Stoner, D.L.; Dugan, P.R.

1991-01-01

Bio processing of coal is a young and emerging technology. Until the early 1980's it consisted primarily of coal depyritization using Thiobacillus ferro oxidans to either oxidize pyritic sulfur or to alter particle wettability or floatation properties by binding to exposed pyrite inclusions. Since then, other major avenues of research have been pursued. One of these is the microbiologically mediated liquefaction of coal. Initial work indicated that microorganisms were able to transform low rank coal into a black liquid that was later identified as water solubilized by alkaline substances produced by the microbes and could be enhanced by the removal of multi valent cations from coal. Current work at the INEL involves of the identification and characterization of microorganisms that are able to alter the structure of polymeric desulfurization of coal. This work initially focused on the ability of microorganisms to oxidatively remove organic sulfur from model compounds that were representative of those sulfur containing moieties identified as being in coals (e.g., dibenzo thiophene). The work also focused on those organisms that were could remove the organic sulfur without degrading the carbon structure. While some organisms that are able to perform such these reactions will effectively remove organo sulfur from coal. These concerns stem from steric hindrance considerations and the thermodynamically unfavourable nature of reaction. Current work at the INEL involves the isolation and biochemical characterization of microorganisms that are able to desulfurize and solubilized coals that have high organic sulfur contents. (author)

Biodesulfurization of Naphthothiophene and Benzothiophene through Selective Cleavage of Carbon-Sulfur Bonds by Rhodococcus sp. Strain WU-K2R

Science.gov (United States)

Kirimura, Kohtaro; Furuya, Toshiki; Sato, Rika; Ishii, Yoshitaka; Kino, Kuniki; Usami, Shoji

2002-01-01

Naphtho[2,1-b]thiophene (NTH) is an asymmetric structural isomer of dibenzothiophene (DBT), and in addition to DBT derivatives, NTH derivatives can also be detected in diesel oil following hydrodesulfurization treatment. Rhodococcus sp. strain WU-K2R was newly isolated from soil for its ability to grow in a medium with NTH as the sole source of sulfur, and growing cells of WU-K2R degraded 0.27 mM NTH within 7 days. WU-K2R could also grow in the medium with NTH sulfone, benzothiophene (BTH), 3-methyl-BTH, or 5-methyl-BTH as the sole source of sulfur but could not utilize DBT, DBT sulfone, or 4,6-dimethyl-DBT. On the other hand, WU-K2R did not utilize NTH or BTH as the sole source of carbon. By gas chromatography-mass spectrometry analysis, desulfurized NTH metabolites were identified as NTH sulfone, 2′-hydroxynaphthylethene, and naphtho[2,1-b]furan. Moreover, since desulfurized BTH metabolites were identified as BTH sulfone, benzo[c][1,2]oxathiin S-oxide, benzo[c][1,2]oxathiin S,S-dioxide, o-hydroxystyrene, 2-(2′-hydroxyphenyl)ethan-1-al, and benzofuran, it was concluded that WU-K2R desulfurized NTH and BTH through the sulfur-specific degradation pathways with the selective cleavage of carbon-sulfur bonds. Therefore, Rhodococcus sp. strain WU-K2R, which could preferentially desulfurize asymmetric heterocyclic sulfur compounds such as NTH and BTH through the sulfur-specific degradation pathways, is a unique desulfurizing biocatalyst showing properties different from those of DBT-desulfurizing bacteria. PMID:12147483

An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

Energy Technology Data Exchange (ETDEWEB)

Dai, Yongchuan; Qi, Yutai [Department of Applied Chemistry, School of Science, Harbin Institute of Technology, Harbin 115001 (China); Zhao, Dezhi [Department of Petroleum Chemical Engineering, Liaoning Shihua University, Fushun 113001 (China); Zhang, Huicheng [Fushun Research Institute of Petroleum and Petrochemicals of SINOPEC Corp., Fushun 113001 (China)

2008-10-15

The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide-acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe{sup 2+}/H{sub 2}O{sub 2} 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 {mu}g/g to 9.50 {mu}g/g. (author)

Desulfurization Sorbents for Transport-Bed Applications

International Nuclear Information System (INIS)

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

1997-01-01

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

Hydrothermal synthesis of Ni_2P nanoparticle and its hydrodesulfurization of dibenzothiophene

International Nuclear Information System (INIS)

Zhao, Qi; Han, Yang; Huang, Xiang; Dai, Jinhui; Tian, Jintao; Zhu, Zhibin; Yue, Li

2017-01-01

Nanosized nickel phosphide (Ni_2P) has been synthesized via hydrothermal reaction with environmental-friendly red phosphorus and nickel chloride. The reaction mechanism has been studied by measurement techniques of IC, XRD ,TEM, EDS, and XPS. The results showed that the particle sizes of as-prepared Ni_2P are in nanoscale ranging from 10 to 30 nm. In hydrothermal reaction, red phosphorus reacts with water to its oxyacids, especially its hypophosphorous acid (or hypophosphite) which can reduce nickel chloride to nickel, and then metallic nickel will penetrate into the rest of red phosphorus to generate nano-Ni_2P. Furthermore, the catalytic performance of as-synthesized Ni_2P for the hydrodesulfurization of dibenzothiophene has been tested. It has been shown that the HDS reaction process over Ni_2P catalyst agrees well with the pseudo-first order kinetic equation, and the HDS conversion can reach up to 43.83% in 5 h with a stable increasing catalytic activity during the whole examination process.

A novel surface imprinted polymer/magnetic hydroxyapatite nanocomposite for selective dibenzothiophene scavenging

Science.gov (United States)

Ali, Hager R.; El-Maghrabi, Heba H.; Zahran, Fouad; Moustafa, Yasser Mohamed

2017-12-01

Highly selective adsorbent for dibenzothiophene (DBT) was successfully designed and prepared. Molecularly imprinted polymer (MIP) and magnetic hydroxyapatite (MHAP) were used as building blocks for the novel nanocomposite adsorbent. MIP/MHAP was synthesized by grafting polymerization and surface molecular imprinting using DBT as a template molecule. The microstructure and morphology of the designed nanoadsorbent were examined via FTIR, SEM and VSM. Specific surface area and pore size distribution were determined by Quantachrome Nova 3200S automated gas sorption apparatus. Additionally, static adsorption experiments, isotherms and selective recognition adsorption studies were carried out. Reversed-phase high performance liquid chromatography (RP-HPLC) was used to determine DBT. The experimental data exhibits excellent adsorption capacity for DBT reaches 247 mg/g within 60 min. Competitive adsorption results proved that MIP/MHAP have a greater affinity towards DBT molecules than benzothiophene analogues. Pseudo-second-order model and the Langmuir isotherm were used to describe the adsorption process.

Desulfurization of petroleum by Co-60 gamma irradiation and analysis of products using GC-MS

International Nuclear Information System (INIS)

Mathuthu, M.; Tshivhase, V.M.; Olobatoke, R.Y.; Gaxela, N.N.

2014-01-01

Sulfur is an undesirable hetero-atom that has negative on motor engines if present in quantities between 50 and 180.000 ppm. Research has shown that sour petroleum can be 'sweetened' by gamma irradiation to de-sulfurize the crude oil. In this research we will report experimental results of desulfurizing petroleum locally procured. The objective is to improve the quality of product delivered to the motor market and also reduce the environmental pollution due to SO 2 emissions from engines. The gamma irradiated (de-sulfurized petroleum was chemically analyzed using GC-MS. The preliminary results show that the petroleum is polymerized by gamma radiation to higher molecular mass. The un-irradiated petroleum had a sulfur concentration of 3.24% and 0.020% wt after gamma irradiation. The sulfur content was reduced by a factor of about 160 when dose was increased from zero to 50 kGys. GC-MS Chromatographs are presented for the identified hydrocarbons after gamma irradiation. (authors)

Process for desulfurizing hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1937-04-12

A process is described for the desulfurization of a mixture of hydrocarbons, and in particular hydrocarbons containing less than 7 atoms of carbon and sulfur compounds of the type of sulfur carbonyl, characterized by the fact that the mixture, preferably in the liquid phase, is brought in contact with a solution of caustic alkali, essentially anhydrous or preferably with a solution of alkali hydroxide in an organic hydroxy nonacid solvent, for example, an alcohol, or with an alkaline alcoholate, under conditions suitable to the formation of hydrogen sulfide which produces a hydrocarbon mixture free from sulfur compounds of the sulfur carbonyl type but containing hydrogen sulfide, and that it is treated, following mixing, having beem submitted to the first treatment, by means of aqueous alkaline hydroxide to eliminate the hydrogen sulfide.

The Biocatalytic Desulfurization Project

Energy Technology Data Exchange (ETDEWEB)

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

2006-03-03

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

Core-in-shell sorbent for hot coal gas desulfurization

Science.gov (United States)

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

2004-02-10

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

Reusing pretreated desulfurization slag to improve clinkerization and clinker grindability for energy conservation in cement manufacture.

Science.gov (United States)

Chen, Ying-Liang; Chang, Juu-En; Shih, Pai-Haung; Ko, Ming-Sheng; Chang, Yi-Kuo; Chiang, Li-Choung

2010-09-01

The purpose of this study was to combine the physical pretreatments of grinding, sieving, and magnetic-separation processes to reclaim iron-rich materials from the desulfurization slag, and to use the remainder for cement clinker production. The iron-rich materials can be separated out efficiently by grinding for 30 min and sieving with a 0.3 mm mesh. The non-magnetic fraction of the particles smaller than 0.3 mm was in the majority, and proved to be suitable for use as a cement raw material. The raw mixes prepared with a pretreated desulfurization slag had a relatively high reactivity, and the temperature at which alite forms was significantly reduced during the clinkerization process. The clinkers produced with 10% desulfurization slag had a high level of alite and good grindability. Generally, the improvements in clinkerization and clinker grindability are beneficial to energy conservation in cement manufacture. 2010 Elsevier Ltd. All rights reserved.

Desulfurization of chemical waste gases and flue gases with economic utilization of air pollutants

Energy Technology Data Exchange (ETDEWEB)

Asperger, K.; Wischnewski, W.

1983-09-01

The technological state of recovery of sulfur dioxide from waste and flue gases in the GDR is discussed. Two examples of plants are presented: a pyrosulfuric acid plant in Coswig, recovering sulfur dioxide from gases by absorption with sodium hydroxide, followed by catalytic oxidation to sulfur trioxide, and a plant for waste sulfuric acid recovery from paraffin refining, where the diluted waste acid is sprayed into a furnace and recovered by an ammonium-sulfite-bisulfite solution from the combustion gas (with 4 to 10% sulfur dioxide content). Investment and operation costs as well as profits of both plants are given. Methods employed for power plant flue gas desulfurization in major industrial countries are further assessed: about 90% of these methods uses wet flue gas scrubbing with lime. In the USA flue gas from 25,000 MW of power plant capacity is desulfurized. In the USSR, a 35,000 m/sup 3//h trial plant at Severo-Donetzk is operating using lime, alkali and magnesite. At the 150 MW Dorogobush power plant in the USSR a desulfurization plant using a cyclic ammonia process is under construction.

Photooxidative desulfurization for diesel using Fe / N - TiO2 photocatalyst

Science.gov (United States)

Khan, Muhammad Saqib; Kait, Chong Fai; Mutalib, Mohd Ibrahim Abdul

2014-10-01

A series of N - TiO2 with different mol% N was synthesized via sol-gel method and characterized using thermal gravimetric analyzer and raman spectroscopy. 0.2 wt% Fe was incorporated onto the calcined (200°C) N - TiO2 followed by calcination at 200°C, 250°C and 300°C. Photooxidative desulfurization was conducted in the presence of 0.2wt% Fe / N - TiO2 with different mol% N with and without oxidant (H2O2). Oxidative desulfurization was only achieved when H2O2 was used while without H2O2 no major effect on the sulfur removal. 0.2Fe -30N - H2O2 photocatalysts showed best performance at all calcination temperatures as compared to other mol% N - H2O2 photocatalysts. 16.45% sulfur removal was achieved using photocatalysts calcined at 300 °C.

Investigation of organic desulfurization additives affecting the calcium sulfate crystals formation

Directory of Open Access Journals (Sweden)

Lv Lina

2017-01-01

Full Text Available In the study, the optimal experimental conditions for gypsum crystals formation were 323 K, 300 rpm stirring speed. The major impurities of Mg2+, Al3+ and Fe3+ were found to inhibit calcium sulfate crystals formation. Fe3+ caused the strongest inhibition, followed by Mg2+ and Al3+. The influence of desulfurization additives on the gypsum crystals formation was explored with the properties of moisture content, particle size distribution and crystal morphology. The organic desulfurization additives of adipic acid, citric acid, sodium citrate and benzoic acid were investigated. Citric acid and sodium citrate were found to improve the quality of gypsum. Moisture contents were reduced by more than 50%, gypsum particle sizes were respectively enlarged by 9.1 and 22.8%, induction time extended from 4.3 (blank to 5.3 and 7.8 min, and crystal morphology trended to be thicker.

Biogas desulfurization with a new developed doped activated carbon. 20 month pilot test; Biogasfeinentschwefelung mittels neu entwickelter dotierter Aktivkohle. 20-monatiger Praxistest

Energy Technology Data Exchange (ETDEWEB)

Rossow, Silvana; Deerberg, Goerge; Goetze, Toralf; Kanswohl, Norbert; Nelles, Michael [Univ. Rostock (Germany). Lehrstuhl fuer Abfall- und Stoffstromwirtschaft

2009-05-15

Doped activated carbon is a special developed activated carbon for the desulfurization of technical gases. Based on its special adsorption properties, it is able to bond a large amount of hydrogen sulfide. By the special manufacturing method it was possible to optimize further the performance for the desulfurization of gases. In a biogas plant with an installed electric capacity of 2 MW the functionality of the doped activated carbon was proofed in a real biogas stream in a 20 month pilot test. The activated carbon was used in a special adsorption system that was tunes on the requirement of the activated carbon and on the site of installation. Because the biogas plant was in the starting period, all the time there were variable operation conditions. In spite of the variable conditions the doped activated carbon shows a permanent complete desulfurization, as in the executed laboratory experiments. By the use of the desulfurization system the concentration of hydrogen sulfide is decreased less than 1 ppm. The prejudices with are often caused by hydrogen sulphide could not identify until now. A positive evidence of the excellent desulfurization is the doubling of the oil lifetime of the block heating station. (orig.)

Deep desulfurization of jet fuel for applications in mobile fuel cell systems; Tiefentschwefelung von Flugturbinenkraftstoffen fuer die Anwendung in mobilen Brennstoffzellensystemen

Energy Technology Data Exchange (ETDEWEB)

Wang, Yong

2012-07-01

Fuel cell powered APUs are promising for the on-board electricity supply in heavy vehicles, aircraft and ships because of their high efficiency and low emission of pollutants. The catalytical reforming with subsequent gas processing units is applied to operate the fuel cell system with onboard available fuels. Within the reformer the liquid fuel is converted into a hydrogen-rich synthesis gas in the presence of metal catalysts. However, an on-board desulfurization of fuels is required to avoid the deactivation of catalysts in the fuel processing unit as well as in the fuel cell. The present work aims at developing a technically feasible deep desulfurization process for fuel cell powered APUs with theoretical and experimental study as well as procedural analysis. The focus of the work is on the desulfurization of jet fuels in liquid phase, since the reformer currently developed in IEK-3 is designed for aviation applications of fuel cell APUs and it can only be operated by liquid jet fuels. In addition, the desulfurization of marine gas oil was investigated to fulfill the sulfur requirement of the fuels for the application of fuel cell A PUs for inland navigation. In the petroleum industry, low-sulfur fuels are often obtained by hydrodesulfurization and the S-Zorb Process. However, these conventional methods are highly inconvenient for reducing sulfur compounds to the desired level in a mobile fuel cell system, since improvements of the desulfurization efficiency are limited by increasingly severe operating conditions and escalating costs. Moreover, the hydrodesulfurization and the S-Zorb Process are not suitable for mobile applications, since hydrogen recycling is required, which is not possible with H{sub 2} syngas. To this end, a large number of processes discussed in the literature were assessed with regard to their application in fuel cell APUs. Three potentially suitable processes were selected: pervaporation, adsorption, and hydrodesulfurization with pre

Desulfurization of waste gases of the incinerator after petroleum refining

International Nuclear Information System (INIS)

Samesova, D.; Ladomersky, J.

2001-01-01

Desulfurization of waste gases of the incinerator after petroleum refining was developed. Mixing of wastes with lime (10% of additive of total volume of waste) was proved before introduction into incinerator. Concentrations of CO, CO 2 , O 2 , NO 2 , SO 2 and temperature of combustion products were measured by automatic analyser

Semi-dry flue gas desulfurization using Ca(OH)2 in a fluidized bed reactor with bed materials

International Nuclear Information System (INIS)

Park, Young Oak; Roh, Hak Jae; Oh, Chang Sup; Kim, Yong Ha

2010-01-01

The main objective of present work is to reduce sulfur dioxide emission from power plant for the environment protection. The fluidized bed (FB) was used as the reactor with bed materials in a new semi-dry flue gas desulfurization (FGD) process to achieve high desulfurization efficiency (>98%). Fine powder of Ca(OH) 2 as sorbent and water were continuously fed separately to the bed reactor where bed materials (2 mm glass beads) were fluidized vigorously with flue gas (flow 720 Nm 3 / hr) using bench scale plant of stainless steel column. We have investigated different effects of water injection flow rate, Ca/ S molar ratio and weight of bed materials on SO 2 removal. The increments in the Ca/ S molar ratio and water injection flow rate have been resulted higher desulfurization efficiency with certain disadvantages such as higher sorbent cost and lower temperature of the treated flue gas, respectively. (author)

Adsorptive removal of dibenzothiophene from model fuels over one-pot synthesized PTA@MIL-101(Cr) hybrid material

Energy Technology Data Exchange (ETDEWEB)

Jia, Shao-Yi; Zhang, Yan-Fei [School of Chemical Engineering and Technology, Tianjin University, Tianjin (China); Liu, Yong [School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin (China); Qin, Feng-Xiang; Ren, Hai-Tao [School of Chemical Engineering and Technology, Tianjin University, Tianjin (China); Wu, Song-Hai, E-mail: songhaiwu@gmail.com [School of Chemical Engineering and Technology, Tianjin University, Tianjin (China)

2013-11-15

Highlights: • One-pot synthesized PTA@MIL-101(Cr) shows high capacity of benzothiophene. • PTA/MIL-101(Cr) obtained via post-modification performs poor in the adsorption. • PTA and MIL-101(Cr) exhibit synergetic effect on adsorption of benzothiophene. • In the presence of aromatics, PTA@MIL-101(Cr) and MIL-101(Cr) remain their capacity. • PTA-dispersed MOFs adsorb dibenzothiophene through acid–base interaction. -- Abstract: Hybrid nanomaterials comprising phosphotungstic acid (PTA) and MIL-101(Cr) were prepared through one-pot synthesis and post-modification methods and then were used as adsorbents of dibenzothiophene (DBT) from simulated diesel fuels. Samples obtained by different ways (encapsulation and impregnation) were characterized by nitrogen adsorption, transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR) and series of adsorption experiments. The equilibrium adsorption capacities of PTA@MIL-101(Cr) illustrated that the direct introduction of PTA into MIL-101(Cr) during synthesis resulted in a 10.7% increase compared with MIL-101(Cr). However, porous hybrid adsorbent PTA/MIL-101(Cr) prepared via post-modification method exhibited lower adsorption capacity than virgin MIL-101(Cr). The theoretical maximum adsorption capacity (Q{sub 0}) of PTA@MIL-101(Cr) is 136.5 mg S/g adsorbent, 4.2 times of MIL-101(Cr). Even in competitive adsorption between aromatic compounds, which possess strong affinity with MOFs, and DBT, PTA@MIL-101(Cr) and MIL-101(Cr) remained their effectiveness in removal of DBT in the system. Based on these results, it can be presumed that MIL-101(Cr), modified properly, can be used as a promising adsorbent for eliminating aromatics and S-compounds in commercial fuels simultaneously.

Bio-desulfurization technology in Japan; Wagakuni ni okeru baio datsuryu gijutsu

Energy Technology Data Exchange (ETDEWEB)

Maruhashi, K. [Petroleum Energy Center, Tokyo (Japan)

2000-05-01

A bio-reaction of microbes (catalytic reaction by an enzyme) is characterized in that the reaction is carried out at a normal temperature and under a normal pressure and has particularly high specificity with respect to substrate (reactant). It is considered that a low loading process of environment harmony type can be constructed by applying the bio-reaction in petroleum refinery process. CO{sub 2} exhaust and energy consumption in the bio-desulfurization (BDS) is estimated to be 70 to 80% lower than those in hydrodesulfurization (HDS). The bio-technologies that can be applied to the petroleum refinery process include, for example, desulfurization, demetallation, dewaxing, denitration, cracking and so on. In this paper, the present state of bio-desulphurization technology is introduced. Particularly, as the research results in Japan, acquirement of mesophile R.erythropolis KA2-5-1 strain, thermophile Paenibacillus sp. A11-2 strain whose optimum temperature is 50 degrees C, BT degradation fungus Rhodococcus sp. T09 and the like are introduced. (NEDO)

Biological flue gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Buisman, C.J.N.; Dijkman, H.; Wijte, G.; Prins, W.L.; Verbraak, P.; Hartog, H.A.J. den [Paper B.V. Blak (Netherlands)

1995-08-01

A new biological flue gas desulfurization process (BIO-FGD) producing sulphur as a by-product was invented by Paques BV and Hoogens Technical Services in 1993. Sulphur dioxide is absorbed from flue gas using a combination of a sodium based scrubber and two biological reactors, an anaerobic and an aerobic biological reactor. The article describes the process and its evaluation in a pilot plant at 2 MW scale, designed to remove 6 kg/hr SO{sub 2} of the 2 million m{sup 3}/hr of flue gas produced at the 600 MW coal fired power station Amer-8 situated in Geertruidenberg in the south of the Netherlands. Research so far has proved the process works successfully and at low cost. A second pilot plant due to start-up in May 1995 will provide data on scale up and further information on sulphur recovery. 5 refs., 5 figs.

Mechanical, Hygric and Thermal Properties of Flue Gas Desulfurization Gypsum

Directory of Open Access Journals (Sweden)

P. Tesárek

2004-01-01

Full Text Available The reference measurements of basic mechanical, thermal and hygric parameters of hardened flue gas desulfurization gypsum are carried out. Moisture diffusivity, water vapor diffusion coefficient, thermal conductivity, volumetric heat capacity and linear thermal expansion coefficient are determined with the primary aim of comparison with data obtained for various types of modified gypsum in the future. 

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

International Nuclear Information System (INIS)

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

2011-01-01

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

BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

International Nuclear Information System (INIS)

Unknown

2000-01-01

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

BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

International Nuclear Information System (INIS)

Unknown

1999-01-01

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

Fractionation of mercury stable isotopes during coal combustion and seawater flue gas desulfurization

International Nuclear Information System (INIS)

Huang, Shuyuan; Yuan, Dongxing; Lin, Haiying; Sun, Lumin; Lin, Shanshan

2017-01-01

In the current study, fractionation of mercury isotopes during coal combustion and seawater flue gas desulfurization (SFGD) in a coal-fired power plant using a SFGD system was investigated. Fourteen samples were collected from the power plant. The samples were pretreated with a combustion-trapping method and were analyzed with a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). Compared with the raw coal, the bottom ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −0.45 to −0.03‰. The fly ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −1.49 to −0.73‰ for Chinese coal and from −1.47 to −0.62‰ for Indonesian coal. The δ 202 Hg of fresh seawater and desulfurized seawater was found to be −1.32 and −0.32‰ respectively. These δ 202 Hg values indicated that the desulfurized seawater was enriched with heavier mercury isotopes. Based upon the calculated results obtained from the mass balance equation, it was suggested that the stack emissions were enriched with lighter mercury isotopes. Mass independent fractionation was observed in most of the samples with a Δ 199 Hg/Δ 201 Hg ratio of approximately 0.96. The results help in improving the understanding of mercury isotope fractionation during coal combustion and SFGD, and are also useful in tracing the mercury emissions from coal fired power plants. - Highlights: • Spread of 1.5‰ was observed in δ 202 Hg values of raw coals and coal related samples. • The δ 202 Hg values were more negative in fly ash than those in the raw coal. • The flue gas had a significant Hg fractionation after desulfurization. • The stack emissions were enriched with lighter isotopes compared with the raw coal.

Feasibility Study of Commercial Sorbent in Coal-derived Syngas Desulfurization Field.

Czech Academy of Sciences Publication Activity Database

Chien, H.-Y.; Chyou, Y.-P.; Svoboda, Karel

2015-01-01

Roč. 6, č. 4 (2015), s. 236-242 ISSN 2078-0737 R&D Projects: GA ČR GC14-09692J Grant - others:MOST(TW) NSC 103-2923-E-042A-001 -MY3 Institutional support: RVO:67985858 Keywords : gasification * desulfurization * sorbent Subject RIV: CI - Industrial Chemistry, Chemical Engineering

Biological (flue) gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Buisman, C.J.N.; Dijkman, H. [PAQUES, Balk (Netherlands); Prins, W.L.; Verbraak, P. [Biostar CV, Balk (Netherlands); Den Hartog, A.J. [Hoogovens Groep BV, IJmuiden (Netherlands)

1995-12-31

Biotechnological research has been carried out to find new micro-organisms and processes to make useful products, and to reveal new ways and biotechnological mechanisms to produce elemental sulfur in waste water treatment. Biotechnological development work has been carried out and the first commercial installation (on 300 m{sup 3}/hr scale) to produce sulfur from polluted waste water was started up in 1992. The importance of this recent research and development in the area of waste water treatment was recognized. In an intensive cooperation between Hoogovens Technical Services and PACQUES the concept for a totally new Biological Flue Gas Desulfurization process (BIO-FGD), producing sulfur as by-product, was invented. It consists of the combination of a sodium scrubber with two biological reactors resulting in a very attractive new concept for a gas cleaning process. A description of the process is given and the pilot plant results are outlined. 4 figs., 5 refs.

Desulfurization Activated Phosphorothioate DNAzyme for the Detection of Thallium.

Science.gov (United States)

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

2015-10-20

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

Highly flexible sub-1 nm tungsten oxide nanobelts as efficient desulfurization catalysts.

Science.gov (United States)

He, Jie; Liu, Huiling; Xu, Biao; Wang, Xun

2015-03-01

Ultrathin tungsten oxide nanobelts are successfully synthesized via a facile solvothermal method. Sub-1 nm thickness and hydrophobic surface property endow the nanobelts with flexibility, viscosity, gelation, and good catalytic performance in oxidative desulfurization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasound-assisted oxidative desulfurization process of liquid fuel by phosphotungstic acid encapsulated in a interpenetrating amine-functionalized Zn(II)-based MOF as catalyst.

Science.gov (United States)

Afzalinia, Ahmad; Mirzaie, Abbas; Nikseresht, Ahmad; Musabeygi, Tahereh

2017-01-01

In this work, ultrasound-assisted oxidative desulfurization (UAOD) of liquid fuels performed with a novel heterogeneous highly dispersed Keggin-type phosphotungstic acid (H 3 PW 12 O 40 , PTA) catalyst that encapsulated into an amino-functionalized MOF (TMU-17-NH 2 ). The prepared composite exhibits high catalytic activity and reusability in oxidative desulfurization of model fuel. Ultrasound-assisted oxidative desulfurization (UAOD) is a new way to performed oxidation reaction of sulfur-contain compounds rapidly, economically, environment-friendly and safely, under mild conditions. Ultrasound waves can be apply as an efficient tool to decrease the reaction time and improves oxidative desulfurization system performance. PTA@TMU-17-NH 2 could be completely performed desulfurization of the model oil by 20mg of catalyst, O/S molar ratio of 1:1 in presence of MeCN as extraction solvent. The obtained results indicated that the conversions of DBT to DBTO 2 achieve 98% after 15min in ambient temperature. In this work, we prepared TMU-17-NH 2 and PTA/TMU-17-NH 2 composite by ultrasound irradiation for first time and employed in UAOD process. Prepared catalyst exhibit an excellent reusability without PTA leaching and loss of activity. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

ADVANCED SULFUR CONTROL CONCEPTS FOR HOT-GAS DESULFURIZATION TECHNOLOGY

Energy Technology Data Exchange (ETDEWEB)

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

1998-10-31

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

Advanced sulfur control concepts for hot-gas desulfurization technology

International Nuclear Information System (INIS)

Lopez Ortiz, A.; Harrison, D.P.; Groves, F.R.; White, J.D.; Zhang, S.; Huang, W.N.; Zeng, Y.

1998-01-01

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

Results using flue gas desulfurization gypsum in soilless substrates for greenhouse crops

Science.gov (United States)

Recent availability of Flue Gas Desulfurization gypsum (FGDG) has led to interested in its possible use in horticulture greenhouse production. Three studies were conducted to determine the effects of increasing rates of FGDG on six greenhouse crops. In the first study, substrates (6:1 pine bark:san...

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

Science.gov (United States)

Wu, Zhilin; Ondruschka, Bernd

2010-08-01

Latest environmental regulations require a very deep desulfurization to meet the ultra-low sulfur diesel (ULSD, 15 ppm sulfur) specifications. Due to the disadvantages of hydrotreating technology on the slashing production conditions, costs and safety as well as environmental protection, the ultrasound-assisted oxidative desulfurization (UAOD) as an alternative technology has been developed. UAOD process selectively oxidizes sulfur in common thiophenes in diesel to sulfoxides and sulfones which can be removed via selective adsorption or extractant. SulphCo has successfully used a 5000 barrel/day mobile "Sonocracking" unit to duplicate on a commercial scale its proprietary process that applies ultrasonics at relatively low temperatures and pressures. The UAOD technology estimate capital costs less than half the cost of a new high-pressure hydrotreater. The physical and chemical mechanisms of UAOD process are illustrated, and the effective factors, such as ultrasonic frequency and power, oxidants, catalysts, phase-transfer agent, extractant and adsorbent, on reaction kinetics and product recovery are discussed in this review. Copyright 2009 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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

2014-01-01

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

Optimization of Deep Oxidative Desulfurization Process Using Ionic Liquid and Potassium Monopersulfate

Directory of Open Access Journals (Sweden)

Yinke Zhang

2018-01-01

Full Text Available Response surface methodology (RSM was selected to optimize a desulfurization process with metal based ionic liquids ([Bmim]Cl/CoCl2 and potassium monopersulfate (PMS together to remove benzothiophene (BT from octane (simulating oil. The four experimental conditions of PMS dosage, [Bmim]Cl/CoCl2 dosage, temperature, and reaction time were investigated. The results showed that the quadratic relationship was built up between BT removal and four experimental variables with 0.9898 fitting coefficient. The optimal conditions were 1.6 g (20 wt% PMS solution, 3.2 g [Bmim]Cl/CoCl2, 46°C, and 23 min, which were obtained based on RSM and experimental results. Under the optimal condition, predicted sulfur removal rate and experimental sulfur removal rate were 96.7% and 95.4%, respectively. The sequence of four experimental conditions on desulfurization followed the order temperature > time > [Bmim]Cl/CoCl2 dosage > PMS solution dosage.

Hydrothermal synthesis of Ni{sub 2}P nanoparticle and its hydrodesulfurization of dibenzothiophene

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Han, Yang; Huang, Xiang, E-mail: materials@ouc.edu.cn; Dai, Jinhui; Tian, Jintao; Zhu, Zhibin; Yue, Li [Ocean University of China, Institute of Materials Science and Engineering (China)

2017-04-15

Nanosized nickel phosphide (Ni{sub 2}P) has been synthesized via hydrothermal reaction with environmental-friendly red phosphorus and nickel chloride. The reaction mechanism has been studied by measurement techniques of IC, XRD ,TEM, EDS, and XPS. The results showed that the particle sizes of as-prepared Ni{sub 2}P are in nanoscale ranging from 10 to 30 nm. In hydrothermal reaction, red phosphorus reacts with water to its oxyacids, especially its hypophosphorous acid (or hypophosphite) which can reduce nickel chloride to nickel, and then metallic nickel will penetrate into the rest of red phosphorus to generate nano-Ni{sub 2}P. Furthermore, the catalytic performance of as-synthesized Ni{sub 2}P for the hydrodesulfurization of dibenzothiophene has been tested. It has been shown that the HDS reaction process over Ni{sub 2}P catalyst agrees well with the pseudo-first order kinetic equation, and the HDS conversion can reach up to 43.83% in 5 h with a stable increasing catalytic activity during the whole examination process.

Cometabolic Degradation of Dibenzofuran and Dibenzothiophene by a Naphthalene-Degrading Comamonas sp. JB.

Science.gov (United States)

Ji, Xiangyu; Xu, Jing; Ning, Shuxiang; Li, Nan; Tan, Liang; Shi, Shengnan

2017-12-01

Comamonas sp. JB was used to investigate the cometabolic degradation of dibenzofuran (DBF) and dibenzothiophene (DBT) with naphthalene as the primary substrate. Dehydrogenase and ATPase activity of the growing system with the presence of DBF and DBT were decreased when compared to only naphthalene in the growing system, indicating that the presence of DBF and DBT inhibited the metabolic activity of strain JB. The pathways and enzymes involved in the cometabolic degradation were tested. Examination of metabolites elucidated that strain JB cometabolically degraded DBF to 1,2-dihydroxydibenzofuran, subsequently to 2-hydroxy-4-(3'-oxo-3'H-benzofuran-2'-yliden)but-2-enoic acid, and finally to catechol. Meanwhile, strain JB cometabolically degraded DBT to 1,2-dihydroxydibenzothiophene and subsequently to the ring cleavage product. A series of naphthalene-degrading enzymes including naphthalene dioxygenase, 1,2-dihydroxynaphthalene dioxygenase, salicylaldehyde dehydrogenase, salicylate hydroxylase, and catechol 2,3-oxygenase have been detected, confirming that naphthalene was the real inducer of expression the degradation enzymes and metabolic pathways were controlled by naphthalene-degrading enzymes.

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

Science.gov (United States)

Zhang, Qi; Gui, Keting; Wang, Xiaobo

2016-02-01

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

Enhanced durability and reactivity for zinc ferrite desulfurization sorbent. Volume 1, Bench-scale testing and analysis

Energy Technology Data Exchange (ETDEWEB)

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

1989-05-02

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

The rationalization of desulfurization by on-line analysis

Energy Technology Data Exchange (ETDEWEB)

Murakami, Y; Kohmura, S; Taketomi, H; Matsumura, S; Sasaki, Y

1986-01-01

Nippon Kokan uses the Takahax and Sulfiban processes for the desulfurization of coke oven gas. The authors outline the Sulfiban Process and describe a recently developed system for the on-line determination of H/sub 2/S in coke oven gas, and of CO/sub 2/ and monoethanolamine (MEA) in the wash oil. This new on-line analysis system has proved effective in rationalizing the Sulfiban Process via lower MEA production costs and decreased power consumption. The introduction of a computerized control system is now being studied. 7 figs., 4 tabs.

Simultaneously saccharification and fermentation approach as a tool for enhanced fossil fuels biodesulfurization.

Science.gov (United States)

Paixão, Susana M; Arez, Bruno F; Roseiro, José C; Alves, Luís

2016-11-01

Biodesulfurization can be a complementary technology to the hydrodesulfurization, the commonly physical-chemical process used for sulfur removal from crude oil. The desulfurizing bacterium Gordonia alkanivorans strain 1B as a fructophilic microorganism requires fructose as C-source. In this context, the main goal of this work was the optimization of a simultaneous saccharification and fermentation (SSF) approach using the Zygosaccharomyces bailii strain Talf1 crude enzymes with invertase activity and sucrose as a cheaper fructose-rich commercial C-source (50% fructose) towards dibenzothiophene (DBT) desulfurization by strain 1B. The determination of optimal conditions, for both sucrose hydrolysis and DBT desulfurization was carried out through two sequential experimental uniform designs according to the Doehlert distribution for two factors: pH (5.5-7.5) and temperature (28-38 °C), with the enzyme load of 1.16 U/g/L; and enzyme load (0-4 U/g/L) and temperature (28-38 °C), with pH at 7.5. Based on 2-hydroxybiphenyl production, the analysis of the response surfaces obtained pointed out for pH 7.5, 32 °C and 1.8 U/g/L as optimal conditions. Further optimized SSF of sucrose during the DBT desulfurization process permitted to attain a 4-fold enhanced biodesulfurization. This study opens a new focus of research through the exploitation of sustainable low cost sucrose-rich feedstocks towards a more economical viable bioprocess scale-up. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-12-01

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

Desulfurization and oxidation behavior of ultra-fine CaO particles prepared from brown coal; Kattan wo mochiite choseishita CaO chobiryushi no datsuryu tokusei to sanka tokusei

Energy Technology Data Exchange (ETDEWEB)

Benjamin, G.; Roman, M.; Yamazaki, Y.; Abe, H.; Harano, Y.; Takarada, Y. [Gunma University, Gunma (Japan). Faculty of Engineering

1996-10-28

The effect of reaction temperature and oxygen concentration on the desulfurization and oxidation behavior of ion-exchanged brown coal by Ca as new desulfurizing agent was studied. In experiment, Yallourn coal was used for ion- exchange, and limestone produced in Tochigi prefecture was also used for comparative study. Ca-exchanged brown coal was prepared by agitating coal in Ca(OH)2 slurry for 24 hours. The desulfurization behavior of a desulfurizing agent was obtained by measuring H2S and sulfur compounds in outlet gas of a reactor, and the oxidation behavior by measuring SO2 emission in outlet gas after oxidation reaction. As the experimental result, CaO produced from Ca-exchanged brown coal offered the extremely high activity to desulfurization reaction in a temperature range of 850-950{degree}C as compared with limestone. Although the oxidation behavior was dependent on oxidation temperature and oxygen concentration, CaS obtained from Ca-exchanged brown coal was more rapidly converted to CaSO4 than limestone. 3 refs., 8 figs., 2 tabs.

Effects of pore sizes and oxygen-containing functional groups on desulfurization activity of Fe/NAC prepared by ultrasonic-assisted impregnation

International Nuclear Information System (INIS)

Shu, Song; Guo, Jia-Xiu; Liu, Xiao-Li; Wang, Xue-Jiao; Yin, Hua-Qiang; Luo, De-Ming

2016-01-01

Graphical abstract: - Highlights: • Fe/NAC-60 exhibits the best desulfurization activity. • Different oscillation time can change surface area and pore volume of catalysts. • Ultrasonic oscillation increases Fe dispersion on carrier and effective pores. • Pore sizes play a crucial role during the SO 2 removal. - Abstract: A series of Fe-loaded activated carbons treated by HNO 3 (Fe/NAC) were prepared by incipient impregnation method with or without ultrasonic assistance and characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy with energy disperse spectroscope (SEM-EDS), transmission electron microscopy (TEM) and N 2 adsorption/desorption. The desulfurization activities were evaluated at a fixed bed reactor under a mixed gas simulated from flue gas. The results showed that desulfurization activity from excellent to poor is as follows: Fe/NAC-60 > Fe/NAC-80 > Fe/NAC-30 > Fe/NAC-15 > Fe/NAC-0 > Fe/NAC-100 > NAC. Fe/NAC-60 exhibits the best desulfurization activity and has breakthrough sulfur capacity of 319 mg/g and breakthrough time of 540 min. The introduction of ultrasonic oscillation does not change the form of Fe oxides on activated carbon but can change the dispersion and relative contents of Fe 3 O 4 . The types of oxygen-containing functional groups have no obvious change for all samples but the texture properties show some differences when they are oscillated for different times. The fresh Fe/NAC-60 has a surface area of 1045 m 2 /g and total pore volume of 0.961 cm 3 /g with micropore volume of 0.437 cm 3 /g and is larger than Fe/NAC-0 (823 m 2 /g, 0.733 and 0.342 cm 3 /g). After desulfurization, surface area and pore volume of all samples decrease significantly, and those of the exhausted Fe/NAC-60 decrease to 233 m 2 /g and 0.481 cm 3 /g, indicating that some byproducts deposit on surface to cover pores. Pore size distribution influences SO 2 adsorption, and fresh Fe/NAC-60 has

Molecular dynamics simulations of the effect of NaCl-doping on the calcination characteristics in desulfurization processes

Energy Technology Data Exchange (ETDEWEB)

Murakami, T.; Kurita, N.; Naruse, I. [Toyohashi University of Technology, Toyohashi (Japan)

2003-03-01

Desulfurization performance of wasted seashells was found to be over twice as high as that of limestone, which was currently used as a desulfurizer in fluidized bed coal combustors. NaCl-doping into limestone was also found to be effective in improving the desulfurization efficiency. From X-ray diffraction (XRD) analyses of calcined seashell, limestone and NaCl-doped limestone, on the other hand, not only the calcined seashell but also the NaCl-doped limestone had strong peaks of CaO crystal, and those two materials also had high desulfurization activity. This improvement was hypothesized to be due to NaCl causing a change in the crystal structure of CaO. In order to elucidate the effect of NaCl addition on the CaO crystal structure in the incineration of CaCO{sub 3} the change of structures was simulated by means of molecular dynamics simulations of CaO. In the simulation one molecule of NaCl was exchanged into one molecule of CaO. A pair correlation functions and the distances between Ca and O atoms, which were obtained by the simulations, were compared with those from the crystal CaO. NaCl-doping affected the crystalization temperature of CaO. The crystallization temperature increased due to adding a little bit of NaCl. From the result of the pair correlation functions obtained in NaCl-doped CaO, the difference of the potential energy of NaCl from that of CaO seemed to contribute to the crystallization of the bulk of CaO. The simulation and experimental results obtained suggested that NaCl-doping contributed to crystallizing the CaO molecules.

CONVERSION EXTRACTION DESULFURIZATION (CED) PHASE III

Energy Technology Data Exchange (ETDEWEB)

James Boltz

2005-03-01

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

Investigations in physical mechanism of the oxidative desulfurization process assisted simultaneously by phase transfer agent and ultrasound.

Science.gov (United States)

Bhasarkar, Jaykumar B; Chakma, Sankar; Moholkar, Vijayanand S

2015-05-01

This paper attempts to discern the physical mechanism of the oxidative desulfurization process simultaneously assisted by ultrasound and phase transfer agent (PTA). With different experimental protocols, an attempt is made to deduce individual beneficial effects of PTA and ultrasound on the oxidative desulfurization system, and also the synergy between the effects of PTA and ultrasound. Effect of PTA is more marked for mechanically stirred system due to mass transfer limitations, while intense emulsification due to ultrasound helps overcome the mass transfer limitations and reduces the extent of enhancement of oxidation by PTA. Despite application of PTA and ultrasound, the intrinsic factors and properties of the reactants such as polarity (and hence partition coefficient) and diffusivity have a crucial effect on the extent of oxidation. The intrinsic reactivity of the oxidant also plays a vital role, as seen from the extent of oxidation achieved with performic acid and peracetic acid. The interfacial transport of oxidant in the form of oxidant-PTA complex reduces the undesired consumption of oxidant by the reducing species formed during transient cavitation in organic medium, which helps effective utilization of oxidant towards desulfurization. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhancing mercury removal across air pollution control devices for coal-fired power plants by desulfurization wastewater evaporation.

Science.gov (United States)

Bin, Hu; Yang, Yi; Cai, Liang; Yang, Linjun; Roszak, Szczepan

2017-10-09

Desulfurization wastewater evaporation technology is used to enhance the removal of gaseous mercury (Hg) in conventional air pollution control devices (APCDs) for coal-fired power plants. Studies have affirmed that gaseous Hg is oxidized and removed by selective catalytic reduction (SCR), an electrostatic precipitator (ESP) and wet flue gas desulfurization (WFGD) in a coal-fired thermal experiment platform with WFGD wastewater evaporation. Effects of desulfurization wastewater evaporation position, evaporation temperature and chlorine ion concentration on Hg oxidation were studied as well. The Hg 0 oxidation efficiency was increased ranging from 30% to 60%, and the gaseous Hg removal efficiency was 62.16% in APCDs when wastewater evaporated before SCR. However, the Hg 0 oxidation efficiency was 18.99% and the gaseous Hg removal efficiency was 40.19% in APCDs when wastewater evaporated before ESP. The results show that WFGD wastewater evaporation before SCR is beneficial to improve the efficiency of Hg oxidized and removed in APCDs. Because Hg 2+ can be easily removed in ACPDs and WFGD wastewater in power plants is enriched with chlorine ions, this method realizes WFGD wastewater zero discharge and simultaneously enhances Hg removal in APCDs.

Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

Science.gov (United States)

Wang, Qin; Liang, Xiaoyi; Qiao, Wenming; Liu, Chaojun; Liu, Xiaojun; Zhang, Rui; Ling, Licheng

2009-01-01

Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO 3, (NH 4) 2S 2O 8, H 2O 2 or H 2 to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N 2 adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO 3 and (NH 4) 2S 2O 8 treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H 2O 2 had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO 3 treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H 2O 2 and (NH 4) 2S 2O 8 treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

Preparation, characterization and application in deep catalytic ODS of the mesoporous silica pillared clay incorporated with phosphotungstic acid.

Science.gov (United States)

Li, Baoshan; Liu, Zhenxing; Liu, Jianjun; Zhou, Zhiyuan; Gao, Xiaohui; Pang, Xinmei; Sheng, Huiting

2011-10-15

Mesoporous silica pillared clay (SPC) materials with different contents of H(3)PW(12)O(40) (HPW) heteropoly acid were synthesized by introducing HPW into clay interlayer template in an acidic suspension using sol-gel method. Samples with similar HPW loadings were also prepared by impregnation method using SPC as the support. The results of the characterizations showed that HPW was dispersed more homogeneously in the encapsulated samples than in the impregnated samples. The encapsulated materials exhibited better catalytic performance than the impregnated samples in oxidative desulfurization of dibenzothiophene-containing model oil. The sulfur removal reached up to 98.6% for the model oil under the experiential conditions. Copyright © 2011 Elsevier Inc. All rights reserved.

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

Science.gov (United States)

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

The Desulfurization of Magnetite Ore by Flotation with a Mixture of Xanthate and Dixanthogen

Directory of Open Access Journals (Sweden)

Jun Yu

2016-07-01

Full Text Available The contamination of sulfur emanating from pyrrhotite in magnetite concentrates has been a problem in iron ore processing. This study utilized froth flotation to float pyrrhotite away from magnetite using collectors of xanthate and dixanthogen. It was found that xanthate or dixanthogen alone could not achieve selective separation between pyrrhotite and magnetite in flotation. A high loss of magnetite was obtained with xanthate, while a low desulfurization degree was obtained with dixanthogen. It was interesting that a high desulfurization ratio was achieved with little loss of magnetite when xanthate was mixed with dixanthogen as the collector. The synergistic effect of the mixed collector on pyrrhotite was studied by electrokinectic studies and FTIR measurements. It was found that xanthate was the anchor on pyrrhotite and determined its selectivity against magnetite, while dixanthogen associated with xanthate, enhancing its hydrophobicity. This study provides new insights into the separation of iron minerals.

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

Science.gov (United States)

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

BENCH-SCALE DEMONSTRATION OF HOT-GAS DESULFURIZATION TECHNOLOGY

International Nuclear Information System (INIS)

Unknown

1999-01-01

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

Effects of pore sizes and oxygen-containing functional groups on desulfurization activity of Fe/NAC prepared by ultrasonic-assisted impregnation

Energy Technology Data Exchange (ETDEWEB)

Shu, Song [College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan (China); Guo, Jia-Xiu, E-mail: guojiaxiu@scu.edu.cn [College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan (China); National Engineering Technology Research Center for Flue Gas Desulfurization, Chengdu 610065, Sichuan (China); Sichuan Provincial Environmental Protection Environmental Catalysis and Materials Engineering Technology Center, Chengdu 610065, Sichuan (China); Liu, Xiao-Li [National Engineering Technology Research Center for Flue Gas Desulfurization, Chengdu 610065, Sichuan (China); Wang, Xue-Jiao [College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan (China); Yin, Hua-Qiang [College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan (China); National Engineering Technology Research Center for Flue Gas Desulfurization, Chengdu 610065, Sichuan (China); Sichuan Provincial Environmental Protection Environmental Catalysis and Materials Engineering Technology Center, Chengdu 610065, Sichuan (China); Luo, De-Ming [National Engineering Technology Research Center for Flue Gas Desulfurization, Chengdu 610065, Sichuan (China)

2016-01-01

Graphical abstract: - Highlights: • Fe/NAC-60 exhibits the best desulfurization activity. • Different oscillation time can change surface area and pore volume of catalysts. • Ultrasonic oscillation increases Fe dispersion on carrier and effective pores. • Pore sizes play a crucial role during the SO{sub 2} removal. - Abstract: A series of Fe-loaded activated carbons treated by HNO{sub 3} (Fe/NAC) were prepared by incipient impregnation method with or without ultrasonic assistance and characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy with energy disperse spectroscope (SEM-EDS), transmission electron microscopy (TEM) and N{sub 2} adsorption/desorption. The desulfurization activities were evaluated at a fixed bed reactor under a mixed gas simulated from flue gas. The results showed that desulfurization activity from excellent to poor is as follows: Fe/NAC-60 > Fe/NAC-80 > Fe/NAC-30 > Fe/NAC-15 > Fe/NAC-0 > Fe/NAC-100 > NAC. Fe/NAC-60 exhibits the best desulfurization activity and has breakthrough sulfur capacity of 319 mg/g and breakthrough time of 540 min. The introduction of ultrasonic oscillation does not change the form of Fe oxides on activated carbon but can change the dispersion and relative contents of Fe{sub 3}O{sub 4}. The types of oxygen-containing functional groups have no obvious change for all samples but the texture properties show some differences when they are oscillated for different times. The fresh Fe/NAC-60 has a surface area of 1045 m{sup 2}/g and total pore volume of 0.961 cm{sup 3}/g with micropore volume of 0.437 cm{sup 3}/g and is larger than Fe/NAC-0 (823 m{sup 2}/g, 0.733 and 0.342 cm{sup 3}/g). After desulfurization, surface area and pore volume of all samples decrease significantly, and those of the exhausted Fe/NAC-60 decrease to 233 m{sup 2}/g and 0.481 cm{sup 3}/g, indicating that some byproducts deposit on surface to cover pores. Pore size distribution

Efficient Air Desulfurization Catalysts Derived from Pig Manure Liquefaction Char

Directory of Open Access Journals (Sweden)

Rajiv Wallace

2017-11-01

Full Text Available Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2 was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H2S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H2S removal can be obtained from pig manure liquefaction wastes.

A realistic approach to modeling an in-duct desulfurization process based on an experimental pilot plant study

Energy Technology Data Exchange (ETDEWEB)

Ortiz, F.J.G.; Ollero, P. [University of Seville, Seville (Spain)

2008-07-15

This paper has been written to provide a realistic approach to modeling an in-duct desulfurization process and because of the disagreement between the results predicted by published kinetic models of the reaction between hydrated lime and SO{sub 2} at low temperature and the experimental results obtained in pilot plants where this process takes place. Results were obtained from an experimental program carried out in a 3-MWe pilot plant. Additionally, five kinetic models, from the literature, of the reaction of sulfation of Ca(OH){sub 2} at low temperatures were assessed by simulation and indicate that the desulfurization efficiencies predicted by them are clearly lower than those experimentally obtained in our own pilot plant as well as others. Next, a general model was fitted by minimizing the difference between the calculated and the experimental results from the pilot plant, using Matlab{sup TM}. The parameters were reduced as much as possible, to only two. Finally, after implementing this model in a simulation tool of the in-duct sorbent injection process, it was validated and it was shown to yield a realistic approach useful for both analyzing results and aiding in the design of an in-duct desulfurization process.

Ultrasound-assisted oxidative desulfurization and denitrogenation of liquid hydrocarbon fuels: A critical review.

Science.gov (United States)

Ja'fari, Mahsa; Ebrahimi, Seyedeh Leila; Khosravi-Nikou, Mohammad Reza

2018-01-01

Nowadays, a continuously worldwide concern for development of process to produce ultra-low sulfur and nitrogen fuels have been emerged. Typical hydrodesulfurization and hydrodenitrogenation technology deals with important difficulties such as high pressure and temperature operating condition, failure to treat some recalcitrant compounds and limitations to meet the stringent environmental regulations. In contrary an advanced oxidation process that is ultrasound assisted oxidative desulfurization and denitrogenation satisfies latest environmental regulations in much milder conditions with more efficiency. The present work deals with a comprehensive review on findings and development in the ultrasound assisted oxidative desulfurization and denitrogenation (UAOD) during the last decades. The role of individual parameters namely temperature, residence time, ultrasound power and frequency, pH, initial concentration and types of sulfur and nitrogen compounds on the efficiency are described. What's more another treatment properties that is role of phase transfer agent (PTA) and solvents of extraction step, reaction kinetics, mechanism of the ultrasound, fuel properties and recovery in UAOD are reviewed. Finally, the required future works to mature this technology are suggested. Copyright © 2017 Elsevier B.V. All rights reserved.

Potential Agricultural Uses of Flue Gas Desulfurization Gypsum in the Northern Great Plains

Energy Technology Data Exchange (ETDEWEB)

DeSutter, T.M.; Cihacek, L.J. [North Dakota State University, Fargo, ND (United States). Department of Soil Science

2009-07-15

Flue gas desulfurization gypsum (FGDG) is a byproduct from the combustion of coal for electrical energy production. Currently, FGDG is being produced by 15 electrical generating stations in Alabama, Florida, Indiana, Iowa, Kentucky, Ohio, North Carolina, South Carolina, Tennessee, Texas, and Wisconsin. Much of this byproduct is used in the manufacturing of wallboard. The National Network for Use of FGDG in Agriculture was initiated to explore alternative uses of this byproduct. In the northern Great Plains (North Dakota, South Dakota, and Montana), FGDG has the potential to be used as a Ca or S fertilizer, as an acid soil ameliorant, and for reclaiming or mitigating sodium-affected soils. Greater than 1.4 million Mg of FGDG could initially be used in these states for these purposes. Flue gas desulfurization gypsum can be an agriculturally important resource for helping to increase the usefulness of problem soils and to increase crop and rangeland production. Conducting beneficial use audits would increase the public awareness of this product and help identify to coal combustion electrical generating stations the agriculturally beneficial outlets for this byproduct.

A density functional theory study on the interactions between dibenzothiophene and tetrafluoroborate-based ionic liquids.

Science.gov (United States)

Lin, Jin; Lü, Renqing; Wu, Chongchong; Xiao, Ye; Liang, Fei; Famakinwa, Temilola

2017-04-01

The interactions between dibenzothiophene (DBT) and N-butyl-N-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), N-butyl-N-methylmorpholinium tetrafluoroborate ([Bmmorpholinium][BF 4 ]), N-butyl-N-methylpiperdinium tetrafluoroborate ([BMPiper][BF 4 ]), N-butyl-N-methylpyrrolidinium tetrafluoroborate ([BMPyrro][BF 4 ]), and N-butylpyridinium tetrafluoroborate ([BPY][BF 4 ]) were investigated using density functional theory approach. Geometric, electron, and topological properties were analyzed using natural bond orbital, atoms in molecules theory, and noncovalent interaction methods in order to understand intermolecular interactions between DBT and ionic liquids. The result shows that hydrogen bond and van der Waals interactions are widespread in all the ionic liquids-DBT systems. Ion-π interactions between DBT and cation or anion are also observed, while π + -π interactions are only found in the [BMIM][BF 4 ]-DBT and [BPY][BF 4 ]-DBT systems. The order of interaction energy is [BPY][BF4]-DBT > [BMIM][BF 4 ]-DBT > [BMPiper][BF 4 ]-DBT > [BMPyrro][BF 4 ]-DBT > [BMmorpholinum][BF 4 ]-DBT. The energies between DBT and the two ionic liquids containing aromatic cations are significantly higher.

Dibenzothiophene adsorption at boron doped carbon nanoribbons studied within density functional theory

Energy Technology Data Exchange (ETDEWEB)

López-Albarrán, P. [Facultad de Ingeniería en Tecnología de la Madera, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Navarro-Santos, P., E-mail: pnavarrosa@conacyt.mx [Instituto de Investigaciones Químico-Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Garcia-Ramirez, M. A. [Research Centre for Innovation in Aeronautical Engineering, Universidad Autónoma de Nuevo León, Ciudad Universitaria, San Nicolás de los Garza, CP 66451 Nuevo León (Mexico); Ricardo-Chávez, J. L. [Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa San José 2055, Lomas 4" asección, CP 78216, San Luis Potosí, S. L. P. (Mexico)

2015-06-21

The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC{sub 3} island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

Silver nanocrystal-decorated polyoxometalate single-walled nanotubes as nanoreactors for desulfurization catalysis at room temperature.

Science.gov (United States)

Zhang, Hao; Xu, Xiaobin; Lin, Haifeng; Ud Din, Muhammad Aizaz; Wang, Haiqing; Wang, Xun

2017-09-14

Ultrathin nanocrystals generally provide a remarkable catalytic performance due to their high specific surface area and exposure of certain active sites. However, deactivation caused by growth and gathering limits the catalytic application of ultrathin nanocrystals. Here we report Ag nanocrystal-decorated polyoxometalate (Ag-POM) single-walled nanotubes assembled via a concise, surfactant-free soaking method as a new kind of well-defined core-sheath nanoreactor. The diameter of Ag nanocrystals inside polyoxometalate nanotubes can be controlled via simply adjusting the reactant concentration. Ag-POM provided outstanding oxidative desulfurization (ODS) catalytic performance for aromatic sulfocompounds at room temperature. It was suggested that Ag nanocrystals decorated on the inner surface played a key role in adjusting the electronic distribution and enhancing the catalytic activity. The as-prepared Ag-POM nanotubes are promising candidate catalysts with enhanced performance for practical catalytic applications in the gasoline desulfurization industry.

Applying ACF to desulfurization process from flue gas

International Nuclear Information System (INIS)

Liu Yi; Zhang Zhigang; Tang Qiang; Cao Zidong

2004-01-01

Inasmuch as the status of environmental pollution caused by SO 2 is more and more serious and the policy of environmental protection is executed more and more strictly, desulfurization from flue gas (FGD) is introduced to a wide-spread field of national economy. By a comparison with lime-limestone method, the application of adsorption method in FGD is more effective in desulfurization and more adapted to the situation of our country in respect of its more valuable byproduct. However, the technique of adsorption method is limited by the large amount of adsorbent used. In this paper, activated carbon fiber (ACF) is proposed as a new type of adsorbent to apply in FGD. A series of experiments have been made in order to compare the performances between ACF and granular activated carbon (GAC) which has been mostly used. Experiments show that under the same working conditions ACF's adsorption capacity is 16.6 times as high as that of GAC, mass loss rate is 1/12 of GAC's, desorption efficiency of ACF can reach 99.9%. The theory of micropore adsorption dynamics is adopted to analyze the characteristics of both adsorbents. It is indicated that adsorbability and perfectibility of desorption are tightly related to the distribution of pores and the surface micromechanism of adsorbent surface. The accessibility of pores for specified adsorptive and the effects of capillary condensation are crucial factors to influence the process of FGD. According to the research of different adsorbents, conclusion can be drawn that ACF is a kind of good material with a strong selectivity for SO 2 . Compared with the traditional methods of FGD, the use of ACF can greatly economize the consumption of adsorbent and obviously reduce the introduction of new adsorbent, and at the same time keep down the equipment investment and operating cost. (authors)

Developing clean fuels: Novel techniques for desulfurization

Science.gov (United States)

Nehlsen, James P.

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

Direct Synthesis of H2O2 over Ti-Containing Molecular Sieves Supported Gold Catalysts: A Comparative Study for In-situ-H2O2-ODS of Fuel

International Nuclear Information System (INIS)

Zhang, Han; Song, Haiyan; Chen, Chunxia; Han, Fuqin; Hu, Shaozheng; Liu, Guangliang; Chen, Ping; Zhao, Zhixi

2013-01-01

Direct synthesis of H 2 O 2 and in situ oxidative desulfurization of model fuel over Au/Ti-HMS and Au/TS-1 catalysts has been comparatively investigated in water or methanol. Maximum amount (82%) of active Au 0 species for H 2 O 2 synthesis was obtained. Au/Ti-HMS and Au/TS-1 exhibited the contrary performances in H 2 O 2 synthesis as CH 3 OH/H 2 O ratio of solvent changed. H 2 O 2 decomposition and hydrogenation in water was inhibited by the introduction of methanol. Effect of O 2 /H 2 ratio on H 2 O 2 concentration, H 2 conversion and H 2 O 2 selectivity revealed a relationship between H 2 O 2 generation and H2 consumption. The highest dibenzothiophene removal rate (83.2%) was obtained over Au/Ti-HMS in methanol at 1.5 of O 2 /H 2 ratio and 60 .deg. C. But removal of thiophene over Au/TS-1 should be performed in water without heating to obtain a high removal rate (61.3%). Meanwhile, H 2 conversion and oxidative desulfurization selectivity of H 2 were presented

Desulfurization of fuels with ionic liquids by extraction and oxidative extraction processes

OpenAIRE

Rodríguez Cabo, Borja

2014-01-01

The excessive emission of pollutants to the atmosphere has been a problem during the last few decades due to, among other reasons, the massive use of transports. In order to avoid this problem, many methods are being investigated as an alternative to the classical hydrodesulfurization technique, such as adsorption, biodesulfurization, extraction and oxidation. The extractive desulfurization is one of the most promising alternatives. Moreover, its enhancement with selective oxidation of sulfur...

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

Science.gov (United States)

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

Desulfurization of the exhaust gas with zeolite synthesized from diatomaceous earth

Energy Technology Data Exchange (ETDEWEB)

Miyamoto, M

1975-07-01

Both A type and X type zeolites were prepared from diatomaceous earth and tested for use in flue gas desulfurization. Several diatomaceous earths of known chemical compositions were mixed to obtain a desired molar ratio of silicates, whose maturation was achieved in two steps; room temperature maturation and reflux maturation by heating. If the second maturation was carried out for more than 12 hr, the X type zeolite formation was low. At the best conditions, 80% pure zeolite could be prepared for both types according to their x-ray diffraction spectra. The synthesized x type zeolite adsorbed sulfur dioxide more efficiently than A type zeolite. When a simulated flue gas containing 680 to 840 ppM sulfur dioxide was passed at a flow rate of 9.0 Nl/min through a 250 g zeolite column, the column breaking time (time required for the SO/sub 2/ concentration of the column effluent to reach 10% of the initial SO/sub 2/ concentration) was 5.3 hr, while that for the commercial zeolite and activated carbon was 6.8 hr and 8.0 hr, respectively. If the flue gas contained more than 1% moisture, the adsorbed water reacted with SO/sub 2/ and the zeolite crystal tended to break down. The use of zeolite for flue gas desulfurization was more costly than the use of activated carbon.

Pb(II) removal from aqueous solution by a low-cost adsorbent dry desulfurization slag

Energy Technology Data Exchange (ETDEWEB)

Wu, Qiong; You, Ruirong [College of Materials Science and Engineering, Fuzhou University, New Campus, Minhou, Fujian Province 350108 (China); Clark, Malcolm [Marine Ecology Research Centre, School of Environment, Science and Engineering, Southern Cross University, P.O. Box 157, Lismore, NSW 2480 (Australia); Yu, Yan, E-mail: yuyan_1972@126.com [College of Materials Science and Engineering, Fuzhou University, New Campus, Minhou, Fujian Province 350108 (China)

2014-09-30

Highlights: • Dry desulfurization slag, solid waste, was an efficient adsorbent for lead removal. • The adsorption of Pb{sup 2+} onto dry desulfurization slag was generally monolayer. • The rate limiting step in the adsorption process of Pb{sup 2+} was chemisorption. • Pb{sup 2+} was absorbed onto the surface of the sample adsorbent only. • The adsorbent was low-cost and could be recycled. - Abstract: A collectable and non-sintered material prepared as hollow cylindrical shaped pellet from dry desulfurization slag (FGD ash) and ordinary Portland cement (OPC) for wastewater treatments is tested. The characteristic results of powder X-ray diffraction (XRD) and infrared absorption spectroscopy (IR) show that –OH, CO{sub 3}{sup 2−}, SO{sub 3}{sup 2−} and SO{sub 4}{sup 2−} are the possible functional groups responsible for Pb uptake. Adsorption data indicate that Pb removal is pH dependent and optimal at pH 6, with a very rapid initial removal that reaches equilibrium in about 90 min. A maximum removal of 99.2% is seen for 5 mg/L (pH of 6); higher initial Pb concentrations reduce overall removal efficiencies, but generate higher surface loadings. Adsorption process correlates well with both Langmuir and Freundlich models, although the Langmuir isotherm is more favored, providing a maximum adsorption capacity (Qm) of 130.2 mg/g (13 wt%). Pseudo-second order rate kinetic model best describes the Pb removal, and calculated R{sub L} values between 0 and 1, indicate a favored adsorption process that is chemisorption limited. SEM and EDAX analysis of the surface and fracture surface show that Pb occurs as surface precipitates and that Pb is not distributed to the inner core of the pellet. This study demonstrates that dry FGD ash could be successfully used for wastewater Pb removal.

Enhanced durability and reactivity for zinc ferrite desulfurization sorbent

Energy Technology Data Exchange (ETDEWEB)

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

1989-10-01

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

4,6-Dimethyl-dibenzothiophene conversion over Al{sub 2}O{sub 3}-TiO{sub 2}-supported noble metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Nunez, Sara [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Escobar, Jose, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico); Vazquez, Armando; Reyes, Jose Antonio de los [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Hernandez-Barrera, Melissa [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico)

2011-03-15

Research highlights: {yields} Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with {approx}1 wt% nominal metal loading. {yields} Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). {yields} In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. {yields} Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. {yields} Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with {approx}1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N{sub 2}-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H{sub 2} flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by

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

Science.gov (United States)

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

2012-04-20

A systematic exploration of thiophilic ability of o-iodoxybenzoic acid (IBX) for oxidative desulfurization to trigger domino reactions leading to new methodologies for synthesis of different azoles is described. A variety of highly substituted oxadiazoles, thiadiazoles, triazoles, and tetrazoles have been successfully synthesized in good to excellent yields, starting from readily accessible thiosemicarbazides, bis-diarylthiourea, 1,3-disubtituted thiourea, and thioamides. © 2012 American Chemical Society

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

Science.gov (United States)

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

2015-07-21

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

Evaluation of Synthetic Gypsum Recovered via Wet Flue-Gas Desulfurization from Electric Power Plants for Use in Foundries

Directory of Open Access Journals (Sweden)

R. Biernacki

2012-09-01

Full Text Available This article investigates possible use of waste gypsum (synthetic, recovered via flue-gas desulfurization from coal-fired electric powerplants, in foundries. Energy sector, which in Eastern Europe is mostly composed from coal-fired electric power plants, is one of the largestproducers of sulfur dioxide (SO2.In order to protect the environment and reduce the amount of pollution flue-gas desulfurization (FGD is used to remove SO2 fromexhaust flue gases of fossil-fuel power plants. As a result of this process gypsum waste is produced that can be used in practicalapplications.Strength and permeability tests have been made and also in-depth analysis of energy consumption of production process to investigateways of preparing the synthetic gypsum for casting moulds application. This paper also assesses the chemical composition, strength andpermeability of moulds made with synthetic gypsum, in comparison with moulds made with traditional GoldStar XL gypsum and withceramic molds. Moreover examination of structure of synthetic gypsum, the investigations on derivatograph and calculations of energyconsumption during production process of synthetic gypsum in wet flue-gas desulfurization were made.After analysis of gathered data it’s possible to conclude that synthetic gypsum can be used as a material for casting mould. There is nosignificant decrease in key properties, and on the other hand there is many additional benefits including low energy consumption,decreased cost, and decreased environmental impact.

Aerobic desulfurization of biogas by acidic biotrickling filtration in a randomly packed reactor

International Nuclear Information System (INIS)

Montebello, Andrea M.; Mora, Mabel; López, Luis R.; Bezerra, Tercia; Gamisans, Xavier; Lafuente, Javier; Baeza, Mireia; Gabriel, David

2014-01-01

Highlights: • Desulfurization of high loads of H 2 S is feasible by acidic biotrickling filtration. • Robustness of the process is demonstrated in the long-term (550 d). • Biosulfur to sulfate oxidation under H 2 S starvation was successfully performed. • Lower sulfate production found at acidic pH compared to that at neutral pH. • Plastic material is recommended for long-term acidic biotrickling filtration. - Abstract: Biotrickling filters for biogas desulfurization still must prove their stability and robustness in the long run under extreme conditions. Long-term desulfurization of high loads of H 2 S under acidic pH was studied in a lab-scale aerobic biotrickling filter packed with metallic Pall rings. Reference operating conditions at steady-state corresponded to an empty bed residence time (EBRT) of 130 s, H 2 S loading rate of 52 g S–H 2 S m −3 h −1 and pH 2.50–2.75. The EBRT reduction showed that the critical EBRT was 75 s and the maximum EC 100 g S–H 2 S m −3 h −1 . Stepwise increases of the inlet H 2 S concentration up to 10,000 ppm v lead to a maximum EC of 220 g S–H 2 S m −3 h −1 . The H 2 S removal profile along the filter bed indicated that the first third of the filter bed was responsible for 70–80% of the total H 2 S removal. The oxidation rate of solid sulfur accumulated inside the bioreactor during periodical H 2 S starvation episodes was verified under acidic operating conditions. The performance under acidic pH was comparable to that under neutral pH in terms of H 2 S removal capacity. However, bioleaching of the metallic packing used as support and chemical precipitation of sulfide/sulfur salts occurred

Aerobic desulfurization of biogas by acidic biotrickling filtration in a randomly packed reactor

Energy Technology Data Exchange (ETDEWEB)

Montebello, Andrea M.; Mora, Mabel; López, Luis R.; Bezerra, Tercia [Department of Chemical Engineering, School of Engineering, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Gamisans, Xavier [Department of Mining Engineering and Natural Resources, Universitat Politècnica de Catalunya, Bases de Manresa 61-73, 08240 Manresa (Spain); Lafuente, Javier [Department of Chemical Engineering, School of Engineering, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Baeza, Mireia [Department of Chemistry, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Gabriel, David, E-mail: david.gabriel@uab.cat [Department of Chemical Engineering, School of Engineering, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)

2014-09-15

Highlights: • Desulfurization of high loads of H{sub 2}S is feasible by acidic biotrickling filtration. • Robustness of the process is demonstrated in the long-term (550 d). • Biosulfur to sulfate oxidation under H{sub 2}S starvation was successfully performed. • Lower sulfate production found at acidic pH compared to that at neutral pH. • Plastic material is recommended for long-term acidic biotrickling filtration. - Abstract: Biotrickling filters for biogas desulfurization still must prove their stability and robustness in the long run under extreme conditions. Long-term desulfurization of high loads of H{sub 2}S under acidic pH was studied in a lab-scale aerobic biotrickling filter packed with metallic Pall rings. Reference operating conditions at steady-state corresponded to an empty bed residence time (EBRT) of 130 s, H{sub 2}S loading rate of 52 g S–H{sub 2}S m{sup −3} h{sup −1} and pH 2.50–2.75. The EBRT reduction showed that the critical EBRT was 75 s and the maximum EC 100 g S–H{sub 2}S m{sup −3} h{sup −1}. Stepwise increases of the inlet H{sub 2}S concentration up to 10,000 ppm{sub v} lead to a maximum EC of 220 g S–H{sub 2}S m{sup −3} h{sup −1}. The H{sub 2}S removal profile along the filter bed indicated that the first third of the filter bed was responsible for 70–80% of the total H{sub 2}S removal. The oxidation rate of solid sulfur accumulated inside the bioreactor during periodical H{sub 2}S starvation episodes was verified under acidic operating conditions. The performance under acidic pH was comparable to that under neutral pH in terms of H{sub 2}S removal capacity. However, bioleaching of the metallic packing used as support and chemical precipitation of sulfide/sulfur salts occurred.

Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

Energy Technology Data Exchange (ETDEWEB)

Wang Qin [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China); Liang Xiaoyi [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China)], E-mail: xyliang@ecust.edu.cn; Qiao Wenming; Liu Chaojun; Liu Xiaojun; Zhang Rui; Ling Licheng [State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China)

2009-01-01

Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO{sub 3}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8}, H{sub 2}O{sub 2} or H{sub 2} to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N{sub 2} adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO{sub 3} and (NH{sub 4}){sub 2}S{sub 2}O{sub 8} treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H{sub 2}O{sub 2} had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO{sub 3} treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H{sub 2}O{sub 2} and (NH{sub 4}){sub 2}S{sub 2}O{sub 8} treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

Multiphase Modeling of Bottom-Stirred Ladle for Prediction of Slag-Steel Interface and Estimation of Desulfurization Behavior

Science.gov (United States)

Singh, Umesh; Anapagaddi, Ravikiran; Mangal, Saurabh; Padmanabhan, Kuppuswamy Anantha; Singh, Amarendra Kumar

2016-06-01

Ladle furnace is a key unit in which various phenomena such as deoxidation, desulfurization, inclusion removal, and homogenization of alloy composition and temperature take place. Therefore, the processes present in the ladle play an important role in determining the quality of steel. Prediction of flow behavior of the phases present in the ladle furnace is needed to understand the phenomena that take place there and accordingly control the process parameters. In this study, first a mathematical model is developed to analyze the transient three-phase flow present. Argon gas bottom-stirred ladle with off-centered plugs has been used in this study. Volume of fluid method is used in a computational fluid dynamics (CFD) model to capture the behavior of slag, steel, and argon interfaces. The results are validated with data from literature. Eye opening and slag-steel interfacial area are calculated for different operating conditions and are compared with experimental and simulated results cited in literature. Desulfurization rate is then predicted using chemical kinetic equations, interfacial area, calculated from CFD model, and thermodynamic data, obtained from the Thermo-Calc software. Using the model, it is demonstrated that the double plug purging is more suitable than the single plug purging for the same level of total flow. The advantage is more distinct at higher flow rates as it leads higher interfacial area, needed for desulfurization and smaller eye openings (lower oxygen/nitrogen pickup).

GRANULATION AND BRIQUETTING OF SOLID PRODUCTS FROM FLUE GAS DESULFURIZATION

Directory of Open Access Journals (Sweden)

Jan J. Hycnar

2015-11-01

Full Text Available Most flue gas desulfurization products can be characterized by significant solubility in water and dusting in dry state. These characteristics can cause a considerable pollution of air, water, and soil. Among many approaches to utilization of this waste, the process of agglomeration using granulation or briquetting has proved very effective. Using desulfurization products a new material of aggregate characteristics has been acquired, and this material is resistant to water and wind erosion as well as to the conditions of transportation and storage. The paper presents the results of industrial trials granulation and briquetting of calcium desulphurization products. The granulation of a mixture of phosphogypsum used with fly ash (in the share 1:5. The resulting granules characterized by a compressive strength of 41.6 MPa, the damping resistance of 70% and 14.2% abrasion. The granulate was used for the production of cement mix. The produced concrete mortar have a longer setting and hardening time, as compared to the traditional ash and gypsum mortar, and have a higher or comparable flexural and compressive strength during hardening. Briquetting trials made of a product called synthetic gypsum or rea-gypsum both in pure form and with the addition of 5% and 10% of the limestone dust. Briquettes have a high initial strength and resistance to abrasion. The values ​​of these parameters increased after 72 hours of seasoning. It was found that higher hardiness of briquettes with rea-gypsum was obtained with the impact of atmospheric conditions and higher resistance to elution of water-soluble components in comparison to ash briquettes.

Descending projections from the dysgranular zone of rat primary somatosensory cortex processing deep somatic input.

Science.gov (United States)

Lee, Taehee; Kim, Uhnoh

2012-04-01

In the mammalian somatic system, peripheral inputs from cutaneous and deep receptors ascend via different subcortical channels and terminate in largely separate regions of the primary somatosensory cortex (SI). How these inputs are processed in SI and then projected back to the subcortical relay centers is critical for understanding how SI may regulate somatic information processing in the subcortex. Although it is now relatively well understood how SI cutaneous areas project to the subcortical structures, little is known about the descending projections from SI areas processing deep somatic input. We examined this issue by using the rodent somatic system as a model. In rat SI, deep somatic input is processed mainly in the dysgranular zone (DSZ) enclosed by the cutaneous barrel subfields. By using biotinylated dextran amine (BDA) as anterograde tracer, we characterized the topography of corticostriatal and corticofugal projections arising in the DSZ. The DSZ projections terminate mainly in the lateral subregions of the striatum that are also known as the target of certain SI cutaneous areas. This suggests that SI processing of deep and cutaneous information may be integrated, to a certain degree, in this striatal region. By contrast, at both thalamic and prethalamic levels as far as the spinal cord, descending projections from DSZ terminate in areas largely distinguishable from those that receive input from SI cutaneous areas. These subcortical targets of DSZ include not only the sensory but also motor-related structures, suggesting that SI processing of deep input may engage in regulating somatic and motor information flow between the cortex and periphery. Copyright © 2011 Wiley-Liss, Inc.

Oxidation of dibenzothiophene (DBT by Serratia marcescens UCP 1549 formed biphenyl as final product

Directory of Open Access Journals (Sweden)

de Araújo Hélvia W

2012-05-01

Full Text Available Abstract Background The desulphurization of dibenzothiophene (DBT, a recalcitrant thiophenic fossil fuel component by Serratia marcescens (UCP 1549 in order for reducing the Sulphur content was investigated. The Study was carried out establishing the growth profile using Luria Bertani medium to different concentrations of DBT during 120 hours at 28°C, and orbital Shaker at 150 rpm. Results The results indicated that concentrations of DBT 0.5, 1.0 and 2.0 mM do not affected the growth of the bacterium. The DBT showed similar Minimum Inhibitory Concentration (MIC and Minimum Bactericidal Concentration (MCB (3.68 mM. The desulphurization of DBT by S. marcescens was used with 96 hours of growth on 2 mM of DBT, and was determined by gas chromatography (GC and GC-mass spectrometry. In order to study the desulphurization process by S. marcescens was observed the presence of a sulfur-free product at 16 hours of cultivation. Conclusions The data suggests the use of metabolic pathway “4S” by S. marcescens (UCP 1549 and formed biphenyl. The microbial desulphurization process by Serratia can be suggest significant reducing sulphur content in DBT, and showed promising potential for reduction of the sulfur content in diesel oil.

Impact of Leaching Conditions on Constituents Release from Flue Gas Desulfurization Gypsum (FGDG) and FGDG-Soil Mixture

Science.gov (United States)

The interest in using Flue Gas Desulfurization Gypsum(FGDG) has increased recently. This study evaluates the leaching characteristics of trace elements in "modern" FGDG (produced after fly ash removal) and FGDG-mixed soil (SF) under different environmental conditions using rece...

THE BIOCATALYTIC DESULFURIZATION PROJECT

Energy Technology Data Exchange (ETDEWEB)

Steven E. Bonde; David Nunn

2003-01-01

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

Desulfurization of 2-thiouracil nucleosides: conformational studies of 4-pyrimidinone nucleosides.

Science.gov (United States)

Kraszewska, Karina; Kaczyńska, Iwona; Jankowski, Stefan; Karolak-Wojciechowska, Janina; Sochacka, Elzbieta

2011-04-01

4-Pyrimidinone ribofuranoside (H(2)o(4)U) and 4-pyrimidinone 2'-deoxyribofuranoside (dH(2)o(4)U) were synthesized by the oxidative desulfurization of parent 2-thiouracil nucleosides with m-chloroperbenzoic acid. The crystal structures of H(2)o(4)U and dH(2)o(4)U and their conformations in solution were determined and compared with corresponding 2-thiouracil and uracil nucleosides. The absence of a large 2-thiocarbonyl/2-carbonyl group in the nucleobase moiety results in C2'-endo puckering of the ribofuranose ring (S conformer) in the crystal structure of H(2)o(4)U, which is not typical of RNA nucleosides. Interestingly, the hydrogen bonding network in the crystals of dH(2)o(4)U stabilizes the sugar moiety conformation in the C3'-endo form (N conformer), rarely found in DNA nucleosides. In aqueous solution, dH(2)o(4)U reveals a similar population of the C2'-endo conformation (65%) to that of 2'-deoxy-2-thiouridine (62%), while the 62% population of the S conformer for H(2)o(4)U is significantly different from that of the parent 2-thiouridine, for which the N conformer is dominant (71%). Such a difference may be of biological importance, as the desulfurization process of natural tRNA 2-thiouridines may occur under conditions of oxidative stress in the cell and may influence the decoding process. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Desulfurization and denitrogenation of coal during multi-stage hydropyrolysis

Energy Technology Data Exchange (ETDEWEB)

Wang, N.; Li, W.; Li, B. [Chinese Academy of Sciences, Taiyuan (China). State Key Lab of Coal Conversion

2001-02-01

The elemental composition of char of high sulfur Hongmiao coal in multi-stage hydropyrolysis (MHyPy) with different heating rates were analysed and compared with that from normal hydropyrolysis (HyPy). The results illustrated that the sulfur removal in MHyPy was greater than that in HyPy, and more sulfur was evolved as the easily recycled gas H{sub 2}S. Similar with the situation of sulfur, more nitrogen transferred to the gas phase easily to be dealt with and the clean char was obtained. During MHyPy the extent of desulfurization and denitrogenation was more remarkable at high rate than that at slow heating rate. 8 refs., 2 figs., 2 tabs.

Increasing draft capability for retrofit flue gas desulfurization systems

International Nuclear Information System (INIS)

Petersen, R.D.; Basel, B.E.; Mosier, R.J.

1992-01-01

The retrofit installation of flue gas desulfurization (FGD) systems results in significantly higher draft losses for existing generating stations. Consequently, the means for increasing draft capability must be included in many FGD retrofit projects. Consideration is given to several alternatives for increasing draft capability. Alternatives are developed for new induced draft (ID) fans to replace the existing ID fans and for new booster fans to supplement the existing ID fans. Both centrifugal and axial fans are evaluated, as are different means of fan volume control. Each alternative is evaluated on the basis of technical merit and economics. Presented are the development of fan alternatives and results of the technical and economic evaluations

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

International Nuclear Information System (INIS)

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

1995-01-01

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

Oxidative desulfurization of thiophene on TiO2/ZSM-12 zeolite

OpenAIRE

Santos,Marília Ramalho Figueiredo dos; Pedrosa,Anne Michelle Garrido; Souza,Marcelo José Barros de

2016-01-01

In this work the hydrothermal synthesis of ZSM-12 zeolite was performed, varying the MTEACl/SiO2 ratio, where the synthesis temperature was 140 ºC and the crystallization time was 144 hours. The catalysts were characterized by XRD, FTIR and TG. TiO2/ZSM-12 catalysts were used with titanium ions concentrations of 5, 10 and 15%. The oxidative desulfurization (ODS) reactions were performed using a model mixture containing n-heptane as solvent and thiophene as sulfur compound, H2O2 as an oxidizin...

Land application uses for dry flue gas desulfurization by-products: Phase 3

Energy Technology Data Exchange (ETDEWEB)

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

1999-01-31

New flue gas desulfurization (FGD) scrubbing technologies create a dry, solid by-product material consisting of excess sorbent, reaction product that contains sulfate and sulfite, and coal fly ash. Generally, dry FGD by-products are treated as solid wastes and disposed in landfills. However, landfill sites are becoming scarce and tipping fees are constantly increasing. Provided the environmental impacts are socially and scientifically acceptable, beneficial uses via recycling can provide economic benefits to both the producer and the end user of the FGD. A study titled ''Land Application Uses for Dry Flue Gas Desulfurization By-Products'' was initiated in December, 1990 to develop and demonstrate large volume, beneficial uses of FGD by-products. Phase 1 and Phase 2 reports have been published by the Electric Power Research Institute (EPRI), Palo Alto, CA. Phase 3 objectives were to demonstrate, using field studies, the beneficial uses of FGD by-products (1) as an amendment material on agricultural lands and on abandoned surface coal mine land, (2) as an engineering material for soil stabilization and raid repair, and (3) to assess the environmental and economic impacts of such beneficial uses. Application of dry FGD by-product to three soils in place of agricultural limestone increased alfalfa (Medicago sativa L.) and corn (Zea may L.) yields. No detrimental effects on soil and plant quality were observed.

A fiber optics system for monitoring utilization of ZnO adsorbent beds during desulfurization for logistic fuel cell applications

Science.gov (United States)

Sujan, Achintya; Yang, Hongyun; Dimick, Paul; Tatarchuk, Bruce J.

2016-05-01

An in-situ fiber optic based technique for direct measurement of capacity utilization of ZnO adsorbent beds by monitoring bed color changes during desulfurization for fuel cell systems is presented. Adsorbents composed of bulk metal oxides (ZnO) and supported metal oxides (ZnO/SiO2 and Cusbnd ZnO/SiO2) for H2S removal at 22 °C are examined. Adsorbent bed utilization at breakthrough is determined by the optical sensor as the maximum derivative of area under UV-vis spectrum from 250 to 800 nm observed as a function of service time. Since the response time of the sensor due to bed color change is close to bed breakthrough time, a series of probes along the bed predicts utilization of the portion of bed prior to H2S breakthrough. The efficacy of the optical sensor is evaluated as a function of inlet H2S concentration, H2S flow rate and desulfurization in presence of CO, CO2 and moisture in feed. A 6 mm optical probe is employed to measure utilization of a 3/16 inch ZnO extrudate bed for H2S removal. It is envisioned that with the application of the optical sensor, desulfurization can be carried out at high adsorbent utilization and low operational costs during on-board miniaturized fuel processing for logistic fuel cell power systems.

Advances on simultaneous desulfurization and denitrification using activated carbon irradiated by microwaves.

Science.gov (United States)

Ma, Shuang-Chen; Gao, Li; Ma, Jing-Xiang; Jin, Xin; Yao, Juan-Juan; Zhao, Yi

2012-06-01

This paper describes the research background and chemistry of desulfurization and denitrification technology using microwave irradiation. Microwave-induced catalysis combined with activated carbon adsorption and reduction can reduce nitric oxide to nitrogen and sulfur dioxide to sulfur from flue gas effectively. This paper also highlights the main drawbacks of this technology and discusses future development trends. It is reported that the removal of sulfur dioxide and nitric oxide using microwave irradiation has broad prospects for development in the field of air pollution control.

Report on coal refining and chemical equipment analogous to coal liquefaction equipment in fiscal 1981. Maintenance of equipment for direct desulfurization, indirect desulfurization, and fluidized catalytic cracking; 1981 nendo sekitan ekika ruiji seiyu seisei oyobi kagaku sochi ni kansuru chosa hokokusho. Chokudatsu, kandatsu, ryudo sesshoku bunkai sochi no hozen

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-07-01

This questionnaire survey was intended to investigate the actual state of maintenance such as materials used, conditions for use, anti-corrosion measures, and cases and handling of damage, concerning primary apparatus in the direct/indirect desulfurization equipment and the fluidized catalytic crackers, which are owned by each oil refinery and which are analogous to coal liquefaction equipment. The questionnaire was intended for the following equipment and apparatus, with the actual state of their maintenance investigated. 1. Questionnaire concerning maintenance of direct desulfurization (reactor, high temperature separation tank, material furnace tube, reactor exit piping, high temperature heat exchanger, low temperature heat exchanger, and pressure reducing valve), 2. Questionnaire concerning maintenance of indirect desulfurization (reactor, high temperature separation tank, material furnace tube, reactor exit piping, high temperature heat exchanger, low temperature heat exchanger, and pressure reducing valve), 3. Questionnaire concerning maintenance of fluidized catalytic cracker (reactor, regeneration tower, riser pipe, and fractionator bottom pump). The questionnaire this time was distributed to 27 domestic oil companies, with the reply received from 23 of them. The replies were summarized by each type of equipment. Shown at the back of the report were the cases of damage and handling in FCC's and reactors. (NEDO)

Effects of foaming and antifoaming agents on the performance of a wet flue gas desulfurization pilot plant

DEFF Research Database (Denmark)

Qin, Siqiang; Hansen, Brian Brun; Kiil, Søren

2014-01-01

Foaming is a common phenomenon in industrial processes, including wet flue gas desulfurization (FGD) plants. A systemic investigation of the influence of two foaming agents, sodium dodecyl sulphate (SDS) and egg white albumin (protein), and two commercial antifoams on a wet FGD pilot plant...

Effect of the type of ammonium salt on the extractive desulfurization of fuels using deep eutectic solvents

NARCIS (Netherlands)

Warrag, Samah E.E.; Adeyemi, Idowu; Rodriguez, Nerea R.; Nashef, Inas M.; van Sint Annaland, Martin; Kroon, Maaike C.; Peters, Cor J.

2018-01-01

In a previous work, we proved that the deep eutectic solvents (DESs) consisting of mixtures of tetraalkylammonium salts with polyols are promising candidates for oil desulfurization based on the obtained liquid-liquid equilibrium (LLE) data. In this study, the capability of DESs containing other

Carbothermal reduction of Ti-modified IRMOF-3: an adaptable synthetic method to support catalytic nanoparticles on carbon.

Science.gov (United States)

Kim, Jongsik; McNamara, Nicholas D; Her, Theresa H; Hicks, Jason C

2013-11-13

This work describes a novel method for the preparation of titanium oxide nanoparticles supported on amorphous carbon with nanoporosity (Ti/NC) via the post-synthetic modification of a Zn-based MOF with an amine functionality, IRMOF-3, with titanium isopropoxide followed by its carbothermal pyrolysis. This material exhibited high purity, high surface area (>1000 m(2)/g), and a high dispersion of metal oxide nanoparticles while maintaining a small particle size (~4 nm). The material was shown to be a promising catalyst for oxidative desulfurization of diesel using dibenzothiophene as a model compound as it exhibited enhanced catalytic activity as compared with titanium oxide supported on activated carbon via the conventional incipient wetness impregnation method. The formation mechanism of Ti/NC was also proposed based on results obtained when the carbothermal reduction temperature was varied.

Two-Phase Phenomena In Wet Flue Gas Desulfurization Process

International Nuclear Information System (INIS)

Minzer, U.; Moses, E.J.; Toren, M.; Blumenfeld, Y.

1998-01-01

In order to reduce sulfur oxides discharge, Israel Electric Corporation (IEC) is building a wet Flue Gas Desulfurization (FGD) facility at Rutenberg B power station. The primary objective of IEC is to minimize the occurrence of stack liquid discharge and avoid the discharge of large droplets, in order to prevent acid rain around the stack. Liquid discharge from the stack is the integrated outcome of two-phase processes, which are discussed in this work. In order to estimate droplets discharge the present investigation employs analytical models, empirical tests, and numerical calculations of two-phase phenomena. The two-phase phenomena are coupled and therefore cannot be investigated separately. The present work concerns the application of Computational Fluid Dynamic (CFD) as an engineering complementary tool in the IEC investigation

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

Science.gov (United States)

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

The functionalities of Pt/{gamma}-Al{sub 2}O{sub 3} catalysts in simultaneous HDS and HDA reactions

Energy Technology Data Exchange (ETDEWEB)

V.G. Baldovino-Medrano; Sonia A. Giraldo; Aristobulo Centeno [Universidad Industrial de Santander (UIS), Bucaramanga (Colombia). Centro de Investigaciones en Catalisis (CICAT)

2008-08-15

A Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was tested in simultaneous hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of naphthalene reactions. Samples of it were subjected to different pretreatments: reduction, reduction-sulfidation, sulfidation with pure H{sub 2}S and non-activation. The reduced catalyst presented the best performance, even comparable to that of Co(Ni)Mo catalysts. All catalyst samples were selective to the HDS reaction over HDA, and to the direct desulfurization pathway of dibenzothiophene HDS over the hydrogenation reaction pathway of HDS. The effect of H{sub 2}S partial pressure on the functionalities of the reduced Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied. The results showed that an increase in H{sub 2}S partial pressure does not cause poisoning, but an inhibition effect, without changing the catalyst selectivity. Accordingly, the activity trends were ascribed to adsorption differences between the different reactive molecules over the same catalytic active site. TPR characterization along with a thermodynamics analysis showed that the active phase of reduced Pt/{gamma}-Al{sub 2}O{sub 3} is constituted by Pt{sup 0} particles. However, presulfidation of the catalyst leads to a mixture of PtS and Pt{sup 0}which has a negative effect on the catalytic performance without changing catalyst functionalities. 61 refs., 4 figs., 1 tab.

Direct Synthesis of H{sub 2}O{sub 2} over Ti-Containing Molecular Sieves Supported Gold Catalysts: A Comparative Study for In-situ-H{sub 2}O{sub 2}-ODS of Fuel

Energy Technology Data Exchange (ETDEWEB)

Zhang, Han; Song, Haiyan; Chen, Chunxia; Han, Fuqin; Hu, Shaozheng [Northeast Forestry Univ., Harbin (China); Liu, Guangliang [Univ. of Connecticut, Storrs (United States); Chen, Ping; Zhao, Zhixi [Xinjiang Normal Univ., Urumqi (China)

2013-10-15

Direct synthesis of H{sub 2}O{sub 2} and in situ oxidative desulfurization of model fuel over Au/Ti-HMS and Au/TS-1 catalysts has been comparatively investigated in water or methanol. Maximum amount (82%) of active Au{sup 0} species for H{sub 2}O{sub 2} synthesis was obtained. Au/Ti-HMS and Au/TS-1 exhibited the contrary performances in H{sub 2}O{sub 2} synthesis as CH{sub 3}OH/H{sub 2}O ratio of solvent changed. H{sub 2}O{sub 2} decomposition and hydrogenation in water was inhibited by the introduction of methanol. Effect of O{sub 2}/H{sub 2} ratio on H{sub 2}O{sub 2} concentration, H{sub 2} conversion and H{sub 2}O{sub 2} selectivity revealed a relationship between H{sub 2}O{sub 2} generation and H2 consumption. The highest dibenzothiophene removal rate (83.2%) was obtained over Au/Ti-HMS in methanol at 1.5 of O{sub 2}/H{sub 2} ratio and 60 .deg. C. But removal of thiophene over Au/TS-1 should be performed in water without heating to obtain a high removal rate (61.3%). Meanwhile, H{sub 2} conversion and oxidative desulfurization selectivity of H{sub 2} were presented.

Development of a portable, modular unit for the optimization of ultrasound-assisted oxidative desulfurization of diesel

Science.gov (United States)

Wan, Meng-Wei

Due to the stringent rules requiring ultra-low sulfur content in diesel fuels, it is necessary to develop alternative methods of desulfurization of fossil fuel derived oil, such as diesel. Current technology is not sufficient to solve this problem. Ultrasound applied to oxidative desulfurization which combined three complementary techniques: ultrasonication, phase transfer catalysis (PTC) and transition metal catalyzed oxidation, has accomplished high sulfur removal in a short contact time at ambient temperature and atmospheric pressure. This research has successfully demonstrated that the higher oxidation efficiency of BT to BTO and free of any by-products by using tetraoctylammonium fluoride as phase transfer agent. The oxidation rate of BT to BTO increased with increasing the carbon chain length of QAS cations. Under the same length of carbon chain, the oxidation rate of BT to BTO increased with decreasing the molecular size of QAS anions. Moreover, for diesel fuels containing various levels of sulfur content, UAOD process followed by solvent extraction has demonstrated that the sulfur reduction can reach above 95 % removal efficiency or final sulfur content below 15 ppm in mild condition. For large-scale commercial production, this research has successfully developed and operated a continuous desulfurization unit, which consists of a sonoractor, an RF amplifier, a function generator, a pretreatment tank, and a pipeline system. A single unit only needed 2' x 4' x 1' space for installation. The results indicated that the remarkable 92% removal efficiency for the sulfur in marine logistic diesel, even at a treatment rate as high as 25 lb/hour which is approximately 2 barrels per day. Therefore, this sonoreactor demonstrated the feasibility of large-scale operation even in a relatively small installation with low capital investment and maintenance cost. It also ensures the safety considerations by operating with diluted hydrogen peroxide under ambient temperature

A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization.

Science.gov (United States)

Du, Shuting; Li, Fen; Sun, Qiming; Wang, Ning; Jia, Mingjun; Yu, Jihong

2016-02-25

Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

Science.gov (United States)

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Effects of surface acidities of MCM-41 modified with MoO3 on adsorptive desulfurization of gasoline

International Nuclear Information System (INIS)

Shao Xinchao; Zhang Xiaotong; Yu Wenguang; Wu Yuye; Qin Yucai; Sun Zhaolin; Song Lijuan

2012-01-01

Highlights: ► The MoO 3 -MCM-41 samples prepared by spontaneous monolayer dispersion and impregnation with a different MoO 3 filling have been studied. ► The relative concentration of hydroxyl groups present on before and after containing MoO 3 samples was monitored by in situ FTIR to speculate the bonding style of MoO 3 and MCM-41. ► The surface acidities of the MoO 3 -MCM-41 adsorbents were investigated systematically and correlated with the desulfurization performance. - Abstract: A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N 2 adsorption–desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO 3 can be highly dispersed up to 0.2 g g −1 in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO 3 contents of 0.26 and 0.32 g g −1 with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO 3 particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO 3 species is related to the abundant surface hydroxy of MCM-41. The host species and guest species undergo solid-state reaction to form Si-O-Mo bonds in the mixtures which enhance both the Lewis acid and Brönsted acid of

A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

Science.gov (United States)

Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

2016-01-04

Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

Electrochemical flue gas desulfurization: Reactions in a pyrosulfate-based electrolyte

International Nuclear Information System (INIS)

Scott, K.; Fannon, T.; Winnick, J.

1988-01-01

A new electrolyte has been found suitable for use in an electrochemical membrane cell for flue gas desulfurization (FGD). The electrolyte is primarily K/sub 2/S/sub 2/O/sub 7/ and K/sub 2/SO/sub 4/ with V/sub 2/O/sub 5/ as oxidation enhancer. This electrolyte has a melting point near 300/sup 0/C which is compatible with flue gas exiting the economizer of coal-burning power plants. Standard electrochemical tests have revealed high exchange current densities around 30 mA/cm/sup 2/, in the free electrolyte. Sulfur dioxide is found to be removed from simulated flue gas in a multiple-step process, the first of which is electrochemical reduction of pyrosulfate

Fiscal 2000 project of inviting proposals for international joint research - invitation for international proposal (Power generation No.1). Achievement report on development of novel high-performance dry type desulfurization agent made from coal ash; 2000 nendo kokusai kyodo kenkyu teian kobo jigyo - kokusai teian kobo (hatsuden No.1). Sekitanbai wo genryo to suru shinki koseino kanshiki datsuryuzai no kaihatsu to riyo seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

Efforts are made to develop a technology of using quicklime instead of slaked lime for a reduction in desulfurization cost, based on the technology of the coal ash utilizing dry type desulfurization device operating on coal ash, slaked lime, and gypsum, as hardened by hydration. Activities are conducted in the three fields of (1) basic study, (2) desulfurization agent bench-scale manufacturing test, and (3) study for putting the technology to practical application. In field (1), the basics are studied of the lime slaking process in the manufacture of a dry type desulfurization agent from quicklime, the mechanism is elucidated of the generation of active desulfurization substances, and effective utilization is studied of the desulfurization agent after use. In field (3), conceptual designs are prepared, cost efficiency of desulfurization systems are evaluated, simplified absorption systems are studied, and the trends of dry type desulfurization systems are surveyed. The cost of desulfurization under development is equivalent to that of the wet type method (limestone-gypsum system) when the used desulfurization agent is discarded, and is approximately 60% of the wet type method when the whole amount is effectively utilized. (NEDO)

(18)O(2) label mechanism of sulfur generation and characterization in properties over mesoporous Sm-based sorbents for hot coal gas desulfurization.

Science.gov (United States)

Liu, B S; Wan, Z Y; Wang, F; Zhan, Y P; Tian, M; Cheung, A S C

2014-02-28

Using a sol-gel method, SmMeOx/MCM-41 or SBA-15 (Me=Fe, Co and Zn) and corresponding unsupported sorbents were prepared. The desulfurization performance of these sorbents was evaluated over a fixed-bed reactor and the effects of reaction temperature, feed and sorbent composition on desulfurization performance were studied. Samarium-based sorbents used to remove H2S from hot coal gas were reported for the first time. The results of successive sulfidation/regeneration cycles revealed that SmFeO3/SBA-15 sorbent was suitable for desulfurization of hot coal gas in the chemical industry. The formation of elemental sulfur during both sulfidation and regeneration processes depended strongly on the catalytic action of Sm2O2S species, which was confirmed for the first time via high sensitive time of flight mass spectrometer (TOF-MS) using 6%vol(18)O2/Ar regeneration gas and can reduce markedly procedural complexity. The sorbents were characterized using N2-adsorption, high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), thermogravimetry (TG) and time-of-flight mass spectrometry (TOF-MS) techniques. Copyright © 2014 Elsevier B.V. All rights reserved.

Prediction of desulfurization in torpedo gas from laboratory scale simulation; Previsao da dessulfuracao do gusa em carro-torpedo a partir de simulacoes em escala de laboratorio

Energy Technology Data Exchange (ETDEWEB)

Souza Costa, Sergio L. de [USIMINAS, Ipatinga, MG (Brazil). Centro de Pesquisa e Desenvolvimento; Figueira, Renato M. [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Escola de Engenharia

1996-12-31

A general criterion for laboratory scale data transposing to industrial practice, based on Navier-Stokes equation is developed. The criterion is a dimensional relation between the rate of energy dissipation, dimensions such as the height and diameter of the reactor and the inertial forces. The criterion was used to predict the evolution of the pig iron desulfurization reaction in torpedo car from results obtained in laboratory scale. The agreement between values predicted from laboratory experiments and data generated from actual industrial desulfurization operation is excellent. (author) 10 refs., 5 figs., 7 tabs.

Polymer-bound oxidovanadium(IV) and dioxidovanadium(V) complexes as catalysts for the oxidative desulfurization of model fuel diesel.

Science.gov (United States)

Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Kuznetsov, Maxim L; Avecilla, Fernando; Costa Pessoa, João

2010-07-19

The Schiff base (Hfsal-dmen) derived from 3-formylsalicylic acid and N,N-dimethyl ethylenediamine has been covalently bonded to chloromethylated polystyrene to give the polymer-bound ligand, PS-Hfsal-dmen (I). Treatment of PS-Hfsal-dmen with [V(IV)O(acac)(2)] in the presence of MeOH gave the oxidovanadium(IV) complex PS-[V(IV)O(fsal-dmen)(MeO)] (1). On aerial oxidation in methanol, complex 1 was oxidized to PS-[V(V)O(2)(fsal-dmen)] (2). The corresponding neat complexes, [V(IV)O(sal-dmen)(acac)] (3) and [V(V)O(2)(sal-dmen)] (4) were similarly prepared. All these complexes are characterized by various spectroscopic techniques (IR, electronic, NMR, and electron paramagnetic resonance (EPR)) and thermal as well as field-emission scanning electron micrographs (FE-SEM) studies, and the molecular structures of 3 and 4 were determined by single crystal X-ray diffraction. The EPR spectrum of the polymer supported V(IV)O-complex 1 is characteristic of magnetically diluted V(IV)O-complexes, the resolved EPR pattern indicating that the V(IV)O-centers are well dispersed in the polymer matrix. A good (51)V NMR spectrum could also be measured with 4 suspended in dimethyl sulfoxide (DMSO), the chemical shift (-503 ppm) being compatible with a VO(2)(+)-center and a N,O binding set. The catalytic oxidative desulfurization of organosulfur compounds thiophene, dibenzothiophene, benzothiophene, and 2-methyl thiophene (model of fuel diesel) was carried out using complexes 1 and 2. The sulfur in model organosulfur compounds oxidizes to the corresponding sulfone in the presence of H(2)O(2). The systems 1 and 2 do not loose efficiency for sulfoxidation at least up to the third cycle of reaction, this indicating that they preserve their integrity under the conditions used. Plausible intermediates involved in these catalytic processes are established by UV-vis, EPR, (51)V NMR, and density functional theory (DFT) studies, and an outline of the mechanism is proposed. The (51)V NMR spectra

GE`s worldwide experience with IFO based gypsum producing flue gas desulfurization systems

Energy Technology Data Exchange (ETDEWEB)

Saleem, A. [GE Environmental Systems, Lebanon, PA (United States)

1994-12-31

The In-Situ Forced Oxidation (IFO) process to produce gypsum in a commercial scale flue gas desulfurization (FGD) system was first demonstrated by GE Environmental Systems in 1980 at the Monticello Generating Station of Texas Utilities. Since then, the IFO technology developed and demonstrated by GE has become the industry standard and is used extensively on a world-wide basis to produce both commercial and disposable-grade gypsum. The paper gives an overview of the development, demonstration, commercial design and current status of the IFO technology.

Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

Energy Technology Data Exchange (ETDEWEB)

Haw, Kok-Giap; Bakar, Wan Azelee Wan Abu; Ali, Rusmidah; Chong, Jiunn-Fat [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Kadir, Abdul Aziz Abdul [Department of Petroleum Engineering, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

2010-09-15

This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 C and 700 C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H{sub 2}O{sub 2}/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed. (author)

Retrofit flue gas desulfurization system at Indianapolis Power and Light Co. Petersburg Station Units 1 and 2

International Nuclear Information System (INIS)

Watson, W.K.; Wolsiffer, S.R.; Youmans, J.; Martin, J.E.; Wedig, C.P.

1992-01-01

This paper briefly describes the status of the retrofit wet limestone flue gas desulfurization system (FGDS) project at Indianapolis Power and Light Company (IPL), Petersburg Units 1 and 2. This project was initiated by IPL in response to the Clean Air Act of 1990 and is intended to treat the flue gas from two base load units with a combined capacity of approximately 700 MW gross electrical output. IPL is the owner and operator of the Petersburg Station located in southwestern Indiana. Stone and Webster Engineering Corporation (Stone and Webster) is the Engineer and Constructor for the project. Radian Corporation is a subcontractor to Stone and Webster in the area of flue gas desulfurization (FGD) process. General Electric Environmental Systems, Inc. (GEESI) is the supplier of the FGDS. The project is organized as a team with each company providing services. The supplier of the new stack is scheduled to be selected and join the team in early 1992. Other material suppliers and field contractors will be selected in 1992

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

Science.gov (United States)

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

2011-02-01

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

Deep-desulfurization of the petroleum diesel using the heterogeneous carboxyl functionalized poly-ionic liquid

OpenAIRE

Kamlesh Rudreshwar Balinge; Avinash Ganesh Khiratkar; Manikandan Krishnamurthy; Dipesh S. Patle; Cheralathan K. K.; Pundlik Rambhau Bhagat

2016-01-01

Acidic carboxyl functionalized poly(ionic liquid) (CFPIL) has been synthesized and characterized by various techniques like FT-NMR, Fourier transform infrared spectroscopy (FTIR). In this work, deep oxidative desulfurization of model oil (thiophene dissolved in iso-octane) by CFPIL catalyst was carried out in presence of 30 wt% H2O2 solution as an oxidant. The effects of the hydrogen peroxide, amount of CFPIL, temperature-time and recyclability are scrutinized systematically. It was found tha...

A Promising PET Tracer for Imaging of α7 Nicotinic Acetylcholine Receptors in the Brain: Design, Synthesis, and in Vivo Evaluation of a Dibenzothiophene-Based Radioligand

Directory of Open Access Journals (Sweden)

Rodrigo Teodoro

2015-10-01

Full Text Available Changes in the expression of α7 nicotinic acetylcholine receptors (α7 nAChRs in the human brain are widely assumed to be associated with neurological and neurooncological processes. Investigation of these receptors in vivo depends on the availability of imaging agents such as radioactively labelled ligands applicable in positron emission tomography (PET. We report on a series of new ligands for α7 nAChRs designed by the combination of dibenzothiophene dioxide as a novel hydrogen bond acceptor functionality with diazabicyclononane as an established cationic center. To assess the structure-activity relationship (SAR of this new basic structure, we further modified the cationic center systematically by introduction of three different piperazine-based scaffolds. Based on in vitro binding affinity and selectivity, assessed by radioligand displacement studies at different rat and human nAChR subtypes and at the structurally related human 5-HT3 receptor, we selected the compound 7-(1,4-diazabicyclo[3.2.2]nonan-4-yl-2-fluorodibenzo-[b,d]thiophene 5,5-dioxide (10a for radiolabeling and further evaluation in vivo. Radiosynthesis of [18F]10a was optimized and transferred to an automated module. Dynamic PET imaging studies with [18F]10a in piglets and a monkey demonstrated high uptake of radioactivity in the brain, followed by washout and target-region specific accumulation under baseline conditions. Kinetic analysis of [18F]10a in pig was performed using a two-tissue compartment model with arterial-derived input function. Our initial evaluation revealed that the dibenzothiophene-based PET radioligand [18F]10a ([18F]DBT-10 has high potential to provide clinically relevant information about the expression and availability of α7 nAChR in the brain.

On the potential of absorption and reactive adsorption for desulfurization of ultra low-sulfur commercial diesel in the liquid phase in the presence of fuel additive and bio-diesel

Energy Technology Data Exchange (ETDEWEB)

Pieterse, J.A.Z.; Van Eijk, S.; Van Dijk, H.A.J.; Van den Brink, R.W. [Energy research Center of the Netherlands, P.O. Box 1, 1755 ZG Petten (Netherlands)

2011-03-15

Sorption of sulfur components in the liquid phase was used to desulfurize ultra low sulfur diesel (ULSD) to below 1 ppmw S. Several concepts of sorption were considered by using both physisorption and chemisorption materials and conditions. Adsorption assisted by reaction with Ni sorbent was found to be most successful. Using a pre-commercial diesel representing a mature diesel on all aspects except for the absence of fuel stabilizers and bio-diesel, a sulfur breakthrough capacity of 2 mg S/g could be achieved using a Ni-sorbent at an acceptable LHSV of 0.7 h{sup -1} on average. However, successive experiments indicated that the desulfurization capacity depended strongly on the presence of fuel-additive and bio-diesel in commercial ULSD. The presence of the cetane improver 2-ethylhexylnitrate (2EHN) was shown to decrease the sulfur capacity by roughly 50%. The presence of bio-diesel (fatty acid methyl ester, abbreviated to FAME) was shown to completely disable the desulfurization process. This was confirmed by comparing BP Ultimate diesel with FAME (obtained in 2008) and without FAME (obtained in 2006). From this evaluation it turned out that the targeted breakthrough capacity of 1 mg S/g sorbent was within reach for commercial ULSD until late 2006 when adding bio-diesel to ULSD became common practice in Europe. Several attempts to remove the additives prior to desulfurization by using copper loaded zeolites, active carbon and silica gel proved unsuccessful to bring the sulfur adsorption capacity for current diesel to the level observed for 2EHN and FAME-free diesel. It is concluded that sorption in the liquid phase does not yet represent a viable desulfurization technology for ultra-low sulfur diesel.

Mercury emission and plant uptake of trace elements during early stage of soil amendment using flue gas desulfurization materials.

Science.gov (United States)

A pilot-scale field study was carried out to investigate the distribution of Hg and other selected elements in the three potential mitigation pathways, i.e., emission to ambient air, uptake by surface vegetation (i.e., grass), and rainfall infiltration, after flue gas desulfurization (FGD) material ...

The control of H2S in biogas using iron ores as in situ desulfurizers during anaerobic digestion process.

Science.gov (United States)

Zhou, Qiying; Jiang, Xia; Li, Xi; Jiang, Wenju

2016-09-01

In this study, five kinds of iron ores, limonite, hematite, manganese ore, magnetite and lava rock, were used as the in situ desulfurizers in the anaerobic digestion reactors to investigate their effects on controlling H2S in biogas. The results show that the addition of the five iron ores could significantly control the content of H2S in biogas, with the best performance for limonite. As limonite dosages increase (10-60 g/L), the contents of H2S in biogas were evidently decreased in the digesters with different initial sulfate concentrations (0-1000 mg/L). After the anaerobic digestion, the removed sulfur was mostly deposited on the surface of limonite. A possible mechanism of H2S control in biogas by limonite was proposed preliminarily, including adsorption, FeS precipitation, and Fe (III) oxidation. The results demonstrated that limonite was a promising in situ desulfurizer for controlling H2S in biogas with low cost and high efficiency.

Metals in soil and runoff from a piedmont hayfield amended with broiler litter and flue gas desulfurization gypsum

Science.gov (United States)

Flue gas desulfurization gypsum (FGDG) from coal-fired power plants is available for agricultural use in many US regions. Broiler litter (BL) provides plant available N, P, and K but may be a source of unwanted arsenic (As), copper (Cu), and zinc (Zn). FGDG provides Ca and S and can reduce runoff lo...

Intensification of oxidative desulfurization of gas oil by ultrasound irradiation: Optimization using Box–Behnken design (BBD)

International Nuclear Information System (INIS)

Jalali, Mohammad Reza; Sobati, Mohammad Amin

2017-01-01

Highlights: • Ultrasound-assisted oxidative desulfurization (UAOD) of gas oil was studied. • The influences of the different operating parameters were investigated. • Response surface methodology (RSM) was used to find the best operating parameters. • An accurate correlation was developed for the sulfur removal. • Ultrasound-assisted desulfurization process was compared with conventional process. - Abstract: In the present work, ultrasound assisted oxidative desulfurization (UAOD) of gas oil as the feedstock with sulfur content of 2210 ppmw was investigated using a mixture of hydrogen peroxide and formic acid as the oxidant and catalyst, respectively. The influences of main process variables such as sonication time (2–30 min), oxidation temperature (40–70 °C), hydrogen peroxide to sulfur molar ratio (10–50), formic acid to oxidant molar ratio (2–4), ultrasound power per gas oil volume (5.56–8.89 W/mL), and number of extraction stages (1–4) on the sulfur removal of gas oil were investigated. Response surface methodology (RSM) based on Box–Behnken design (BBD) and single-factor experiments were employed. The best performance of UAOD process for gas oil was achieved at 50 °C of reaction temperature, oxidant to sulfur molar ratio of 46.36, formic acid to oxidant molar ratio of 3.22, sonication time of 19.81 min, and 7.78 W/mL as the ultrasound power per gas oil volume. The sulfur removal of UAOD process was evaluated after oxidation under the abovementioned conditions followed by (a) one stage extraction and (b) four stages extraction using acetonitrile as solvent. The observed sulfur removal was 87 for case (a) and 96.2% for case (b). The UAOD process was also compared with conventional ODS process. Considerable improvement on the sulfur removal was observed specially in lower reaction time in the case of using ultrasound irradiation in comparison with conventional mixing.

Influence of the size of MoS{sub 2} particles supported on alumina on the activity and the selectivity of hydro-treating reactions; Influence de la taille des particules de MoS{sub 2} supportees sur alumine sur l`activite et la selectivite des reactions d`hydrotraitement

Energy Technology Data Exchange (ETDEWEB)

Da Silva, P.

1998-01-14

The influence of the size of molybdenum disulfide particles supported on alumina on hydro-desulfurization and hydrogenation reactions has been studied. Different methods have been used to modify the length and the stacking of MoS{sub 2} slabs. MoS{sub 2} slab length measured from Electron Microscopy is increased from 20 to 40 angstroms by increasing loading from 4 to 22 % pds in Mo. These catalysts have been tested and characterised by different techniques. Increasing the sulfiding temperature also leads to an increase in MoS{sub 2} slab length. Bulk MoS{sub 2} and MoS{sub 2}/Al{sub 2}O{sub 3} showing high MoS{sub 2} slab stacking have been prepared from ammonium tetra-thio-molybdate salt. Sulfide phase characterisation results and an hexagonal MoS{sub 2} slab model have been used to estimate a number of edge and corner Mo ions. Catalysts have been characterised by Temperature Programmed Reduction and by CO adsorption at low temperatures (infra-red). Edge and corner Mo ions site densities determined by these techniques are linearly correlated with the number of sites calculated from the hexagonal MoS{sub 2} slab model and the characterisation results. Catalysts have been tested at 350 deg. C, under a total pressure of 4,5 MPa for dibenzo-thiophene hydro-desulfurization and 1-methyl naphthalene hydrogenation in the presence of nitrogen compounds. Linear correlations have been obtained between the catalytic activity and the number of edge and corner Mo sites estimated from different techniques. These results obtained from independent techniques clearly show the essential part played by edge and corner sites on catalytic activity. MoS{sub 2} slab length has no influence on the selectivity hydrogenation/hydro-desulfurization of tested catalysts. On the other side, the increase o stacking of MoS{sub 2} slab un-favours the hydrogenation reaction when compared to the hydro-desulfurization reaction. (author) 169 refs.

Carbonate Minerals with Magnesium in Triassic Terebratula Limestone in the Term of Limestone with Magnesium Application as a Sorbent in Desulfurization of Flue Gases

Science.gov (United States)

Stanienda-Pilecki, Katarzyna

2017-09-01

This article presents the results of studies of Triassic (Muschelkalk) carbonate rock samples of the Terebratula Beds taken from the area of the Polish part of the Germanic Basin. It is the area of Opole Silesia. The rocks were studied in the term of possibility of limestone with magnesium application in desulfurization of flue gases executed in power plants. Characteristic features of especially carbonate phases including magnesium-low-Mg calcite, high-Mg calcite, dolomite and huntite were presented in the article. They were studied to show that the presence of carbonate phases with magnesium, especially high-Mg calcite makes the desulfurization process more effective. Selected rock samples were examined using a microscope with polarized, transmitted light, X-ray diffraction, microprobe measurements and FTIR spectroscopy. The results of studies show a domination of low magnesium calcite in the limestones of the Terebratula Beds. In some samples dolomite and lower amounts of high-Mg calcite occurred. Moreover, huntite was identified. The studies were very important, because carbonate phases like high-Mg calcite and huntite which occurred in rocks of the Triassic Terebratula Beds were not investigated in details by other scientists but they presence in limestone sorbent could influence the effectiveness of desulfurization process.

Marble waste characterization as a desulfurizing slag component for steel

International Nuclear Information System (INIS)

Coleti, J.L.; Grillo, F.F.; Tenorio, J.A.S.; De Oliveira, J.R.

2014-01-01

The current steel market requires from steel plants better quality of its products. As a result, steel plants need to search for improvements and costs reduction in its process. Hence, the residue of marble containing significant quantities of calcium and magnesium carbonates, raw materials of steel refining slag, was characterized in order to replace the conventional lime used. Therefore, it will be possible to reduce the cost and volume of waste produced by the ornamental rock industry. The following methods were applied to test the waste potential: SEM with EDS, x-ray diffraction, x-ray fluorescence (EDX), Thermogravimetry (TG) and analysis of surface area and particle size by the BET method using dispersion leisure. The results indicated the feasibility of waste as raw material in the composition of desulfurizing slags. (author)

Adsorptive desulfurization with CPO-27/MOF-74: an experimental and computational investigation.

Science.gov (United States)

Van de Voorde, Ben; Hezinová, Markéta; Lannoeye, Jeroen; Vandekerkhove, Annelies; Marszalek, Bartosz; Gil, Barbara; Beurroies, Isabelle; Nachtigall, Petr; De Vos, Dirk

2015-04-28

By combining experimental adsorption isotherms, microcalorimetric data, infrared spectroscopy and quantum chemical calculations the adsorption behaviour of the CPO-27/MOF-74 series (Ni, Co, Mg, Cu, and Zn) in the desulfurization of fuels is evaluated. The results show a clear influence of the metal ion on the adsorption capacity and affinity for S-heterocyclic compounds, with CPO-27(Ni) being the best performing material both in terms of capacity and affinity. The microcalorimetric data and infrared spectroscopy confirm the high affinity of CPO-27(Ni) for thiophene and similar compounds, while the computational data reveal that the origin of this outstanding adsorption performance is the strong sulfur-metal interaction.

Flue gas desulfurization: Physicochemical and biotechnological approaches

Energy Technology Data Exchange (ETDEWEB)

Pandey, R.A.; Biswas, R.; Chakrabarti, T.; Devotta, S. [National Environmental Engineering Research Institute, Nagpur (India)

2005-07-01

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

Experimental study and mechanism analysis of modified limestone by red mud for improving desulfurization

Energy Technology Data Exchange (ETDEWEB)

Liu, Hongtao; Han, Kuihua; Niu, Shengli; Lu, Chunmei; Liu, Mengqi; Li, Hui [Shandong Univ., Jinan (China). School of Energy and Power Engineering

2013-07-01

Red mud is a type of solid waste generated during alumina production from bauxite, and how to dispose and utilize red mud in a large scale is yet a question with no satisfied answer. This paper attempts to use red mud as a kind of additive to modify the limestone. The enhancement of the sulfation reaction of limestone by red mud (two kinds of Bayer process red mud and one kind of sintering process red mud) are studied by a tube furnace reactor. The calcination and sulfation process and kinetics are investigated in a thermogravimetric (TG) analyzer. The results show that red mud can effectively improve the desulfurization performance of limestone in the whole temperature range (1,073-1,373K). Sulfur capacity of limestone (means quality of SO{sub 2} which can be retained by 100mg of limestone) can be increased by 25.73, 7.17 and 15.31% while the utilization of calcium can be increased from 39.68 to 64.13%, 60.61 and 61.16% after modified by three kinds of red mud under calcium/metallic element (metallic element described here means all metallic elements which can play a catalytic effect on the sulfation process, including the Na, K, Fe, Ti) ratio being 15, at the temperature of 1,173K. The structure of limestone modified by red mud is interlaced and tridimensional which is conducive to the sulfation reaction. The phase composition analysis measured by XRD of modified limestone sulfated at high temperature shows that there are correspondingly more sulphates for silicate and aluminate complexes of calcium existing in the products. Temperature, calcium/metallic element ratio and particle diameter are important factors as for the sulfation reaction. The optimum results can be obtained as calcium/metallic element ratio being 15. Calcination characteristic of limestone modified by red mud shows a migration to lower temperature direction. The enhancement of sulfation by doping red mud is more pronounced once the product layer has been formed and consequently the promoting

Effects of surface acidities of MCM-41 modified with MoO{sub 3} on adsorptive desulfurization of gasoline

Energy Technology Data Exchange (ETDEWEB)

Shao Xinchao, E-mail: sxc86@yahoo.cn [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); Zhang Xiaotong; Yu Wenguang; Wu Yuye [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); Qin Yucai [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 257061 (China); Sun Zhaolin [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China); School of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Song Lijuan, E-mail: lsong56@263.net [Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning ShiHua University, Fushun 113001 (China) and College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 257061 (China)

2012-12-15

Highlights: Black-Right-Pointing-Pointer The MoO{sub 3}-MCM-41 samples prepared by spontaneous monolayer dispersion and impregnation with a different MoO{sub 3} filling have been studied. Black-Right-Pointing-Pointer The relative concentration of hydroxyl groups present on before and after containing MoO{sub 3} samples was monitored by in situ FTIR to speculate the bonding style of MoO{sub 3} and MCM-41. Black-Right-Pointing-Pointer The surface acidities of the MoO{sub 3}-MCM-41 adsorbents were investigated systematically and correlated with the desulfurization performance. - Abstract: A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N{sub 2} adsorption-desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO{sub 3} can be highly dispersed up to 0.2 g g{sup -1} in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO{sub 3} contents of 0.26 and 0.32 g g{sup -1} with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO{sub 3} particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO{sub 3} species is related to the abundant surface hydroxy of MCM-41. The host species and guest

The Stability of Lubricant Oil Acidity of Biogas Fuelled Engine due to Biogas Desulfurization

Science.gov (United States)

Gde Tirta Nindhia, Tjokorda; Wayan Surata, I.; Wardana, Ari

2017-05-01

This research is established for the purpose of the understanding the stability of the acidity of lubricant oil in biogas fuelled engine due to the absence of hydrogen sulfide (H2S). As was recognized that other than Methane (CH4), there are also other gas impurities in the biogas such as carbon dioxide (CO2), hydrogen sulfide (H2S), moisture (H2O) and ammonia (NH3). Due to H2S contents in the biogas fuel, the engine was found failure. This is caused by corrosion in the combustion chamber due to increase of lubricant acidity. To overcome this problem in practical, the lubricant is increased the pH to basic level with the hope will be decrease to normal value after several time use. Other method is by installing pH measurement sensor in the engine lubricant so that when lubricant is known turn to be acid, then lubricant replacement should be done. In this research, the effect of biogas desulfurization down to zero level to the acidity of lubricant oil in the four stroke engine was carried out with the hope that neutral lubrication oil to be available during running the engine. The result indicates that by eliminating H2S due desulfurization process, effect on stability and neutrality of pH lubricant. By this method the engine safety can be obtained without often replacement the lubricant oil.

Hot coal gas desulfurization with manganese-based sorbents. Final report, September 1992--December 1994

Energy Technology Data Exchange (ETDEWEB)

Hepworth, M.T.; Slimane, R.B.

1994-11-01

The focus of much current work being performed by the Morgantown Energy Technology Center (METC) of the Department of Energy on hot coal-derived fuel gas desulfurization is in the use of zinc-based sorbents. METC has shown interest in formulating and testing manganese-based pellets as alternative effective sulfur sorbents in the 700 to 1200{degree}C temperature range. To substantiate the potential superiority of Mn-based pellets, a systematic approach toward the evaluation of the desulfurizing power of single-metal sorbents is developed based on thermodynamic considerations. This novel procedure considered several metal-based sorbents and singled out manganese oxide as a prime candidate sorbent capable of being utilized under a wide temperature range, irrespective of the reducing power (determined by CO{sub 2}/CO ratio) of the fuel gas. Then, the thermodynamic feasibility of using Mn-based pellets for the removal of H{sub 2}S from hot-coal derived fuel gases, and the subsequent oxidative regeneration of loaded (sulfided) pellets was established. It was concluded that MnO is the stable form of manganese for virtually all commercially available coal-derived fuel gases. In addition, the objective of reducing the H{sub 2}S concentration below 150 ppMv to satisfy the integrated gasification combined cycle system requirement was shown to be thermodynamically feasible. A novel process is developed for the manufacture of Mn-based spherical pellets which have the desired physical and chemical characteristics required.

Effect of gasoline composition on oxidative desulfurization using a phosphotungstic acid/activated carbon catalyst with hydrogen peroxide

International Nuclear Information System (INIS)

Xiao, Jing; Wu, Luoming; Wu, Ying; Liu, Bing; Dai, Lu; Li, Zhong; Xia, Qibin; Xi, Hongxia

2014-01-01

Highlights: • Concerned with the question why ODS catalyst is not effective for real gasoline. • Reported the strong inhibiting effect of gasoline composition on ODS for the 1st time. • ODS reactivity is suggested to be determined by partial charge on S atom of thiophene. • Proposed approaches to improve ODS selectivity for real gasoline desulfurization. - Abstract: This work is concerned with the question of why oxidative desulfurization (ODS) catalyst that show good catalytic performance for ODS of model gasoline thiophenic compounds is not effective for real gasoline. For the first time, the effects of gasoline composition on ODS using a phosphotungstic acid/activated carbon (HPW/AC) catalyst with H 2 O 2 were investigated. ODS of thiophene, one of the most difficult thiophenic compounds to be oxidized, was studied in a model fuel system, where a high thiophene conversion rate of 90% could be reached in 2 h at 90 °C. However, when applying the ODS to a real gasoline, the ODS conversion rate decreased to only 32%, suggesting a strong inhibiting effect of gasoline composition on ODS. The ODS studies in different model fuels suggested that the inhibiting effect can be ascribed to the competitive adsorption and oxidation with the presence of the alkenes and alkylated aromatic hydrocarbons in real gasoline. The active pi-electrons in alkenes and alkyl groups in alkylated aromatic hydrocarbons may react with polyoxoperoxo species or peroxo-metallate complexes formed by phosphotungstic acid–H 2 O 2 interaction. Additionally, it was indicated that the ODS selectivity followed the order of benzothiophene > trimethylthiophene > dimethylthiophene ∼ methylthiophene > thiophene, suggesting the partial charge on the electron-rich sulfur atom may play a decisive role for its oxidation reactivity. To mitigate the inhibiting effect of gasoline composition on ODS, we propose (a) implementation of selective separation–oxidation processes; (b) choice of suitable

Oxidative desulfurization of diesel with TBHP/isobutyl aldehyde/air oxidation system

Energy Technology Data Exchange (ETDEWEB)

Guo, Wei; Wang, Chengyong; Lin, Peng; Lu, Xiaoping [Institute of Sonochemical Engineering, Nanjing University of Technology, Nanjing 210009, Jiangsu (China)

2011-01-15

Oxidative desulfurization of hydrogenation diesel (40 mL) was studied using air as oxidant, tert-butyl hydroperoxide (TBHP) as radical initiator at ambient pressure and moderate temperature in the presence of isobutyl aldehyde. TBHP could accelerate the production of carbonyl radical and its peroxidation. When the molar fraction of TBHP was 5 mmol, the conversion of DBT could reach 96.1% in the present of 20 mmol isobutyl aldehyde and air, which was more than that of 85.5% without initiator. The air was an effective oxidant and acetonitrile was an optimal solvent in this process. The sulfur content of the hydrogenation diesel could be reduced from 403 to 13 ppm (96.8% removed) under the synergistic effect of air, TBHP and isobutyl aldehyde. (author)

The Flakt-Hydro process: flue gas desulfurization by use of seawater

Energy Technology Data Exchange (ETDEWEB)

Xia, W.Z. [ABB China Limited, Shanghai (China)

1999-07-01

ABB's seawater scrubbing process (the Flakt-Hydro process) for flue gas desulfurization has recently triggered interest among power producers because of its simple operating principle and high reliability. The process uses seawater to absorb and neutralize sulfur dioxide in flue gases. The absorbed gas is oxidized and returned to the ocean in the form it originated in the first place, namely as dissolved sulfate salts. The process uses the seawater downstream of the power plant condensers. This paper gives an introduction to the basic principle of the process and presents some of the recent power plant applications, namely at the Paiton Private Power Project; Phase 1 (2 x 670 MWe) in Indonesia and at the Shenzhen West Power Plant, Unit 2 (300 MWe) in China.

Optimisation of Experimental Conditions for Ex-Bed Desulfurization

Energy Technology Data Exchange (ETDEWEB)

Sanchez, J. M.; Ruiz, E.; Otero, J.

2010-12-22

This report compiles the results of the work conducted by CIEMAT for Task 6.3 Sulfur and Nitrogen Compounds Abatement of the FLEXGAS project Near Zero Emission Advanced Fluidized Bed Gasification, which has been carried out with financial support from the Research Fund for Coal and Steel, RFCR-CT-2007-00005. The assignment of CIEMAT in Task 6.3 has dealt with the experimental study of ex-bed desulfurization at high temperature and high pressure. Based on a review of the state of the art, a zinc oxide sorbent was chosen as a promising candidate for bulk sulfur removal in highly reducing gases such as those from coal and waste oxygen gasification or for a polishing stage in low sulfur content gases, which is typically the case in biomass gasification gases. The work accomplished has included the study of the sulfidation and regeneration stages in order to determine successful operating conditions and the assessment of the long term performance of the sorbent over subsequent sulfidation and regeneration cycles. (Author) 36 refs.

Experimental study on the mechanism of SO2 emission and calcium-based desulfurization in the coal oxygen-enriched combustion

International Nuclear Information System (INIS)

Tian, Luning; Chen, Hanping; Yang, Haiping; Wang, Xianhua; Zhang, Shihong

2010-01-01

Full text: The emission of SO 2 , CO 2 brings serious harm to the ecological environment, human health and the global climate change. The largest source of SO 2 , CO 2 is the combustion of fossil fuels for power generation. So developing the new technology for controlling pollutants emissions from coal combustion was imperative. Oxygen-enriched combustion technology is such a new technology which can realize CO 2 zero emission, enhance the combustion efficiency and reduce pollutants emission. Due to the high concentration of CO 2 , it has many different aspects in the SO 2 emission and calcium-based desulfurization compare with the conventional combustion. In this article, experiments have been done to investigate the behavior and mechanism of SO 2 emissions and removal in oxygen-enriched combustion. First, in TGA and fixed bed reactor, the SO 2 emission characteristics were investigated under various bed temperature, particle size and O 2 / CO 2 concentration. It was observed that SO 2 released faster and the emission peak was higher than air atmosphere. SO 2 emission concentration increased with the reaction temperature increasing. Simultaneously, the mechanism of SO 2 emission was obtained by analyzing the sulfur compounds in the gas products and solid products in different reaction times. Then, the impacts of reaction temperature, particle size, O 2 / CO 2 concentration and SO 2 concentration etc. on the efficiency of SO 2 removal were analyzed. The phase analysis, pore diameter distribution and microstructure of the solid product were investigated. The experimental results showed that the sulphur capture takes place by direct sulphation reaction at high CO 2 concentration which attributes to light sinter, better porous structure, higher optimal desulfurization temperature and high desulfurization efficiency of calcium-based sorbent. (author)

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

Science.gov (United States)

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.

Monometallic Pd and Pt and Bimetallic Pd-Pt/Al2O3-TiO2 for the HDS of DBT: Effect of the Pd and Pt Incorporation Method

Directory of Open Access Journals (Sweden)

Reynaldo Martínez Guerrero

2014-01-01

Full Text Available The effect of the preparation method of monometallic Pd and Pt and bimetallic Pd-Pt/Al2O3-TiO2 catalysts on the hydrodesulfurization (HDS of dibenzothiophene (DBT was investigated in this study. The synthesis was accomplished using three methods: (A impregnation, (B metal organic chemical vapor deposition (MOCVD, and (C impregnation-MOCVD. The bimetallic Pd-Pt catalyst prepared by the impregnation-MOCVD method was most active for the HDS of DBT compared to those prepared by the single impregnation or MOCVD method due to the synergetic effect between both noble metals. The greater selectivity toward biphenyl indicated that this bimetallic Pd-Pt catalyst preferentially removes sulfur via the direct desulfurization mechanism. However, the bimetallic Pd-Pt catalyst prepared using the single MOCVD method did not produce any cyclohexylbenzene, which is most likely associated with the hydrogenation/dehydrogenation sites.

Investigation on gasoline deep desulfurization for fuel cell applications

International Nuclear Information System (INIS)

Zhang, J.C.; Song, L.F.; Hu, J.Y.; Ong, S.L.; Ng, W.J.; Lee, L.Y.; Wang, Y.H.; Zhao, J.G.; Ma, R.Y.

2005-01-01

The effect of adding some amounts of cerium into Zn-Fe-O/Al 2 O 3 sorbent on its performance of removal of organic sulfur compounds from gasoline by adsorption was studied in this paper. It showed that the ideal compositions for the preparation of Zn-Fe-Ce-O/Al 2 O 3 consisted of 4.54 wt.% ZnO, 2.25 wt.% Fe 2 O 3 and 2.5 wt.% CeO 2 , respectively, shortened as AZFC 0.52 . Further study indicated that this sorbent could be well regenerated at 250 deg. C with gas mixtures containing 6.0 vol.% steam + air and 2400 ml h -1 ml -1 gas space velocity. At those regenerated conditions and 60 deg. C adsorption temperature, the AZFC 0.52 sorbent had better desulfurization stability, which was confirmed by typical characterization results using BET, XRD and SEM apparatus. This implied that the AZFC 0.52 sorbent could be an ideal sorbent for removal of organic sulfur compounds from gasoline

Speciation of Raney Copper Oxide during High-Temperature Desulfurization

International Nuclear Information System (INIS)

Wang, T. C.; Chen, C. Y.; Huang, H.-L.; Wang, H. Paul; Wei Yuling

2007-01-01

Speciation of copper in the Raney copper oxides (R-CuO) during high-temperature desulfurization has been studied by X-ray absorption spectroscopy. The preedge XANES spectra (8975-8979 eV) of R-CuO exhibit a very weak 1s-to-3d transition forbidden by the selection rule in the case of the perfect octahedral symmetry. A shoulder at 8985-8988 eV and an intense band at 8994-9002 eV can be attributed to the 1s-to-4p transition that indicates the existence of the Cu(II) species. The preedge band at 8981-8984 eV can be attributed to the dipole-allowed 1s-to-4p transition of Cu(I), suggesting an existence of Cu2S during sulfurization. An enhanced absorbance at 9003 eV shows that Cu(0) species may be formed in the sulfurized R-CuO. The main copper species in regenerated R-CuO are CuO (96%) and Cu2S (4%)

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

Science.gov (United States)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

Microbial Desulfurization of a Crude Oil Middle-Distillate Fraction: Analysis of the Extent of Sulfur Removal and the Effect of Removal on Remaining Sulfur

Science.gov (United States)

Grossman, M. J.; Lee, M. K.; Prince, R. C.; Garrett, K. K.; George, G. N.; Pickering, I. J.

1999-01-01

Rhodococcus sp. strain ECRD-1 was evaluated for its ability to desulfurize a 232 to 343°C middle-distillate (diesel range) fraction of Oregon basin (OB) crude oil. OB oil was provided as the sole source of sulfur in batch cultures, and the extent of desulfurization and the chemical fate of the residual sulfur in the oil after treatment were determined. Gas chromatography (GC), flame ionization detection, and GC sulfur chemiluminesce detection analysis were used to qualitatively evaluate the effect of Rhodococcus sp. strain ECRD-1 treatment on the hydrocarbon and sulfur content of the oil, respectively. Total sulfur was determined by combustion of samples and measurement of released sulfur dioxide by infrared absorption. Up to 30% of the total sulfur in the middle distillate cut was removed, and compounds across the entire boiling range of the oil were affected. Sulfur K-edge X-ray absorption-edge spectroscopy was used to examine the chemical state of the sulfur remaining in the treated OB oil. Approximately equal amounts of thiophenic and sulfidic sulfur compounds were removed by ECRD-1 treatment, and over 50% of the sulfur remaining after treatment was in an oxidized form. The presence of partially oxidized sulfur compounds indicates that these compounds were en route to desulfurization. Overall, more than two-thirds of the sulfur had been removed or oxidized by the microbial treatment. PMID:9872778

A non-chemically selective top-down approach towards the preparation of hierarchical TS-1 zeolites with improved oxidative desulfurization catalytic performance.

Science.gov (United States)

Du, Shuting; Chen, Xiaoxin; Sun, Qiming; Wang, Ning; Jia, Mingjun; Valtchev, Valentin; Yu, Jihong

2016-02-28

Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction.

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

Science.gov (United States)

Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

2007-01-01

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Preparation of Active Absorbent for Flue Gas Desulfurization From Coal Bottom Ash: Effect of Absorbent Preparation Variables

Directory of Open Access Journals (Sweden)

Chang Chin Li, Lee Keat Teong, Subhash Bhatia and Abdul Rahman Mohamed

2012-08-01

Full Text Available An active absorbent for flue gas desulfurization was prepared from coal bottom ash, calcium oxide (CaO and calcium sulfate by hydro-thermal process. The absorbent was examined for its micro-structural properties. The experiments conducted were based on Design Of Experiments (DOE according to 23 factorial design. The effect of various absorbent preparation variables such as ratio of CaO to bottom ash (A, hydration temperature (B and hydration period (C towards the BET (Brunauer-Emmett-Teller specific surface area of the absorbent were studied. At a CaO to bottom ash ratio = 2, hydration temperature = 200 ?C and hydration period = 10 hrs, absorbent with a surface area of 90.1 m2/g was obtained. Based on the analysis of the factorial design, it was concluded that factor A and C as well as the interaction of factors ABC and BC are the significant factors that effect the BET surface area of the absorbent. A linear mathematical model that describes the relation between the independent variables and interaction between variables towards the BET specific surface area of the absorbent was also developed. Analysis of variance (ANOVA showed that the model was significant at 1% level.Key Words: Absorbent, Bottom Ash, Design Of Experiments, Desulfurization, Surface Area.

Adsorptive removal of dibenzothiophene from model fuels over one-pot synthesized PTA@MIL-101(Cr) hybrid material.

Science.gov (United States)

Jia, Shao-Yi; Zhang, Yan-Fei; Liu, Yong; Qin, Feng-Xiang; Ren, Hai-Tao; Wu, Song-Hai

2013-11-15

Hybrid nanomaterials comprising phosphotungstic acid (PTA) and MIL-101(Cr) were prepared through one-pot synthesis and post-modification methods and then were used as adsorbents of dibenzothiophene (DBT) from simulated diesel fuels. Samples obtained by different ways (encapsulation and impregnation) were characterized by nitrogen adsorption, transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR) and series of adsorption experiments. The equilibrium adsorption capacities of PTA@MIL-101(Cr) illustrated that the direct introduction of PTA into MIL-101(Cr) during synthesis resulted in a 10.7% increase compared with MIL-101(Cr). However, porous hybrid adsorbent PTA/MIL-101(Cr) prepared via post-modification method exhibited lower adsorption capacity than virgin MIL-101(Cr). The theoretical maximum adsorption capacity (Q0) of PTA@MIL-101(Cr) is 136.5mg S/g adsorbent, 4.2 times of MIL-101(Cr). Even in competitive adsorption between aromatic compounds, which possess strong affinity with MOFs, and DBT, PTA@MIL-101(Cr) and MIL-101(Cr) remained their effectiveness in removal of DBT in the system. Based on these results, it can be presumed that MIL-101(Cr), modified properly, can be used as a promising adsorbent for eliminating aromatics and S-compounds in commercial fuels simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

Selective desulfurization of cysteine in the presence of Cys(Acm) in polypeptides obtained by native chemical ligation.

Science.gov (United States)

Pentelute, Brad L; Kent, Stephen B H

2007-02-15

Increased versatility for the synthesis of proteins and peptides by native chemical ligation requires the ability to ligate at positions other than Cys. Here, we report that Raney nickel can be used under standard conditions for the selective desulfurization of Cys in the presence of Cys(Acm). This simple and practical tactic enables the more common Xaa-Ala junctions to be used as ligation sites for the chemical synthesis of Cys-containing peptides and proteins. [reaction: see text].

Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization.

Science.gov (United States)

Nishino, Kota; Minato, Kohei; Miyazaki, Takahiro; Ogiwara, Yohei; Sakai, Norio

2017-04-07

In this study an InI 3 -TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with 1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the subsequent oxidative desulfurization of an in situ formed 1,3-dithiolane derivative, which led to the preparation of the corresponding aldehydes.

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors.

Science.gov (United States)

Calcio Gaudino, Emanuela; Carnaroglio, Diego; Boffa, Luisa; Cravotto, Giancarlo; Moreira, Elizabeth M; Nunes, Matheus A G; Dressler, Valderi L; Flores, Erico M M

2014-01-01

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H2O2/CH3COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors' laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S≤5 ppmw, N≤1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors. Copyright © 2013 Elsevier B.V. All rights reserved.

Producing ammonium sulfate from flue gas desulfurization by-products

Science.gov (United States)

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

2005-01-01

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

Simultaneous desulfurization and denitrification of flue gas by electron beam

International Nuclear Information System (INIS)

Baumann, W.; Jordan, S.; Maetzing, H.; Paur, H.R.; Schikarski, W.; Wiens, H.

1987-05-01

The simultaneous desulfurization and denitrification by the irradiation with 300 keV electrons in the presence of stoichiometric amounts of ammonia yields removal efficiencies of more than 90%. NO X -removal efficiencies depend on the absorbed dose, NO X -concentration and NH 3 -stoichiometry. SO 2 -removal proceeds by thermal and radiation induced mechanisms. The efficiency of the SO 2 -removal process is highest for low temperatures and high NH 3 -stoichiometries. By recycling of scrubbed gas into the reaction chamber (multiple irradiation) the efficiency of the process is increased by 50%. The product aerosol has mass median diameters of 2 and NO x removals in the absence of NH 3 are predicted with reasonable accuracy by the computer model. In the presence of NH 3 experimental data show higher SO 2 removal efficiencies than calculated. This is probably due to additional heterogeneous reactions on particles, which are not covered by the computer model. With 119 figs., 86 refs [de

Removal of hazardous gaseous pollutants from industrial flue gases by a novel multi-stage fluidized bed desulfurizer.

Science.gov (United States)

Mohanty, C R; Adapala, Sivaji; Meikap, B C

2009-06-15

Sulfur dioxide and other sulfur compounds are generated as primary pollutants from the major industries such as sulfuric acid plants, cupper smelters, catalytic cracking units, etc. and cause acid rain. To remove the SO(2) from waste flue gas a three-stage counter-current multi-stage fluidized bed adsorber was developed as desulfurization equipment and operated in continuous bubbling fluidization regime for the two-phase system. This paper represents the desulfurization of gas mixtures by chemical sorption of sulfur dioxide on porous granular calcium oxide particles in the reactor at ambient temperature. The advantages of the multi-stage fluidized bed reactor are of high mass transfer and high gas-solid residence time that can enhance the removal of acid gas at low temperature by dry method. Experiments were carried out in the bubbling fluidization regime supported by visual observation. The effects of the operating parameters such as sorbent (lime) flow rate, superficial gas velocity, and the weir height on SO(2) removal efficiency in the multistage fluidized bed are reported. The results have indicated that the removal efficiency of the sulfur dioxide was found to be 65% at high solid flow rate (2.0 kg/h) corresponding to lower gas velocity (0.265 m/s), wier height of 70 mm and SO(2) concentration of 500 ppm at room temperature.

In situ synthesis, characterization, and catalytic performance of tungstophosphoric acid encapsulated into the framework of mesoporous silica pillared clay.

Science.gov (United States)

Li, Baoshan; Liu, Zhenxing; Han, Chunying; Ma, Wei; Zhao, Songjie

2012-07-01

Mesoporous silica pillared clay (SPC) incorporated with tungstophosphoric acid (HPW) has been synthesized via in situ introducing P and W source in the acidic suspension of the clay interlayer template during the formation of the silica pillared clay. The samples were characterized by XRD, XRF, FT-IR, TG-DTA, N(2) adsorption-desorption, and SEM techniques. The results showed that the HPW formed by in situ method has been effectively introduced into the framework of mesoporous silica pillared clay and its Keggin structure remained perfectly after formation of the materials. In addition, samples with similar HPW loadings were also prepared by impregnation method using SPC as the support. HPW in the incorporated samples was better dispersed into the silica pillared clay than in the impregnated samples. The results of catalytic tests indicated that the encapsulated materials demonstrated better catalytic performance than the impregnated samples in oxidative desulfurization (ODS) of dibenzothiophene (DBT). Copyright © 2012 Elsevier Inc. All rights reserved.

What controls intermediate depth seismicity in subduction zones?

Science.gov (United States)

Florez, M. A.; Prieto, G. A.

2017-12-01

Intermediate depth earthquakes seem to cluster in two distinct planes of seismicity along the subducting slab, known as Double Seismic Zones (DSZ). Precise double difference relocations in Tohoku, Japan and northern Chile confirm this pattern with striking accuracy. Furthermore, past studies have used statistical tests on the EHB global seismicity catalog to suggest that DSZs might be a dominant global feature. However, typical uncertainties associated with hypocentral depth prevent us from drawing meaningful conclusions about the detailed structure of intermediate depth seismicity and its relationship to the physical and chemical environment of most subduction zones. We have recently proposed a relative earthquake relocation algorithm based on the precise picking of the P and pP phase arrivals using array processing techniques [Florez and Prieto, 2017]. We use it to relocate seismicity in 24 carefully constructed slab segments that sample every subduction zone in the world. In all of the segments we are able to precisely delineate the structure of the double seismic zone. Our results indicate that whenever the lower plane of seismicity is active enough the width of the DSZ decreases in the down dip direction; the two planes merge at depths between 140 km and 300 km. We develop a method to unambiguously pick the depth of this merging point, the end of the DSZ, which appears to be correlated with the slab thermal parameter. We also confirm that the width of the DSZ increases with plate age. Finally, we estimate b-values for the upper and lower planes of seismicity and explore their relationships to the physical parameters that control slab subduction.

Design and simulation of a 1.2 MeV electron accelerator used for desulfuration and denitrogenation

International Nuclear Information System (INIS)

Zhou Jun; Zhu Dajun; Liu Shenggang

2005-01-01

This paper presents the structural design and functional analysis of a new kind of 1.2 MeV industrial electron accelerator. PIC (Particle-In-Cell) method is used to simulate this accelerator and to optimize the design, the results show that the optics property of this accelerator has been improved. This electron accelerator is used for desulfuration and denitrogenation in environmental industry. This application purifies flue gases of the thermal power station from Sulphurous oxide and Nitrogen oxide in order to reduce the pollution in the air. (author)

Deep desulfurization of middle distillates. Process adaptation to oil fractions' compositions

Energy Technology Data Exchange (ETDEWEB)

Pedernera, Esteban; Reimert, Rainer; Nguyen, Ngoc Luan; Van Buren, Vincent [Division of Fuel Technology, Universitat Karlsruhe TH, Engler-Bunte-Ring 1, 76131 Karlsruhe (Germany)

2003-04-30

The influence of oil fractions' compositions on the conversion of sulfurous components was investigated in a trickle-bed reactor in laboratory scale. A commercially available NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst was used throughout the investigations. Experimental results including sulfur conversion of different oil fractions and residence time distributions under reacting conditions are presented. The hydrogen consumption is ascribed to the conversion of sulfur and of nitrogen, to the hydrogenation of aromatics and to hydrocracking based on a simulation applying ASPEN Plus. Various configurations of the desulfurization process are evaluated but no advantage is found by separate treatment of individual oil fractions. In addition, experiments were carried out to determine liquid distribution and wetting efficiency in a catalyst bed by using magnetic resonance imaging (MRI) technique.

Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

Science.gov (United States)

Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki

2007-06-21

A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

Species Differences in the Oxidative Desulfurization of a Thiouracil-Based Irreversible Myeloperoxidase Inactivator by Flavin-Containing Monooxygenase Enzymes.

Science.gov (United States)

Eng, Heather; Sharma, Raman; Wolford, Angela; Di, Li; Ruggeri, Roger B; Buckbinder, Leonard; Conn, Edward L; Dalvie, Deepak K; Kalgutkar, Amit S

2016-08-01

N1-Substituted-6-arylthiouracils, represented by compound 1 [6-(2,4-dimethoxyphenyl)-1-(2-hydroxyethyl)-2-thioxo-2,3-dihydropyrimidin-4(1H)-one], are a novel class of selective irreversible inhibitors of human myeloperoxidase. The present account is a summary of our in vitro studies on the facile oxidative desulfurization in compound 1 to a cyclic ether metabolite M1 [5-(2,4-dimethoxyphenyl)-2,3-dihydro-7H-oxazolo[3,2-a]pyrimidin-7-one] in NADPH-supplemented rats (t1/2 [half-life = mean ± S.D.] = 8.6 ± 0.4 minutes) and dog liver microsomes (t1/2 = 11.2 ± 0.4 minutes), but not in human liver microsomes (t1/2 > 120 minutes). The in vitro metabolic instability also manifested in moderate-to-high plasma clearances of the parent compound in rats and dogs with significant concentrations of M1 detected in circulation. Mild heat deactivation of liver microsomes or coincubation with the flavin-containing monooxygenase (FMO) inhibitor imipramine significantly diminished M1 formation. In contrast, oxidative metabolism of compound 1 to M1 was not inhibited by the pan cytochrome P450 inactivator 1-aminobenzotriazole. Incubations with recombinant FMO isoforms (FMO1, FMO3, and FMO5) revealed that FMO1 principally catalyzed the conversion of compound 1 to M1. FMO1 is not expressed in adult human liver, which rationalizes the species difference in oxidative desulfurization. Oxidation by FMO1 followed Michaelis-Menten kinetics with Michaelis-Menten constant, maximum rate of oxidative desulfurization, and intrinsic clearance values of 209 μM, 20.4 nmol/min/mg protein, and 82.7 μl/min/mg protein, respectively. Addition of excess glutathione essentially eliminated the conversion of compound 1 to M1 in NADPH-supplemented rat and dog liver microsomes, which suggests that the initial FMO1-mediated S-oxygenation of compound 1 yields a sulfenic acid intermediate capable of redox cycling to the parent compound in a glutathione-dependent fashion or undergoing further oxidation to a more

Synthesis of geminal difluorides by oxidative desulfurization-difluorination of alkyl aryl thioethers with halonium electrophiles in the presence of fluorinating reagents and its application for 18F-radiolabeling.

Science.gov (United States)

Hugenberg, Verena; Wagner, Stefan; Kopka, Klaus; Schober, Otmar; Schäfers, Michael; Haufe, Günter

2010-09-17

Various ω-substituted 1,1-difluoroalkanes are synthesized in good yields from alkyl aryl thioethers by a new oxidative desulfurization-difluorination protocol with the reagents combination of 1,3-dibromo-5,5-dimethylhydantoin (DBH) as an oxidizer and pyridine·9HF (Py·9HF) as a fluoride source. The reaction proceeds via a fluoro-Pummerer-type rearrangement followed by an oxidative desulfurization-fluorination step. Starting from α-fluorinated thioethers, this reaction is promising for (18)F-labeling (τ(1/2) = 110 min) of ligands applicable for positron emission tomography (PET). Using the combination of DBH and carrier-added Py·9H[(18)F]F, an (18)F-labeled difluoride was synthesized from the corresponding α-fluoro thioether with a radiochemical yield of 9%.

On the high-temperature desulfurization of coal gas: The development of a regenerable absorbent

Energy Technology Data Exchange (ETDEWEB)

Van Yperen, Renee

1994-05-18

There is actually no solid absorbent based on bulk metal oxides available that meets the conditions for application in high-temperature desulfurization processes. This research was aimed to develop an absorbent that fulfills all the specifications for employment in hot-gas clean up. Chapter 2 deals with the development of amorphous aluminium phosphate as a support material. The influence of the preparation conditions onto the specific surface area, pore structure, thermal and chemical stability, and acidity of amorphous aluminium phosphate was investigated. The application of iron oxide onto amorphous aluminium phosphate by means of deposition-precipitation from a homogeneous solution is discussed in chapter 3. The influence of amorphous aluminium phosphate onto the stability, activity, and capacity of the iron oxide is described in detail. Chapter 4 surveys the activity and capacity of several active materials in the absorption of hydrogen sulphide. It is shown that the most promising active material is a mixture of iron oxide and molybdenum oxide. In chapter 5 the properties of iron-molybdenum mixed oxide absorbents are discussed. The effect of the iron to molybdenum ratio onto the formation of iron-(III)-sulphates and the stability of the molybdenum compound is examined. Chapter 6 deals with the preparation of iron-molybdenum mixed oxide absorbents by means of impregnation of modified pre-shaped alumina support bodies. In chapter 7 the effect of the hydrogen and carbon monoxide concentration and in chapter 8 the effect of the water concentration in the coal gas on the activity and the capacity of the iron-molybdenum mixed oxide absorbents is described. Regeneration of the loaded absorbents is an important part of the desulfurization process, dealt with in chapter 9. A number of regeneration procedures have been tested. (Abstract Truncated)

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: Effect of calcination temperature of catalysts

International Nuclear Information System (INIS)

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-01-01

Highlights: ► Oxidative desulfurization was studied with WO x /ZrO 2 calcined at different temp. ► The importance of the phases of zirconia and tungsten oxide was suggested. ► The catalyst was analyzed thoroughly with Raman and XRD techniques. ► The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO x /ZrO 2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO x /ZrO 2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO 2 ) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO 3 and monoclinic ZrO 2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO x /ZrO 2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Tecnología de desulfuración de fundiciones grises con el fin de obtener hierro con grafito esferoidal // A desulfuration technology for gray iron in order to obtain spheroidal graphite iron

Directory of Open Access Journals (Sweden)

A. Batista Cabrera

1999-01-01

Full Text Available En el siguiente trabajo se describe una tecnología de desulfuracíon del hierro fundido gris, tomando como base el ya conocidométodo de Volianik (1. En este caso se modificaron algunos parámetros del citado método, adecuándolos a las condicionesexistentes en la Empresa de Fundición de Hierro y Acero de Holguín.( E.F. H. A.Como agente desulfurante se empleó carburo de calcio empleado por Volianik. Como agente activador del desulfurante seutilizó aire comprimido seco. El desulfurante con la granulometría apropiada fue introducido en la cazuela con hierro fundido a1460 oC, por medio de un dispositivo diseñado y construido para este fin.Una gráfica con la dependencia entre el tiempo de soplado y el rendimiento fue obtenida. Como resultado se logró estableceruna tecnología de desulfuración que permite disminuir el contenido de azufre en el hierro fundido desde 0,067 hasta 0,0148%para un rendimiento de 78%.Palabras claves: Hierro gris, desul furación, hierro nodular._____________________________________________________________________AbstractA desulfuration technology for gray cast iron is shown based on the well-known Volianik’s desulfuration method. In this casesome of its parameters were modified, for fitting them to the existent conditions in the Empresa de Hierro Fundido y Acero deHolguín (E.F. H. A..As desulfuration agent calcium carbide was used instead of lime, as it is usually employed by Volianik.Dry compressed air was used as activating agent for the calcium carbide. This one, with the proper grain size it was introducedin a ladle containing 160 RG of melted gray iron at 1460 oC, by means of a mixing device designed and constructed by theauthors.A graphic dependence between air compressed blowing time and desulfuration efficiency was obtained.As a result, a desulfuration technology which permits decrease melted gray iron sulfur contain, from 0,067 till 0,0148 %, wasobtained for a yield of 78 %.Key words: Gray iron, desul

Preparation of MoO2/g-C3N4 composites with a high surface area and its application in deep desulfurization from model oil

Science.gov (United States)

Hou, Liang-pei; Zhao, Rong-xiang; Li, Xiu-ping; Gao, Xiao-han

2018-03-01

A series of catalysts of composition X-MoO2/g-C3N4 (X = 0, 0.5, 1, 3, 5 wt.%) were successfully synthesized by calcination of a mixture of (NH4)6Mo7O24·4H2O and g-C3N4. Oxidative desulfurization experiments were conducted using X-MoO2/g-C3N4 as a catalyst, H2O2 as an oxidant, and ionic liquids (ILs) as extraction agents. Catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and Brunauer-Emmett-Teller analysis (BET). Characterization results suggested that MoO2 was present in the catalyst and its crystallinity improved with increased Mo-loading. The catalysts had a larger specific surface area due to the presence of MoO2 dispersed on g-C3N4. Experimental results showed that 3%-MoO2/g-C3N4 had the highest catalytic activity among all the catalysts tested. A desulfurization rate of 96.0% was achieved under optimal conditions. Through gas chromatography-mass spectrometry (GC-MS) analysis, it was shown that dibenzothoiphene sulfone was the sole product of the oxidation desulfurization reaction. An apparent activation energy of 61.1 kJ/mol was estimated based on Arrhenius equation. The activity of 3%-MoO2/g-C3N4 slightly decreased after six runs. A possible mechanism for the reaction has been proposed.

Evaporation and crystallization of a droplet of desulfurization wastewater from a coal-fired power plant

International Nuclear Information System (INIS)

Liang, Zhengxing; Zhang, Li; Yang, Zhongqing; Qiang, Tang; Pu, Ge; Ran, Jingyu

2017-01-01

Highlights: • Evaporation and crystallization characteristics of the droplets of desulfurization wastewater. • TGA and DSC methods were used to investigate the evaporation and crystallization processes. • Evaporation and crystallization rates increase with the increase of temperature increasing rate. • Increasing volume of the droplet increases the evaporation rate, but decreases the crystallization rate. • Structure of the crystals changes significantly when the temperature increasing rate and the volume of the droplet change. - Abstract: Relationship between evaporation and crystallization characteristics of a droplet of desulfurization wastewater from a coal-fired power plant and some operating conditions was studied experimentally using a thermogravimetric analyzer (TGA) with differential scanning calorimetry (DSC) function and a scanning electron microscope (SEM). The results shows that, between 15 °C/min and 45 °C/min, a higher temperature increasing rate leads to higher evaporation and crystallization rates. The increment in the evaporation rate, caused by the same increment of temperature increasing rate, is larger, when the temperature increasing rate is lower. In addition, the final temperatures, ranging from 90 °C to 150 °C, have little impact on the evaporation and crystallization rates of the 0.5 μL droplet. Ultimately, for the droplets, ranging from 0.2 μL to 2.5 μL, evaporation rate increases with increasing volumes of the droplets, but the crystallization rate decreases. From the SEM results, it can be observed that the quantity of cracks on the surface of the crystals also declines with the increase in volumes. Furthermore, the Stefan flow becomes a significant and unneglectable factor in order to decrease the evaporation rate at the end of the evaporation period.

Recovery of SO2 and MgO from By-Products of MgO Wet Flue Gas Desulfurization.

Science.gov (United States)

Yan, Liyun; Lu, Xiaofeng; Wang, Quanhai; Guo, Qiang

2014-11-01

An industrial demonstration unit using natural gas as a heat source was built to calcine the by-products of MgO wet flue gas desulfurization from power plants; influencing factors on the SO 2 content in calciner gas were comprehensively analyzed; and an advantageous recycling condition of MgO and SO 2 from by-products was summarized. Results showed that the SO 2 content in the calciner gas was increased by more than 10 times under a lower excess air coefficient, a higher feed rate, a lower crystal water in by-products, and a higher feed port position. For the tests conducted under the excess air coefficient above and below one, the effect of the furnace temperature on the SO 2 content in the calciner gas was reversed. Results of activity analysis indicate that particles of MgO generated under the calcination temperature of 900-1,000°C had a high activity. In contrast, due to the slight sintering, MgO generated under the calcination temperature of 1,100°C had a low activity. To recycle SO 2 as well as MgO, a temperature range of 900-927°C for TE103 is proposed. These studies will prompt the desulfurization market diversification, reduce the sulfur's dependence on imports for making sulfuric acid, be meaningful to balance the usage of the natural resource in China, and be regarded as a reference for the development of this technology for other similar developing countries.

GeoChip-based analysis of the microbial community functional structures in simultaneous desulfurization and denitrification process.

Science.gov (United States)

Yu, Hao; Chen, Chuan; Ma, Jincai; Liu, Wenzong; Zhou, Jizhong; Lee, Duu-Jong; Ren, Nanqi; Wang, Aijie

2014-07-01

The elemental sulfur (S°) recovery was evaluated in the presence of nitrate in two development models of simultaneous desulfurization and denitrification (SDD) process. At the loading rates of 0.9 kg S/(m³·day) for sulfide and 0.4 kg N/(m³·day) for nitrate, S° conversion rate was 91.1% in denitrifying sulfide removal (DSR) model which was higher than in integrated simultaneous desulfurization and denitrification (ISDD) model (25.6%). A comprehensive analysis of functional diversity, structure and metabolic potential of microbial communities was examined in two models by using functional gene array (GeoChip 2.0). GeoChip data indicated that diversity indices, community structure, and abundance of functional genes were distinct between two models. Diversity indices (Simpson's diversity index (1/D) and Shannon-Weaver index (H')) of all detected genes showed that with elevated influent loading rate, the functional diversity decreased in ISDD model but increased in DSR model. In contrast to ISDD model, the overall abundance of dsr genes was lower in DSR model, while some functional genes targeting from nitrate-reducing sulfide-oxidizing bacteria (NR-SOB), such as Thiobacillus denitrificans, Sulfurimonas denitrificans, and Paracoccus pantotrophus were more abundant in DSR model which were highly associated with the change of S(0) conversion rate obtained in two models. The results obtained in this study provide additional insights into the microbial metabolic mechanisms involved in ISDD and DSR models, which in turn will improve the overall performance of SDD process. Copyright © 2014. Published by Elsevier B.V.

Simultaneous desulfurization and denitrification of flue gas by ·OH radicals produced from O2+ and water vapor in a duct.

Science.gov (United States)

Bai, Mindi; Zhang, Zhitao; Bai, Mindong

2012-09-18

In the present study, simultaneous flue gas desulfurization and denitrification are achieved with ·OH radicals generated from O(2)(+) reacting with water vapor in a duct. The O(2)(+) ions are generated by a strong ionization dielectric barrier discharge and then injected into the duct. Compared with conventional gas discharge treatment, the present method does not need a plasma reaction reactor, additional catalysts, reductants, or oxidants. The main recovered products are the liquids H(2)SO(4) and HNO(3), which can be used in many processes. Removal rates of 97% for NO and 82% for SO(2) are obtained under the following optimal experimental conditions: molar ratio of reactive oxygen species (O(2)(+), O(3)) to SO(2) and NO, 5; inlet flue gas temperature, 65 °C; reaction time, 0.94 s; and H(2)O volume fraction, 8%. Production of O(2)(+) and the plasma reaction mechanisms are discussed, and the recovered acid is characterized. The experimental results show that the present method performs better for denitrification than for desulfurization. Compared with conventional air discharge flue gas treatments, the present method has lower initial investment and operating costs, and the equipment is more compact.

Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

Science.gov (United States)

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.

Desulfurization from thiophene by SO42-/ZrO2 catalytic oxidation at room temperature and atmospheric pressure

International Nuclear Information System (INIS)

Wang Bo; Zhu Jianpeng; Ma Hongzhu

2009-01-01

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO 4 2- /ZrO 2 (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO 4 2- /ZrO 2 catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S 6+ and S 2- ) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S 6+ ). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5 h and SZB-3 h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5 h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO 4 2- /ZrO 2 catalytic oxidation reaction

A review on prospects and challenges of biological H₂S removal from biogas with focus on biotrickling filtration and microaerobic desulfurization

DEFF Research Database (Denmark)

Khoshnevisan, Benyamin; Tsapekos, Panagiotis; Alfaro, Natalia

2017-01-01

The production of biogas from sulfate-rich materials under anaerobic digestion results in the formation of hydrogen sulfide (H2S). The recommended level of H2S in the produced biogas for direct combustion purposes is in the range of 0.02 to 0.05% w/w (200 to 500 ppm), therefore, desulfurization i...

Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization.

Science.gov (United States)

Wang, Xu-Sheng; Huang, Yuan-Biao; Lin, Zu-Jin; Cao, Rong

2014-08-21

Highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) encapsulated in the mesocages of amine-functionalized metal-organic frameworks MIL-101(Cr)-NH2 has been prepared by an anion-exchange method. PTA anions (PW12O40(3-)) are stabilized in the mesocages via the electrostatic interaction with amino groups of the MIL-101(Cr)-NH2. The obtained catalyst (denoted PTA@MIL-101(Cr)-NH2) exhibits high catalytic activity in the extractive and catalytic oxidative desulfurization (ECODS) system under mild conditions. Moreover, it can be easily recovered and recycled several times without leaching and loss of activity.

The design of the extraction window of high power electron accelerator used in flue gas desulfurization

International Nuclear Information System (INIS)

He Tongqi; Chinese Academy of Sciences, Shanghai; Hu Wei; Sun Guangkui; Shi Weiguo; Li Minxi; Zhang Yutian; Pu Gengqiang

2007-01-01

Recently, the pollution caused by industrial exhaust gas, especially, the air pollution and acid rain resulting from the sulfur of exhaust gas, is increasingly drawing people's attention. The flue gas desulfurization by electron beam produced by high-power electron accelerator has the characteristics of high efficiency and non-secondary contamination. As one of the most pivotal part of accelerator, the service lifetime of this extraction window directly effects the stable operation of the device. In this paper, a brief review is given to summarize the advantages, material selecting, structure, replacing, maintaining of the extraction window of high-power electron accelerator developed by SINAP. (authors)

Research improvement in Zn-based sorbent for hot gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

X. Bu; Y. Ying; C. Zhang; W. Peng [China Coal Research Institute (CCRI), Beijing (China). Beijing Research Institute of Coal Chemistry

2005-07-01

Two Zn-based sorbents, named as L-991 and L-992, used for hot gas desulfurization were developed. The L-992, which was prepared by changing the Zn/Ti ratio and adding a certain proportion of Cu and Mn metal oxide, acquired better performance than L-991. The suitable desulfurisation temperature was 600-700{sup o}C for the L-991 and 600-800{sup o}C for the L-992. The sulfur capacity was about 16 g/100 g and 19-21 g/100 g of L-991 and L-992 respectively. After 17 multi-cycles sulfidation/regeneration tests, the sulfur capacity of the L-991 decreased greatly, while that of the L-992 still remained at 17 g/100 g. Both the sorbents showed orderly crystalline orientation and the particle size did not change. Sulfidation and regeneration tests were done both on lab micro-fixed bed reactor and SMOVEN equipment. During the continuous tests, the H{sub 2}S concentration can be reduced from about 10 g/m{sup 3} to less than 20 mg/m{sup 3}, the H{sub 2}S removal efficiency being {gt} 99%. 14 refs., 9 figs., 2 tabs.

Sulfur transformations related to revegetation of flue gas desulfurization sludge disposal sites

Energy Technology Data Exchange (ETDEWEB)

Barlas, S.A.; Artiola, J.F.; Salo, L.F.; Goodrich-Mahoney, J.W. [University of Arizona, Tucson, AZ (United States). Dept. of Soil, Water and Environmental Sciences

1999-10-01

This study investigated factors controlling redox conditions in flue gas desulfurization (FGD) sludge and identified ways to minimize the production of phytotoxic reduced sulfur species at FGD sludge disposal sites. The oxidation of reduced FGD sludge (Eh-385 mV) appears to be a two-step process mostly controlled by water content. Eighty percent of total sulfide in reduced sludge was oxidized within 20 h of exposure to air with constant water evaporation. When organic carbon (OC) was added to saturated oxidized sludge, the Eh dropped exponentially. Sulfate reduction began at an Eh of about -75 mV and reached a maximum at -265 to -320 mV. Water content, degree of mixing, concentration of OC, and temperature control the rate and extent of reduction of FGD sludge. This suggests that water saturation and OC inputs to revegetated disposal sites should be controlled, especially during warm temperatures, to prevent production of phytotoxic levels of sulfides.

Reactive Adsorption Desulfurization by Nanocrystalline ZnO/Zeolite A Molecular Sieves

Directory of Open Access Journals (Sweden)

Nada Sadoon Ahmedzeki

2017-09-01

Full Text Available Nanocrystalline ZnO/Zeolite type A composite was prepared by simple method of operation by . the precipitation of zinc oxide and loading on zeolite 5A in one step. Characterization was made by X-ray diffraction (XRD, X-ray fluorescence(XRF, N2 adsorption- desorption for BET surface area, and Atomic force microscopy (AFM. Results showed that zinc oxide was loaded on zeolite as noticed by the characteristic peaks and was of nano scale having an average diameter of 88.57nm. The percentage loading of ZnO on zeolite A was 28.37% and the surface area was 222m2/g. The activity of the prepared catalyst was examined in the desulfurization of double hydrogenated diesel fuel. The process was investigated in a controlled autoclave with temperature range studied 100220 oC. Results indicated an oxidation of thiophenic compounds on the surface of the catalyst coupled with adsorption. About 35% reduction was obtained and the capacity was 10.56 mg S/g catalyst.

Evidences for CYP3A4 autoactivation in the desulfuration of dimethoate by the human liver.

Science.gov (United States)

Buratti, Franca M; Testai, Emanuela

2007-11-20

Dimethoate (DIM) is an organophosphorothionate (OPT) pesticide used worldwide as a systemic insecticide and acaricide. It is characterized by low-to-moderate acute mammalian toxicity; similarly to the other OPT pesticides, its mode of action is mediated by the inhibition of acetylcholinesterase (AChE), exerted by its toxic metabolite dimethoate-oxon or omethoate (OME), which is also used as a direct acting pesticide. Human hepatic DIM bioactivation to the toxic metabolite OME has been characterized by using c-DNA expressed human CYPs and human liver microsomes (HLM) also in the presence of CYP-specific chemical inhibitors, with a method based on AChE inhibition. The obtained kinetic parameters and AChE IC(50) have been compared with those previously obtained with other OPTs, indicating a lower efficiency in DIM desulfuration reaction and a lower potency in inhibiting AChE. Results showed that, similarly to the other OPTs tested so far, at low DIM concentration OME formation is mainly catalysed by CYP1A2, while the role of 3A4 is relevant at high DIM levels. Differently from the other OPTs, DIM desulfuration reaction showed an atypical kinetic profile, likely due to CYP3A4 autoactivation. The sigmoidicity degree of the activity curve increased with the level of CYP3A4 in HLM or disappeared in the presence of a CYP3A4 chemical inhibitor. This atypical kinetic behaviour can be considered one of the possible explanations for the recent findings that among patients hospitalized following OPT intoxication, DIM ingestion gave different symptoms and more severe poisoning (23.1% of fatal cases versus total) than chlorpyrifos (8% of deaths), which has a lower LD(50) value. Since DIM-poisoned patients poorly responded to pralidoxime, the possibility to use CYP3A4 inhibitors could be considered as a complementary treatment.

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure.

Science.gov (United States)

Wang, Bo; Zhu, Jianpeng; Ma, Hongzhu

2009-05-15

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.

A Systematic Study on the Effect of Desilication of Clinoptilolite Zeolite on its Deep-Desulfurization Characteristics

Directory of Open Access Journals (Sweden)

Rahman Mahmoudi

2016-07-01

Full Text Available Natural clinoptilolite zeolite (CLP in its original or metal ion- exchanged form (Ni2+ is a weak adsorbent for relatively large thiophene derivative molecules like benzothiophene (BT and di-benzothiophene (DBT, due to its rather restricted micro-channel structure. A novelty of this work is that upon desilication treatments, it is possible to enhance the adsorption behavior of Ni2+-exchanged CLP for such large sulfur- containing molecules. A natural CLP zeolite has been desilicated using NaOH solutions in a concentration range of 0.2-2.0 M. The resulting powders have been subjected to XRF, XRD, FTIR, nitrogen adsorption/desorption, TEM and TGA analyses. The adsorption isotherms for the removal of thiophene (TP, BT, DBT and iso-propyl mercaptan (IPM have been obtained experimentally at 20 °C from simulated liquid fuels using iso-octane as solvent. The sample treated with 1.5 M NaOH solution showed the most significant enhancement in adsorptive properties. The selectivity order is IPM > TP > BT > DBT. Regenerability tests show a quasi constant adsorption capacity after the first cycle. The observed phenomena have been thoroughly discussed based on the physico-chemical analyses of the samples.

Desulfurization of petroleum induced by ionization radiation: benzothiophene behavior

International Nuclear Information System (INIS)

Andrade, Luana S.; Calvo, Wilson A.P.; Duarte, Celina L.

2013-01-01

Hydrodesulfurization (HDS) is currently the most common method used by refineries; this removes significantly sulfur compounds from petroleum fractions, however, is not highly effective for removing thiophene compounds such as benzothiophene, and generates high costs for the oil industry. Another factor, are the environmental laws, which over the years has become increasingly strict, especially regarding the sulfur content. This compound cause incalculable damage both to the industry and to the environment. Therefore new methods for petroleum desulfurization should be studied in order to minimize the impacts that these compounds cause. In the present study it was used ionizing radiation, a promising method of advanced oxidation in reducing sulfur compounds. The analysis were performed after purge and trap concentration of samples, followed by gas chromatography-mass spectrometry (GC-MS). Then benzothiophene samples with the same concentration from 27 mg.L -1 to 139 mg.L -1 were irradiated with different absorbed doses of radiation ranging from 1 kGy to 20 kGy in gamma irradiator Cobalt-60, Gammacell. These samples were analyzed by the same procedure used for the calibration curve, and the removals of benzothiophene after ionizing radiation treatment were calculated. It was observed that at higher doses there was a greater degradation of this compound and the formation of fragments, such as 1,2-dimethylbenzene and toluene, which may be removed by simple processes. (author)

Deep desulfurization of diesel oil oxidized by Fe (VI) systems

Energy Technology Data Exchange (ETDEWEB)

Shuzhi Liu; Baohui Wang; Baochen Cui; Lanlan Sun [Daqing Petroleum Institute, Daqing (China). College of Chemistry and Chemical Engineering

2008-03-15

Fe (VI) compound, such as K{sub 2}FeO{sub 4}, is a powerful oxidizing agent. Its oxidative potential is higher than KMnO{sub 4}, O{sub 3} and Cl{sub 2}. Oxidation activity of Fe (VI) compounds can be adjusted by modifying their structure and pH value of media. The reduction of Fe (VI), differing from Cr and Mn, results in a relatively non-toxic by-product Fe (III) compounds, which suggests that Fe (VI) compound is an environmentally friendly oxidant. Oxidation of model sulfur compound and diesel oil by K{sub 2}FeO{sub 4} in water-phase, in organic acid and in the presence of phase-transfer catalysts is investigated, respectively. The results show that the activity of oxidation of benzothiophene (BT) and dibenzothiophene (DBT) is low in water-phase, even adding phase-transfer catalyst to the system, because K{sub 2}FeO{sub 4} reacts rapidly with water to form brown Fe(OH){sub 3} to lose ability of oxidation of organic sulfur compounds. The activity of oxidation of the BT and DBT increases markedly in acetic acid. Moreover, the addition of the solid catalyst to the acetic acid medium promotes very remarkably oxidation of organic sulfur compounds. Conversions of the DBT and BT are 98.4% and 70.1%, respectively, under the condition of room temperature, atmospheric pressure, acetic acid/oil (v/v) = 1.0, K{sub 2}FeO{sub 4}/S (mol/mol) = 1.0 and catalyst/K{sub 2}FeO{sub 4} (mol/mol) = 1.0. Under the same condition, diesel oil is oxidized, followed by furfural extraction, the results display sulfur removal rate is 96.7% and sulfur content in diesel oil reduces from 457 ppm to 15.1 ppm. 11 refs., 9 figs., 5 tabs.

Synthesis of 2-azaindolizines by using an iodine-mediated oxidative desulfurization promoted cyclization of N-2-pyridylmethyl thioamides and an investigation of their photophysical properties.

Science.gov (United States)

Shibahara, Fumitoshi; Kitagawa, Asumi; Yamaguchi, Eiji; Murai, Toshiaki

2006-11-23

Iodine-mediated, oxidative desulfurization promoted cyclization of N-2-pyridylmethyl thioamides serves as an efficient and versatile method for the preparation of 2-azaindolizines (imidazo[1,5-a]pyridines) and rare 2-azaindolizine sulfur-bridged dimers. The 2-azaindolizines prepared in this manner are readily converted to a variety of fluorescent compounds by using transition-metal-catalyzed cross-coupling reactions. [reaction: see text].

Mercury isotope signatures of seawater discharged from a coal-fired power plant equipped with a seawater flue gas desulfurization system.

Science.gov (United States)

Lin, Haiying; Peng, Jingji; Yuan, Dongxing; Lu, Bingyan; Lin, Kunning; Huang, Shuyuan

2016-07-01

Seawater flue gas desulfurization (SFGD) systems are commonly used to remove acidic SO2 from the flue gas with alkaline seawater in many coastal coal-fired power plants in China. However, large amount of mercury (Hg) originated from coal is also transferred into seawater during the desulfurization (De-SO2) process. This research investigated Hg isotopes in seawater discharged from a coastal plant equipped with a SFGD system for the first time. Suspended particles of inorganic minerals, carbon residuals and sulfides are enriched in heavy Hg isotopes during the De-SO2 process. δ(202)Hg of particulate mercury (PHg) gradually decreased from -0.30‰ to -1.53‰ in study sea area as the distance from the point of discharge increased. The results revealed that physical mixing of contaminated De-SO2 seawater and uncontaminated fresh seawater caused a change in isotopic composition of PHg isotopes in the discharging area; and suggested that both De-SO2 seawater and local background contributed to PHg. The impacted sea area predicted with isotopic tracing technique was much larger than that resulted from a simple comparison of pollutant concentration. It was the first attempt to apply mercury isotopic composition signatures with two-component mixing model to trace the mercury pollution and its influence in seawater. The results could be beneficial to the coal-fired plants with SFGD systems to assess and control Hg pollution in sea area. Copyright © 2016 Elsevier Ltd. All rights reserved.

Economic assessment of advanced flue gas desulfurization processes. Final report

Energy Technology Data Exchange (ETDEWEB)

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

1981-09-01

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

A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

Science.gov (United States)

Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

2015-02-23

A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amelioration of alkali soil using flue gas desulfurization byproducts: productivity and environmental quality

Energy Technology Data Exchange (ETDEWEB)

Wang, S.J.; Chen, C.H.; Xu, X.C.; Li, Y.J. [Tsing Hua University, Beijing (China). Ministry of Education

2008-01-15

In this study, flue gas desulfurization (FGD) byproducts are used to ameliorate alkali soil. The average application rates for soils with low exchangeable sodium percentage (ESP), mid ESP, and high ESP are 20.9, 30.6, and 59.3 Mg ha{sup -1} respectively. The experimental results obtained for 3 consecutive years reveal that the emergence ratios and yields of the crops were 1.1-7.6 times and 1.1-13.9 times those of the untreated control, respectively. The concentrations of Cr, Pb, Cd, As, and Hg in the treated soils are far below the background values stipulated by the Environmental Quality Standard for Soils (GB 15618-1995). Their concentrations in the seeds of corn and alfalfa grown in the treated soils are far below the tolerance limits regulated by National Food Standards of China. The results of this research demonstrate that the amelioration of alkali soils using FGD byproducts is promising.

Growing Cu2S Thin Films by Exposing a Copper Substrate to Gas-Phase Products of Brown Coal Hydrothermal Desulfurization

Science.gov (United States)

Savitskii, D. P.; Stanishevskii, Ya. M.

2018-01-01

Thin films of copper(I) sulfide (Cu2S) are synthesized on a copper substrate by exposing it to vapor-phase sulfur-containing products resulting from the hydrothermal desulfurization of brown coal. The synthesized 0.1-mm-thick films have grain sizes in the range of 10‒20 μm, electrical resistivity ρ = 0.92 Ω cm at T = 300 K, and bang gap E g = 1.91 eV. The roughness of the films, in terms of the arithmetic mean deviation of the assessed profile, is R a = 2.46 μm.

Industrial application of gasoline aromatization and desulfurization technology in Hohhot refinery

Directory of Open Access Journals (Sweden)

Li Zixia

2017-01-01

Full Text Available Gasoline aromatization and desulfurization (GARDES technology is extensively used in refineries of Petrochina, aiming to produce high quality ultraclean fluid catalytic cracking (FCC gasoline. This article introduces the industrial application results on the hydrodesulfurization unit of the Hohhot refinery, which plays an important role in guiding next round gasoline upgrading. The characteristics and the principle of GARDES technology were elaborated by analyzing the distribution of sulfur and hydrocarbon compounds in the feed and product. The analysis results proved that the presence of broad ranged sulfur types in the feed can be removed at different stages. Olefin can be decreased by saturation and conversion into i-paraffins and aromatics. The sulfur content of the blend product can be limited under 10 mg/kg, showing GARDES technology has excellent sulfur removal ability. The olefin reduction can also satisfy the ever-increasing severe requirement about the olefin limitation, while the loss of research octane number (RON can be minimized to an acceptable level. Furthermore, according to the demand of gasoline upgrading, GARDES technology has great flexibility by adjusting operation condition without any further investment, which brings more economic benefits for refinery.

LIFAC flue gas desulfurization process an alternative SO{sub 2} control strategy

Energy Technology Data Exchange (ETDEWEB)

Patel, J.G. [Tampella Power Corp., Atlanta, GA (United States); Vilala, J. [Tampella Power Inc., Tampere (Finland)

1995-12-01

This paper discusses the results from two recently completed LIFAC flue gas desulfurization plants - 300 MW Shand lignite powered station owned by Saskatchewan Power Corporation and 60 MW Whitewater Valley high sulfur coal fired station owned by Richmond Powerand Light. LIFACis a dry FGD process in which limestone is injected into the upper regions of the boiler furnace and an activation reactor is used to humidify the unreacted limestone to achieve additional sulfur capture. The performance in both plants indicates that 70 to 80% sulfur is removed at a Ca/S ratio of 2. Cost performance data from these plants has shown that LI FAC both on construction cost and $/ton SO{sub 2} removed basis is very cost competitive compared to other SO{sub 2} control technologies. The Richmond plant has been realized under the auspices of the U.S. Department of Energy`s Clean Coal Technology program. The Shand plant is the first commercial installation in North America. The paper also discusses highlights of operating and maintenance experience, availability and handling of the solid waste product.

Management of dry flue gas desulfurization by-products in underground mines. Annual report, October 1994--September 1995

Energy Technology Data Exchange (ETDEWEB)

Chugh, Y.P.; Dutta, D.; Esling, S. [and others

1995-10-01

On September 30, 1993, the U.S. Department of Energy-Morgantown Energy Technology Center (DOE-METC) and Southern Illinois University at Carbondale (SIUC) entered into a cooperative research agreement entitled {open_quotes}Management of Dry Flue Gas Desulfurization By-Products in Underground Mines{close_quotes} (DE-FC21-93MC30252). Under the agreement Southern Illinois University at Carbondale will develop and demonstrate several technologies for the placement of coal combustion residues (CCBs) in abandoned coal mines, and will assess the environmental impact of such underground CCB placement. This report describes progress in the following areas: environmental characterization, mix development and geotechnical characterization, material handling and system economics, underground placement, and field demonstration.

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

Energy Technology Data Exchange (ETDEWEB)

1994-08-01

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

A briefing paper for the status of the flue gas desulfurization system at Indianapolis Power ampersand Light Company Petersburg Station Units 1 and 2

International Nuclear Information System (INIS)

Rutledge, C.K.; Wolsiffer, S.R.; Gray, S.M.; Martin, J.E.; Wedig, C.P.

1992-01-01

This paper presents a brief description of the status of the retrofit wet limestone flue gas desulfurization system project at Indianapolis Power ampersand Light Company (IPL) Petersburg Units 1 and 2. This project was initiated by IPL in response to the Clean Air Act of 1990 and is intended to treat the flue gas from two base load units with a combined capacity of approximately 700 MW gross electrical output

Mechanism of extractive/oxidative desulfurization using the ionic liquid inimidazole acetate: a computational study.

Science.gov (United States)

Wang, Hanlu; Xu, Mingsheng; Zhou, Rujin

2017-02-01

The dual role of the ionic liquid 1-butyl-3-methyl-imidazolium trifluoroacetic acid ([C 4 mim]TFA) as an extractant for thiophene (TH) and a catalyst for the oxidation of TH was explored at the molecular level by performing density functional theory (DFT) calculations. The calculated interaction energies demonstrated why [C 4 mim]TFA is a better extractant for thiophene sulfone (THO 2 ) than for TH. Two pathways were proposed for the oxidation of TH to THO 2 with [C 4 mim]TFA acting as a catalyst. In the dominant pathway, a peracid is formed which then oxidizes TH to the sulfoxide and sulfones. The presence of [C 4 mim]TFA was found to greatly reduce the barrier to the oxidative desulfurization (ODS) of TH using H 2 O 2 as an oxidant. Graphical Abstract Possible reaction mechanisms of TH with the aid of [C4mim]TFAᅟ.

Research program for environmentally-friendly coal utilization system. Follow-up project for simplified desulfurizers (Weifang Chemical Industry Works); Kankyo chowagata sekitan riyo system donyu shien jigyo. Kan`i datsuryu setsubi ni kakawaru follow up jigyo (Weifang kakosho)

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

To suppress the emission of environmental pollutants from coal utilization in China and to contribute to stable security of Japan`s energy, demonstration of clean coal technology and consolidation of diffusion base to be introduced into China have been promoted. Demonstration program for diffusing simplified desulfurizers has been promoted. For accelerating the achievement, experts of desulfurizers were delegated to Weifang Chemical Industry Works, to support the program. Exhaust gas is introduced from boiler via water spray dust remover, suction fan and centralized stack into absorption tower of the simplified wet-type desulfurizer. In the ascending process, the exhaust gas contacts with absorbent, to remove SO2 and dust. The absorbent is blasted up through the spray nozzle. The absorbent is oxidized by the air into sulfate ion in the liquid chamber at the lower part of tower, and neutralized by hydrated lime to form gypsum. Through the continuous operation for two years, understandings were remarkably increased. However, good treatment of the tax system is required for further diffusion. Though there are no problems for ordinary start and stop, emergency operation is insufficient. There are some problems in the maintenance due to the delay of finding failures. 16 figs., 1 tab.

The Economic Cost of China's New De-sulfur Policy During Her Gradual Accession to WTO: The Case of Industrial SO2 Emission

OpenAIRE

Jie He

2004-01-01

To understand the potential impacts of China's accession to WTO in her new de-sulfur policy (gradual reduction of 10% of annual SO2 emission by 2005 with respect to that of 2000), we construct a CGE model in which SO2 emission is directly linked to energy input consumption in production. The model equally considers the substitution possibility between energies of different SO2 effluent ratio by including energy as traditional production factor as labor and capital in the constant elasticity o...

Distribution of sulfur-containing aromatics between [hmim][Tf2N] and supercritical CO2: a case study for deep desulfurization of oil refinery streams by extraction with ionic liquids

Czech Academy of Sciences Publication Activity Database

Planeta, Josef; Karásek, Pavel; Roth, Michal

2006-01-01

Roč. 8, č. 1 (2006), s. 70-77 ISSN 1463-9262 R&D Projects: GA AV ČR IAA4031301 Institutional research plan: CEZ:AV0Z40310501 Keywords : ionic liquid * diesel fuel desulfurization * supercritical carbon dioxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.192, year: 2006

Revegetation of flue gas desulfurization sludge pond disposal sites

International Nuclear Information System (INIS)

Artiola, J.F.

1994-12-01

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

Oxidative desulfurization of benzothiophene and thiophene with WO{sub x}/ZrO{sub 2} catalysts: Effect of calcination temperature of catalysts

Energy Technology Data Exchange (ETDEWEB)

Hasan, Zubair; Jeon, Jaewoo [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

2012-02-29

Highlights: Black-Right-Pointing-Pointer Oxidative desulfurization was studied with WO{sub x}/ZrO{sub 2} calcined at different temp. Black-Right-Pointing-Pointer The importance of the phases of zirconia and tungsten oxide was suggested. Black-Right-Pointing-Pointer The catalyst was analyzed thoroughly with Raman and XRD techniques. Black-Right-Pointing-Pointer The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO{sub x}/ZrO{sub 2} catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO{sub x}/ZrO{sub 2} catalyst is around 700 Degree-Sign C. The most active catalyst is composed of tetragonal zirconia (ZrO{sub 2}) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO{sub 3} and monoclinic ZrO{sub 2} for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO{sub x}/ZrO{sub 2} catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Fundamental studies of desulfurization processes: reaction of methanethiol on ZnO and Cs/ZnO

Science.gov (United States)

Dvorak, Joseph; Jirsak, Tomas; Rodriguez, José A.

2001-05-01

The reaction of methanethiol on ZnO and Cs promoted ZnO surfaces has been studied with synchrotron based photoemission and thermal desorption spectroscopy. On ZnO, methanethiol undergoes selective reaction to produce carbon monoxide (37-58%), methane (23-38%), formaldehyde (12-15%), ethane (1-11%), and a mixture of ethylene and acetylene (3-13%). At low temperatures (cleavage occurs to yield methyl intermediate and atomic S. Carbon is removed from the surface as gaseous products above 500 K, and atomic sulfur remains bound to the zinc sites of the surface. Submonolayer amounts of cesium do not have a significant promotional effect on C-S bond cleavage, whereas Cs multilayers are found to significantly lower the activation barrier for C-S bond cleavage. This study illustrates the chemistry associated with the desulfurization of thiols on a catalytically relevant oxide surface.

Enhanced Hg{sup 2+} removal and Hg{sup 0} re-emission control from wet fuel gas desulfurization liquors with additives

Energy Technology Data Exchange (ETDEWEB)

Tingmei Tang; Jiang Xu; Rongjie Lu; Jingjing Wo; Xinhua Xu [Zhejiang University, Hangzhou (China). Department of Environmental Engineering

2010-12-15

Secondary atmospheric pollutions may result from wet flue gas desulfurization (FGD) systems caused by the reduction of Hg{sup 2+} to Hg{sup 0}. The present study employed three agents: Na{sub 2}S, 2,4,6-trimercaptotiazine, trisodium salt nonahydrate (TMT) and sodium dithiocarbamate (DTCR) to precipitate aqueous Hg{sup 2+} in simulated desulfurization solutions. The effects of the precipitator's dosing quantity, the initial pH value, the reaction temperature, the concentrations of Cl{sup -} and other metal ions (e.g. Cu{sup 2+} and Pb{sup 2+}) on Hg{sup 2+} removal were studied. A linear relationship was observed between Hg{sup 2+} removal efficiency and the increasing precipitator's doses along with initial pH. The addition of chloride and metal ions impaired the Hg{sup 2+} removal from solutions due to the complexation of Cl{sup -} and Hg{sup 2+} as well as the chelating competition between Hg{sup 2+} and other metal ions. Based on a comprehensive comparison of the treatment effects, DTCR was found to be the most effective precipitating agent. Moreover, all the precipitating agents were potent enough to inhibit Hg{sup 2+} reduction as well as Hg{sup 0} re-emission from FGD liquors. More than 90% Hg{sup 2+} was captured by precipitating agents while Hg{sup 2+} reduction efficiency decreased from 54% to just less than 3%. The additives could efficiently control the secondary Hg{sup 0} pollution from FGD liquors. 21 refs., 6 figs.

Desulfurization of fuel oils using an advanced oxidation method; Desulfuracion de combustibles usando un metodo de oxidacion avanzada

Energy Technology Data Exchange (ETDEWEB)

Flores Velazquez, Roberto; Rodas Grapain, Arturo [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

2008-07-01

In the present work, the oxidative desulfurization of fuel oils assisted by ultrasound was analyzed. It was studied the effect of hydrogen peroxide concentration, the fuel oil to aqueous solution volumetric ratio, and type of catalyst. The Fenton-like catalysts studied were ferric chloride and copper sulfate. [Spanish] En esta investigacion se analiza la desulfuracion oxidativa de combustoleo asistida con ultrasonido. Tambien se estudia el efecto de la concentracion de peroxido de hidrogeno (H{sub 2}O{sub 2}), la relacion volumetrica combustoleo/solucion acuosa y el tipo de catalizador. Los catalizadores tipo Fenton que se estudiaron fueron el cloruro ferrico (FeCl{sub 3}) y el sulfato de cobre (CuSO{sub 4}).

Spin lattice coupling in multiferroic hexagonal YMnO3

Indian Academy of Sciences (India)

phonon and spin waves involving deviations out of the spiral magnetic plane. This ... collimations were used to fully benefit from the focusing effects. ... following spin Hamiltonian based on the Heisenberg model H = JSiSj − hSini +. DSz i Sz.

Desulfurization reaction of high sulfur content flue gas treated by electron beam

International Nuclear Information System (INIS)

Hirosawa, Shojiro; Suzuki, Ryoji; Aoki, Shinji; Kojima, Takuji; Hashimoto, Shoji

2002-01-01

Experiments of flue gas treatment by electron beam were carried out, using simulated ligniteburning flue gas containing SO 2 (5500 ppm), NO (390 ppm) and H 2 O (22%). Removal efficiency of SO 2 was more than 90% at a dose of 1-2 kGy. It shows applicability of electron beam for treatment of lignite-burning flue gas. Another removal reaction besides the radiation-induced radical reaction and the thermal reaction occurring without irradiation was suggested by the facts that removal of SO 2 by the radical reaction is only a few hundreds of ppm and the removal amounts by thermal reaction under irradiation is lower than a half of total desulfurization. The mechanism similar to thermal reaction was proposed, assuming simultaneous uptake reaction of SO 2 and NH 3 on the surface of liquid aerosol. It was suggested that ammonium nitrate having deliquescence relative humidity (DRH) of 60% at 25 deg C plays an important role in producing liquid aerosols. Decrease of DRH of ammonium nitrate with elevating temperature and with formation of double salt of ammonium sulfate results in enhancement of formation of liquid aerosols. (author)

Simulation of the operation of an industrial wet flue gas desulfurization system

International Nuclear Information System (INIS)

Kallinikos, L.E.; Farsari, E.I.; Spartinos, D.N.; Papayannakos, N.G.

2010-01-01

In this work the simulation of a wet flue gas desulfurization (FGD) unit with spray tower of a power plant is presented, aiming at an efficient follow-up and the optimization of the FGD system operation. The dynamic model developed to simulate the performance of the system has been validated with operation data collected over a long period of time. All the partaking physical and chemical processes like the limestone dissolution, the crystallization of calcium sulfite and gypsum and the oxidation of sulfite ions have been taken into account for the development of the simulation model while the gas absorption by the liquid droplets was based on the two-film theory. The effect of the mean diameter of the slurry droplets on the performance of the system was examined, as it was used as an index factor of the normal operation of the system. The operation limits of the system were investigated on the basis of the model developed. It is concluded that the model is capable of simulating the system for significantly different SO 2 loads and that the absorption rate of SO 2 is strongly affected by the liquid dispersion in the tower. (author)

Integrated photooxidative extractive deep desulfurization using metal doped TiO2 and eutectic based ionic liquid

Science.gov (United States)

Zaid, Hayyiratul Fatimah Mohd; Kait, Chong Fai; Mutalib, Mohamed Ibrahim Abdul

2016-11-01

A series of metal doped TiO2 namely Fe/TiO2, Cu/TiO2 and Cu-Fe/TiO2 were synthesized and characterized, to be used as a photocatalyst in the integrated photooxidative extractive deep desulfurization for model oil (dodecane) and diesel fuel. The order of the photocatalytic activity was Cu-Fe/TiO2 followed by Cu/TiO2 and then Fe/TiO2. Cu-Fe/TiO2 was an effective photocatalyst for sulfur conversion at ambient atmospheric pressure. Hydrogen peroxide was used as the source of oxidant and eutectic-based ionic liquid as the extractant. Sulfur conversion in model oil reached 100%. Removal of sulfur from model oil was done by two times extraction with a removal of 97.06% in the first run and 2.94% in the second run.

Surface coal mine land reclamation using a dry flue gas desulfurization product: Short-term and long-term water responses.

Science.gov (United States)

Chen, Liming; Stehouwer, Richard; Tong, Xiaogang; Kost, Dave; Bigham, Jerry M; Dick, Warren A

2015-09-01

Abandoned coal-mined lands are a worldwide concern due to their potential negative environmental impacts, including erosion and development of acid mine drainage. A field study investigated the use of a dry flue gas desulfurization product for reclamation of abandoned coal mined land in USA. Treatments included flue gas desulfurization product at a rate of 280 Mg ha(-1) (FGD), FGD at the same rate plus 112 Mg ha(-1) yard waste compost (FGD/C), and conventional reclamation that included 20 cm of re-soil material plus 157 Mg ha(-1) of agricultural limestone (SOIL). A grass-legume sward was planted after treatment applications. Chemical properties of surface runoff and tile water (collected from a depth of 1.2m below the ground surface) were measured over both short-term (1-4 yr) and long-term (14-20 yr) periods following reclamation. The pH of surface runoff water was increased from approximately 3, and then sustained at 7 or higher by all treatments for up to 20 yr, and the pH of tile flow water was also increased and sustained above 5 for 20 yr. Compared with SOIL, concentrations of Ca, S and B in surface runoff and tile flow water were generally increased by the treatments with FGD product in both short- and long-term measurements and concentrations of the trace elements were generally not statistically increased in surface runoff and tile flow water over the 20-yr period. However, concentrations of As, Ba, Cr and Hg were occasionally elevated. These results suggest the use of FGD product for remediating acidic surface coal mined sites can provide effective, long-term reclamation. Copyright © 2015. Published by Elsevier Ltd.

Carbon behavior in the cyclic operation of dry desulfurization process for oxy-fuel integrated gasification combined cycle power generation

International Nuclear Information System (INIS)

Kobayashi, Makoto; Akiho, Hiroyuki

2016-01-01

Highlights: • Power plant with semi-closed gas turbine and O_2–CO_2 coal gasifier was studied. • Dry gas sulfur removal sorbent was improved for durability to carbon deposition. • The improved sorbent showed very low amount of deposited carbon during operation. • The sorbent is regenerable to be used repeatedly in the cyclic operation. • The sorbent exhibited high sulfur-removal performance in the cyclic operation. - Abstract: The dry sulfur-removal process is essential to provide suitable syngas treatment for the oxy-fuel integrated gasification combined cycle power generation plant. It is required that the dry sulfur-removal process to be durable to the carbon deposition due to syngas containing high concentration of carbon monoxide in addition to achieve sufficient performance for sulfur removal. Zinc ferrite sorbent is the most promising candidate for the dry sulfur-removal process. The sorbent was improved to enhance durability to the carbon deposition by modifying preparation. The improved sorbent was prepared from sulfates as the raw materials of zinc ferrite, while the former sorbent was using nitrates as the raw materials. The improved sorbent as well as the former sorbent were evaluated on the performance and carbon deposition tendency in oxy-fuel syngas condition in a fixed bed reactor at elevated pressure and temperature. The results expressed that the improved sorbent has higher desulfurization performance and durability to carbon deposition in the condition expected for cyclic operation of the sulfur-removal process in comparison with the former sorbent. The improved sorbent possessed the superior desulfurization performance as well as the capability for inhibit carbon deposition in the oxy-fuel syngas conditions. The results confirmed the enhanced feasibility of the dry sulfur-removal process by utilizing the improved sorbent.

Production of ultra-low-sulfur gasoline: an equilibrium and kinetic analysis on adsorption of sulfur compounds over Ni/MMS sorbents.

Science.gov (United States)

Subhan, Fazle; Liu, B S; Zhang, Q L; Wang, W S

2012-11-15

High performance nickel-based micro-mesoporous silica (Ni/MMS) sorbent was prepared by incipient wetness impregnation with ultrasonic aid (IWI-u) for adsorptive desulfurization (ADS) of commercial gasoline and simulated fuels. The sorbents were characterized with BET, XRD, TPR, SEM, HRTEM and TG/DTG. These results show that 20 wt%Ni/MMS (IWI-u) can still retain the framework of MMS and nickel particles were homogeneously distributed in the MMS channels without any aggregation, which improved significantly the ADS performance of the sorbents. The studies on the ADS kinetics indicate that the adsorption behavior of thiophene (T), benzothiophene (BT) and dibenzothiophene (DBT) over 20 wt%Ni/MMS (IWI-u) can be described appropriately by pseudo second-order kinetic model. The intraparticle diffusion model verified that the steric hindrance and intraparticle diffusion were the rate controlling step of the adsorption process of DBT molecules. Langmuir model can be used to describe the adsorption isotherms for T, BT and DBT due to low coverage. The regeneration sorbent maintains the sulfur removal efficiency of 85.9% for 6 cycles. Copyright © 2012 Elsevier B.V. All rights reserved.

Evaluation of the polysubstituted pyridinium ionic liquid [hmmpy][Ntf2] as a suitable solvent for desulfurization: Phase equilibria

International Nuclear Information System (INIS)

Arce, Alberto; Francisco, Maria; Soto, Ana

2010-01-01

Suitability of a pyridinium ionic liquid as a solvent in desulfurization has been analyzed. (Liquid + liquid) equilibria for ternary systems composed by 1-hexyl-3,5-dimethyl pyridinium {bis[trifluoromethylsulfonyl]imide, thiophene, and three hydrocarbons representative of fuel (n-heptane, 2,2,4 trimethylpentane, and toluene) have been determined at T = 298.15 K and atmospheric pressure. High solubility of thiophene in the ionic liquid and also of toluene have been found, being this solvent practically immiscible with 2,2,4 trimethylpentane and heptane. Equilibrium data of these systems have been well correlated with UNIQUAC equations finding the highest deviations for the ternary system involving toluene. NRTL model drove to worse results being considered as not suitable model to correlate the experimental results.

Improvement of Biodesulfurization Rate of Alginate Immobilized Rhodococcus erythropolis R1.

Science.gov (United States)

Derikvand, Peyman; Etemadifar, Zahra

2014-03-01

Sulfur oxides released from the burning of oil causes severe environmental pollution. The sulfur can be removed via the 4S pathway in biodesulfurization (BDS). Immobilization approaches have been developed to prevent cell contamination of oil during the BDS process. The encapsulation of Rhodococcus erythropolis R1 in calcium alginate beads was studied in order to enhance conversion of dibenzothiophene (DBT) to 2-hydroxy biphenyl (2-HBP) as the final product. Also the effect of different factors on the BDS process was investigated. Calcium alginate capsules were prepared using peristaltic pumps with different needle sizes to control the beads sizes. Scanning electron microscopy and flow cytometry methods were used to study the distribution and viability of encapsulated cells, respectively. Two non-ionic surfactants and also nano Ƴ-Al2O3were used with the ratio of 0.5% (v/v) and 1:5 (v/v) respectively to investigate their BDS efficiency. In addition, the effect of different bead sizes and different concentrations of sodium alginate in BDS activity was studied. The 2% (w/v) sodium alginate beads with 1.5mm size were found to be the optimum for beads stability and efficient 2-HBP production. The viability of encapsulated cells decreased by 12% after 20 h of desulfurization, compared to free cells. Adding the non-ionic surfactants markedly enhanced the rate of BDS, because of increasing mass transfer of DBT to the gel matrix. In addition, Span 80 was more effective than Tween 80. The nanoƳ-Al2O3 particles could increase BDS rate by up to two-folds greater than that of the control beads. The nano Ƴ-Al2O3 can improve the immobilized biocatalyst for excellent efficiency of DBT desulfurization. Also the BDS activity can be enhanced by setting the other explained factors at optimum levels.

Increasing the production of desulfurizing biocatalysts by means of fed - batch culture

International Nuclear Information System (INIS)

Berdugo, C I; Mena, J A; Acero, J R; Mogollon, L

2001-01-01

Over the past years, environmental regulations have driven a lot of effort for the development of new technologies for the upgrading of fossil fuels. Biotechnology offers an alternative way to process fossil fuels by means of a biodesulfurization technology where the production of the biocatalyst is one of the key topics. Traditionally, the production is carried out in batch culture where the maximum cellular concentration is restricted by inherent limitations of the culture type and the microorganism growth rate. This work addresses the production of two desulfurizing microorganisms: Rhodococcus erythropolis IGTS8 and gordona rubropertinctus ICP172 using fed-batch culture. Fed-batch cultures were conducted in a 12 L fermentor using ICP 4 medium containing glucose and DMSO as carbon and sulfur sources. As a result, cell concentration was increased 1.5 and 3 times with fed-batch cultures using constant and exponential flow respectively, achieving a maximum cell concentration of 7.3 g DCW/L of biocatalyst igts8 and 12.85 gGDCW/L of the new biocatalyst ICP172. Both biocatalysts presented biodesulfurization activity in a spiked matrix DBT/HXD and in diesel matrix with the detection of 2-HBP which is the end-product of DBT degradation pathway

Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

Energy Technology Data Exchange (ETDEWEB)

Wang, Lei; Zhao, Liang, E-mail: liangzhao@cup.edu.cn; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

2017-03-31

Highlights: • Electronic characteristics determined adsorption characteristics of transition metals. • Cobalt has the similar adsorption ability of thiophene as nickel. • Adsorption capacity of Cr and Mo was extremely fierce, while Cu has the potential ability for adsorbing thiophene. • The preference adsorption site for thiophene was hollow site on all the seven surface. - Abstract: To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

Desulfurization of coal by pyrolysis and hydropyrolysis with addition of KOH/NaOH

Energy Technology Data Exchange (ETDEWEB)

Quanrun Liu; Haoquan Hu; Shengwei Zhu; Qiang Zhou; Wenying Li; Xianyong Wei; Kechang Xie [Dalian University of Technology, Dalian (China). Institute of Coal Chemical Engineering

2005-08-01

In this paper, a two-step desulfurization process for high-sulfur coal was investigated. Two Chinese coals with the addition of 10 wt % potassium hydroxide or sodium hydroxide were pyrolyzed under an atmosphere of nitrogen or hydrogen in a fixed-bed reactor at 600{sup o}C, and then the obtained chars were washed with hot water. The results indicated that, without the addition of an alkali component, the sulfur removal of these two coals by pyrolysis and hydropyrolysis is {approximately}40%-50% and the sulfur content of chars is reduced only slightly, in comparison with the original coals; with the addition of 10 wt % potassium hydroxide or sodium hydroxide into the original coals and the chars being washed with hot water, the sulfur removal is {approximately}70%-80% and the sulfur content in chars is reduced dramatically. The combustion behavior of chars was also investigated, using thermogravimetric analysis. The results showed that those chars that had an added alkali component and were subjected to water-washing were more reactive and can be burned more easily than those without added alkali, which was also confirmed by a kinetics analysis of char combustion. 21 refs., 3 figs., 6 tabs.

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents by X-ray photoelectron spectroscopy and scanning electron microscopy

Science.gov (United States)

Siriwardane, Ranjani V.; Poston, James A.

1993-05-01

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents was performed by X-ray photoelectron spectroscopy and scanning electron microscopy/energy-dispersive spectroscopy at temperatures of 298 to 823 K. Analysis of copper oxides indicated that the satellite structure of the Cu22p region was absent in the Cu(I) state but was present in the Cu(II) state. Reduction of CuO at room temperature was observed when the ion gauge was placed close to the sample. The satellite structure was absent in all the copper oxides at 823 K in vacuum. Differentiation of the oxidation state of copper utilizing both Cu(L 3M 4,5M 4,5) X-ray-induced Auger lines and Cu2p satellite structure, indicated that the copper in zinc copper ferrite was in the + 1 oxidation state at 823 K. This + 1 state of copper was not significantly changed after exposure to H 2, CO, and H 2O. There was an increase in Cu/Zn ratio and a decrease in Fe/Zn ratio on the surface of zinc copper ferrite at 823 K compared to that at room temperature. These conditions of copper offered the best sulfidation equilibrium for the zinc copper ferrite desulfurization sorbent. Analysis of iron oxides indicated that there was some reduction of both Fe 2O 3 and FeO at 823K. The iron in zinc copper ferrite was similar to that of Fe 2O 3 at room temperature but there was some reduction of this Fe(III) state to Fe(II) at 823 K. This reduction was more enhanced in the presence of H 2 and CO. Reduction to Fe(II) may not be desirable for the lifetime of the sorbent.

Gasoline Biodesulfurization DE-FC07-97ID13570 FINAL REPORT; FINAL

International Nuclear Information System (INIS)

Pienkos, Philip T.

2002-01-01

Nine strains were identified to grow with gasoline as sole sulfur source. Two different genes were cloned from Gordonia terrae KGB1 and tested for the ability to support gasoline BDS. The first of these, fmoA, was cloned by screening a KGB1 gene library for the ability to convert indole to indigo (a sulfur-regulated capability in KGB1). The fmoA gene was overexpressed in a gasoline tolerant strain of Pseudomonas putida PpG1 and the recombinant strain was shown to convert thiophene to a dimer of thiophene sulfoxide at rates nearly two orders of magnitude higher than KGB1 could catalyze the reaction. Despite this high activity the recombinant PpG1 was unable to demonstrate any activity against gasoline either in shake flask or in bench-scale gasoline BDS bioreactor. A second gene (toeA) was cloned from KGB1 and shown to support growth of Rhodococcus erythropolis JB55 on gasoline. The toeA gene was also identified in another gasoline strain T. wratislaviensis EMT4, and was identified as a homolog of dszA from R. erythropolis IGTS8. Expression of this gene in JB55 supported conversion of DBTO2 (the natural substrate for DszA) to HPBS, but activity against gasoline was low and BDS results were inconsistent. It appeared that activity was directed against C2- and C3-thiophenes. Efforts to increase gene expression by plasmid manipulation, by addition of flavin reductase genes, or by expression in PpG1 were unsuccessful. The DszC protein (DBT monooxygenase) from IGTS8 has very little activity against the sulfur compounds in gasoline, but a mutant enzyme with a substitution of phenylalanine for valine at position 261 was shown to have an altered substrate range. This alteration resulted in increased activity against gasoline, with activity towards mainly C3- and C4-thiophenes and benzothiophene. A mutant library of dszB was constructed by RACHITT (W. C. Coco et al., DNA shuffling method for generating highly recombined genes and evolved enzymes. 2001. Nature Biotech. 19

Gasoline Biodesulfurization DE-FC07-97ID13570 FINAL REPORT

Energy Technology Data Exchange (ETDEWEB)

Pienkos, Philip T.

2002-01-15

Nine strains were identified to grow with gasoline as sole sulfur source. Two different genes were cloned from Gordonia terrae KGB1 and tested for the ability to support gasoline BDS. The first of these, fmoA, was cloned by screening a KGB1 gene library for the ability to convert indole to indigo (a sulfur-regulated capability in KGB1). The fmoA gene was overexpressed in a gasoline tolerant strain of Pseudomonas putida PpG1 and the recombinant strain was shown to convert thiophene to a dimer of thiophene sulfoxide at rates nearly two orders of magnitude higher than KGB1 could catalyze the reaction. Despite this high activity the recombinant PpG1 was unable to demonstrate any activity against gasoline either in shake flask or in bench-scale gasoline BDS bioreactor. A second gene (toeA) was cloned from KGB1 and shown to support growth of Rhodococcus erythropolis JB55 on gasoline. The toeA gene was also identified in another gasoline strain T. wratislaviensis EMT4, and was identified as a homolog of dszA from R. erythropolis IGTS8. Expression of this gene in JB55 supported conversion of DBTO2 (the natural substrate for DszA) to HPBS, but activity against gasoline was low and BDS results were inconsistent. It appeared that activity was directed against C2- and C3-thiophenes. Efforts to increase gene expression by plasmid manipulation, by addition of flavin reductase genes, or by expression in PpG1 were unsuccessful. The DszC protein (DBT monooxygenase) from IGTS8 has very little activity against the sulfur compounds in gasoline, but a mutant enzyme with a substitution of phenylalanine for valine at position 261 was shown to have an altered substrate range. This alteration resulted in increased activity against gasoline, with activity towards mainly C3- and C4-thiophenes and benzothiophene. A mutant library of dszB was constructed by RACHITT (W. C. Coco et al., DNA shuffling method for generating highly recombined genes and evolved enzymes. 2001. Nature Biotech. 19

Oxidative desulfurization-fluorination of thioethers. Application for the synthesis of fluorinated nitrogen containing building blocks.

Science.gov (United States)

Hugenberg, Verena; Fröhlich, Roland; Haufe, Günter

2010-12-21

An oxidative desulfurization-fluorination protocol has been used to synthesize (2S)-2-(difluoromethyl)-N-tosylpyrrolidine (6a) and (2S)-2-(trifluoromethyl)-N-tosylpyrrolidine (7a) from the (2S)-prolinol-derived (2S)-2-(4-chlorophenylthiomethyl)-N-tosylpyrrolidine (9) or (2S)-2-(dithian-2-yl)-N-tosylpyrrolidine (5). Efforts to prepare 3,3-difluoroalanine similarly from an N-protected S-aryl-cysteine ester 17 gave only traces of the target compound 18. Instead, an unique N-(α,α-difluorobenzyl)-N-α',α'-dibromoglycine ester 19 was formed by an unprecedented sequence of reaction steps. A plausible mechanism is suggested involving a sulfur-assisted deoxygenation-difluorination of an imino oxygen and a haloform reaction like carbon-carbon bond fission as key-steps. Efforts to prepare (2S)-2-(fluoromethyl)-N-tosylpyrrolidine (12) from (2S)-N-tosylprolinol (3) by treatment with Fluolead™ (1-tert-butyl-4-trifluorosulfanyl-3,5-dimethylbenzene) gave only 5% of the target compound, but 95% of (3R)-3-fluoro-N-tosylpiperidine (11a) by ring enlargement.

Anaerobic desulphurisation of thiophenes by mixed microbial communities from oilfields

NARCIS (Netherlands)

Marcelis, C.L.M.; Ivanova, A.E.; Janssen, A.J.H.; Stams, A.J.M.

2003-01-01

Anaerobic enrichment cultures obtained from oil fields degraded various thiophenic compounds i.e. thiophene, benzothiophene and dibenzothiophene, with the concomitant formation of sulphide using hydrogen, lactate and ethanol as possible electron donors. It was demonstrated that dibenzothiophene was

Study of slag-refractory system in iron desulfurization process by isopleths from Ca O-Si O{sub 2}-Al{sub 2} O{sub 3} equilibrium diagram; Analise da interacao escoria de dessulfuracao de gusa - refratario do carro-torpedo a partir de projecao vertical no diagrama de equilibrio CaO-SiO{sub 2}-Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Lima, Marco Antonio; Tenorio, Jorge Alberto Soares [Sao Paulo Univ., SP (Brazil). Escola Politecnica

1996-12-31

The sulfur withdrawal from liquid iron to compatible levels in steels plant processes capability is an important task of high quality rolled products fabrication. Mixture of lime forms a family of desulfurization agent frequently used, mainly their lower cost if injected in iron to reach not so lower levels of desulfurization. The use of this desulfurization agents produces approximately 7.0 Kg/t of slag, that results between 10 to 30 Kg/t of total slag. This slag interacts with the refractory lining of torpedo car, normally high alumina. In the present case it was analyzed an interaction between a slag formed by the use of the agent plus a blast furnace slag with a high alumina tar bonded lining. Isopleths of Ca O-Si O{sub 2}-Al{sub 2} O{sub 3} equilibrium diagram were constructed to represent the slag-refractory interaction. The results show that the use of the agent formed by lime and aluminium by-product is more deleterious to studied lining, what confirm the observations carried out in industrial plant. (author) 11 refs., 9 figs., 3 tabs.

The Influence of Micro-Oxygen Addition on Desulfurization Performance and Microbial Communities during Waste-Activated Sludge Digestion in a Rusty Scrap Iron-Loaded Anaerobic Digester

Directory of Open Access Journals (Sweden)

Renjun Ruan

2017-02-01

Full Text Available In this study, micro-oxygen was integrated into a rusty scrap iron (RSI-loaded anaerobic digester. Under an optimal RSI dosage of 20 g/L, increasing O2 levels were added stepwise in seven stages in a semi-continuous experiment. Results showed the average methane yield was 306 mL/g COD (chemical oxygen demand, and the hydrogen sulphide (H2S concentration was 1933 ppmv with RSI addition. O2 addition induced the microbial oxidation of sulphide by stimulating sulfur-oxidizing bacteria and chemical corrosion of iron, which promoted the generation of FeS and Fe2S3. In the 6th phase of the semi-continuous test, deep desulfurization was achieved without negatively impacting system performance. Average methane yield was 301.1 mL/g COD, and H2S concentration was 75 ppmv. Sulfur mass balance was described, with 84.0%, 11.90% and 0.21% of sulfur present in solid, liquid and gaseous phases, respectively. The Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE analysis revealed that RSI addition could enrich the diversity of hydrogenotrophic methanogens and iron-reducing bacteria to benefit methanogenesis and organic mineralization, and impoverish the methanotroph (Methylocella silvestris to reduce the consumption of methane. Micro-oxygen supplementation could enhance the diversity of iron-oxidizing bacteria arising from the improvement of Fe(II release rate and enrich the sulphur-oxidising bacteria to achieved desulfurization. These results demonstrated that RSI addition in combination with micro-oxygenation represents a promising method for simultaneously controlling biogas H2S concentration and improving digestion performance.

Time Variability of the Dust Sublimation Zones in Pre-Main Sequence Disk Systems

Science.gov (United States)

Sitko, Michael L.; Carpenter, W. J.; Grady, C. A.; Russel, R. W.; Lynch, D. K.; Rudy, R. J.; Mazuk, S. M.; Venturini, C. C.; Kimes, R. L.; Beerman, L. C.;

Evaluation of revegetation techniques of a saline flue gas desulfurization sludge pond

Energy Technology Data Exchange (ETDEWEB)

Salo, L.F.; Artiola, J.F.; Goodrich-Mahoney, J.W. [University of Arizona, Tucson, AZ (United States). Renewable National Resources

1999-01-01

Codisposal of flue gas desulfurization (FGD) sludge with low-volume generating station waste simplifies disposal but creates a saline, high boron (B) waste that may be difficult to revegetate after site closure. Studies on a delta of waste material in a codisposal pond at the coal-fired Coronado Generating Station in eastern Arizona evaluated management techniques, amendments, and plants for revegetating this material. One study investigated leaching and ridging techniques and a second evaluated amendment with manure, wood shavings, and fly ash, Four salt-tolerant grass species and four saltbushes (A triplex spp,) were evaluated in the two studies. Criteria for success were high survival rates and growth, as measured by grass height and shrub height x width. Leaching salts and B from the waste was not necessary for establishment and growth of transplanted shrubs and grasses. Ridging was not a successful technique, due to limited moisture and high levels of salinity and B on these structures. Gardner saltbush (A, gardneri (Moq.) D, Dietr.) and a fourwing saltbush (A. canescens (Pursh) Nutt,) accession from the site were the most successful shrubs and alkali sactonn (Sporobolus airoides (Torr,) Torr. `Saltalk`) was the most successful grass at this disposal pond. Amendment with manure, wood shavings, or fly ash did not increase plant survival. Growth of grasses was improved with all amendments and was greatest with manure, but growth of shrubs was not improved with any amendment. 33 refs., 8 tabs.

Mechanistic studies of chemical looping desulfurization of Mn-based oxides using in situ X-ray absorption spectroscopy

International Nuclear Information System (INIS)

König, C.F.J.; Nachtegaal, M.; Seemann, M.; Clemens, F.; Garderen, N. van; Biollaz, S.M.A.; Schildhauer, T.J.

2014-01-01

Highlights: • Mn sorbents remove H 2 S from hot syngas in chemical looping desulfurization process. • State of Mn followed by in situ X-ray absorption spectroscopy and mass spectrometry. • Two-step mechanism explains the formation of SO 2 under reducing conditions. - Abstract: Cleaning of producer gas from biomass gasification is required for further processing, e.g. to avoid catalyst poisoning in subsequent conversion steps. High-temperature gas cleaning, of which sulfur removal is an important part, is a promising way to improve the overall efficiency of biomass conversion. In a high temperature “chemical looping desulfurization” process, a sorbent material, here manganese oxide, is cycled between producer gas from the gasifier to remove sulfur species, and an oxidizing atmosphere, in which the sulfur species are released as SO 2 . Alternatively, the use of such material as reactive bed material could be integrated into an allothermal dual fluidized bed gasifier. In a laboratory reactor, we subjected manganese-based materials to a periodically changing gas atmosphere, simulating a “chemical looping desulfurization” reactor. The “fuel reactor” gas contained H 2 , CO, CH 4 and H 2 S, similar as in the producer gas, and the “oxidizing reactor” contained diluted O 2 . Mass spectrometry showed that most of the H 2 S is taken up by the sample in the “fuel reactor” part, while also some unwanted SO 2 is generated in the “fuel reactor” part. Most of the sulfur is released in the oxidizing reactor. Simultaneous in situ X-ray absorption spectroscopy (XAS) of the Mn materials during different stages of the chemical looping desulfurization process showed that the initial Mn 3 O 4 is transformed in the presence of H 2 S to MnS via a MnO intermediate in the fuel reactor. Oxygen from the reduction of Mn 3 O 4 oxidizes some H 2 S to the undesired SO 2 in the fuel reactor. Upon exposure to O 2 , MnS is again oxidized to Mn 3 O 4 via MnO, releasing SO

Process of desulfurizing dephenolating, and cracking raw pitch obtained by dry distilling lignite, shale, etc

Energy Technology Data Exchange (ETDEWEB)

1932-12-21

A process is described of desulfurizing, dephenelating, and cracking the dry pitch obtained by dry distillation of lignite, bituminous shale, asphaltic rocks, and peat and fossil coals, that is characterized by the raw material being distilled in a retort together with calcium oxide, the vapors escaping from the still being compelled to pass through a catalyst tube containing calcium oxide mixed with other metallic oxide, the catalyst being helped by suitable heating to a temperature higher than that of the retort mentioned. For the purpose of lessening the quantity of phenolic groups contained in the raw tar to eliminate a great part of the sulfur belonging to the thiophenols and hydrogen sulfide without removing the organic radical to which they are attached, to accomplish a pyrogenic dissociation at the temperature of distillation of the pitch by means of using bone acid (phosphoric) to obtain a greater yield of light hydrocarbon from heavy hydrocarbons. Another purpose is the elimination of sulfur and thiophene and whatever neutral sulfur is contained in the primary pitch, by means of iron sulfate and copper in the anhydrous state or by means of other sulfates whose metals have the ability to form sulfides with sulfur.

Flue-gas desulfurization gypsum effects on urea-degrading bacteria and ammonia volatilization from broiler litter.

Science.gov (United States)

Burt, Christopher D; Cabrera, Miguel L; Rothrock, Michael J; Kissel, D E

2017-08-01

A major concern of the broiler industry is the volatilization of ammonia (NH3) from the mixture of bedding material and broiler excretion that covers the floor of broiler houses. Gypsum has been proposed as a litter amendment to reduce NH3 volatilization, but reports of NH3 abatement vary among studies and the mechanism responsible for decreasing NH3 volatilization is not well understood. The goal of this study was to evaluate the effect of adding 20 or 40% flue-gas desulfurization gypsum (FGDG) to broiler litter on pH, electrical conductivity (EC), water potential, urea-degrading bacteria abundance, NH3 and carbon dioxide (CO2) evolution, and nitrogen (N) mineralization in several 21-d experiments. The addition of FGDG to broiler litter increased EC by 24 to 33% (P mineralization by 10 to 11% (P = 0.0001) as compared to litters not amended with FGDG. Furthermore, the addition of FGDG to broiler litter decreased NH3 volatilization by 18 to 28% (P litter pH values compared to un-amended litter (P litter with 20% FGDG can decrease NH3 volatilization and increase the fertlizer value of broiler litter. © 2017 Poultry Science Association Inc.

Selected species and amendments for revegetating saline flue gas desulfurization sludge: greenhouse study

Energy Technology Data Exchange (ETDEWEB)

Salo, L.F.; Artiola, J.F.; Goodrich-Mahoney, J.W. [University of Arizona, Tuscon, AZ (United States). Dept. of Soil, Water and Environmental Science

1997-07-01

Codisposing low-volume wastes from electrical generating stations with flue gas desulfurization (FGD) scrubber sludge simplifies waste disposal but produces a saline waste that presents unique challenges to revegetation. This greenhouse study identified plants and amendments for revegetating a saline FGD sludge disposal pond in eastern Arizona. Survival and growth of 16 sown accessions plus two vegetatively propagated accessions of inland saltgrass were investigated in saline FGD sludge. Amendments used included two soils from the disposal site, Claysprings gravelly clay and Sheppard sand, composted steer manure, and N-P-K fertilizers. Sols and manure were added at 2:1 sludge/amendment (v/v). Plants were irrigated with a 1:1 mixture of disposal pond water and untreated well water. One accession of inland saltgrass, two cultivars of tall wheatgrass, Altai wildrye tall fescue and alkali sacaton show promise for revegetating saline FGD sludge disposal sites. Survival rates were the same in unamended sludge and in sludge amended with the clay soil or with N-P-K fertilizer. Plant dry matter produced was the same in unamended sludge and in sludge amended with either of the soils or with N-P-K. Although survival rates were significantly lower with manure than with any other amendment, growth was significantly greater by all measurements, due to the high fertility of this treatment. 34 refs., 5 tabs.

Adsorptive Desulfurization of Model Gasoline by Using Different Zn Sources Exchanged NaY Zeolites

Directory of Open Access Journals (Sweden)

Jingwei Rui

2017-02-01

Full Text Available A series of Zn-modified NaY zeolites were prepared by the liquid-phase ion-exchange method with different Zn sources, including Zn(NO32, Zn(Ac2 and ZnSO4. The samples were tested as adsorbents for removing an organic sulfur compound from a model gasoline fuel containing 1000 ppmw sulfur. Zn(Ac2-Y exhibited the best performance for the desulfurization of gasoline at ambient conditions. Combined with the adsorbents’ characterization results, the higher adsorption capacity of Zn(Ac2-Y is associated with a higher ion-exchange degree. Further, the results demonstrated that the addition of 5 wt % toluene or 1-hexene to the diluted thiophene (TP solution in cyclohexane caused a large decrease in the removal of TP from the model gasoline fuel. This provides evidence about the competition through the π-complexation between TP and toluene for adsorption on the active sites. The acid-catalyzed alkylation by 1-hexene of TP and the generated complex mixture of bulky alkylthiophenes would adsorb on the surface active sites of the adsorbent and block the pores. The regenerated Zn(Ac2-Y adsorbent afforded 84.42% and 66.10% of the initial adsorption capacity after the first two regeneration cycles.

Transition Metal Complexes of Cr, Mo, W and Mn Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene and Dibenzothiophene Ligands

Energy Technology Data Exchange (ETDEWEB)

Reynolds, Michael [Iowa State Univ., Ames, IA (United States)

2000-09-21

The UV photolysis of hexanes solutions containing the complexes M(CO)₆ (M=Cr, Mo, W) or CpMn(CO)₃ (Cp=η⁵-C₅H₅) and excess thiophene (T*) (T*=2,5-dimethylthiophene (2,5-Me₂T), benzothiophene (BT), and dibenzothiophene (DBT)) produces the η¹(S)-T* complexes (CO)₅M(η¹(S)-T*) 1-8 or Cp(CO)₂Mn(η¹(S)-T*)9-11, respectively. However, when T*=DBT, and M=Mo, a mixture of two products result which includes the η¹(S)-DBT complex (CO)₅Mo(η¹(S)-DBT) 4a and the unexpected π-complex (CO)₃Mo(η{sup 6}-DBT) 4b as detected by ¹H NMR. The liability of the η¹(S)-T* ligands is illustrated by the rapid displacement of DBT in the complex (CO)₅W(η¹(S)-DBT) (1) by THF, and also in the complexes (CO)₅Cr(η¹(S)-DBT) (5) and CpMn(CO)₂(η¹(S)-DBT) (9) by CO (1 atm) at room temperature. Complexes 1-11 have been characterized spectroscopically (¹H NMR, IR) and when possible isolated as analytically pure solids (elemental analysis, EIMS). Single crystal, X-ray structural determinations are reported for (Cη)₅W(η¹(S)-DBT) and Cp(CO)₂Mn(η¹(S)-DBT).

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

Science.gov (United States)

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-02-29

Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO(x)/ZrO2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WOx/ZrO2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO2) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO3 and monoclinic ZrO2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WOx/ZrO2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS. Copyright © 2012 Elsevier B.V. All rights reserved.

Efficient oxidative desulfurization (ODS) of model fuel with H{sub 2}O{sub 2} catalyzed by MoO{sub 3}/{gamma}-Al{sub 2}O{sub 3} under mild and solvent free conditions

Energy Technology Data Exchange (ETDEWEB)

Jia, Yuhua; Li, Gang; Ning, Guiling [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology (China)

2011-01-15

An efficient process to remove organic sulfur compounds from model fuel has been explored. Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) can be completely oxidized into their corresponding sulfones by H{sub 2}O{sub 2} over 14 wt.% MoO{sub 3}/{gamma}-Al{sub 2}O{sub 3} catalyst under mild conditions in 15 min. The effects of solvent, initial sulfide concentration, loading of MoO{sub 3} and amount of catalyst on oxidative removal of DBT were studied. The employments of solvents have decreased the reaction rate of DBT, which can be attributed to the competitive adsorption between the sulfide and solvent. The oxidative reactivity increases in the order of thiophene (Th) < benzothiophene (BT) < DBT < 4, 6-DMDBT. The catalyst can be regenerated by methanol washing at 333 K. (author)

Efficient assessment of modified nucleoside stability under conditions of automated oligonucleotide synthesis: characterization of the oxidation and oxidative desulfurization of 2-thiouridine.

Science.gov (United States)

Sochacka, E

2001-01-01

In order to efficiently assess the chemical stability of modified nucleosides to the reagents and conditions of automated oligonucleotide synthesis, we designed, developed and tested a scheme in which the modified nucleoside, directly attached to a solid support, is exposed to the cyclic chemistry of the instrument. Stability of 2-thiouridine against different oxidizers was investigated. Tertbutyl hydroperoxide (1 M) in anhydrous acetonitrile was a more effective oxidizer for the incorporation of 2-thiouridine into oligonucleotide chains than the same oxidizer in methylene chloride. Carbon tetrachloride/water in the presence of a basic catalyst was superior in maintaining the thiocarbonyl function, but its utility for RNA synthesis has yet to be fully tested, whereas 2-phenylsulfonyloxaziridine was a very efficient reagent for oxidative desulfurization of 2-thiouridine.

A model for dry sodium bicarbonate duct injection flue gas desulfurization

Energy Technology Data Exchange (ETDEWEB)

Changfa Wu; Soon-Jai Khang; Tim C. Keener; Sang-Kwun Lee [University of Cincinnati, Cincinnati, OH (United States). Department of Chemical Engineering

2004-03-01

A mathematical model is developed for simulation of dry sodium bicarbonate (NaHCO{sub 3}) duct injection for the removal of sulfur dioxide (SO{sub 2}) in flue gases across a fabric filter (baghouse). The model employs parallel reaction kinetics and assumes that the sodium bicarbonate injection process can be separated into two stages. The first stage is a transport duct section where NaHCO{sub 3} particles are injected into the sulfur dioxide laden gas stream. The second stage is the fabric filter section where sodium sorbents are collected and behave as a variable depth fixed bed reactor. The process simulation for the efficiency of desulfurization in flue gas is performed and evaluated for a variety of operating conditions. It is found that the removal of SO{sub 2} within the duct section is small and negligible for most practical conditions, with a contribution normally less than 5% of total SO{sub 2} removal. The major removal of SO{sub 2} occurs across the filter cake, which accumulates the sorbent particles on the fabric filter. These particles are periodically disposed as the filter is cleaned. The major factors for the process are temperature, particle size and SO{sub 2} gas concentration for all operating conditions. At low temperatures, the removal of SO{sub 2} increases as temperature increases, but the removal decreases at higher temperatures due to the impact of the thermal decomposition reaction of NaHCO{sub 3} on SO{sub 2} removal. It was found that the temperature for the highest removal of SO{sub 2} is within the range of 127-150{sup o}C and the removal efficiency also depends on particle size.

Utilization of desulfurization gypsum to producing SO{sub 2} and CaO in multi-stage fluidized bed

Energy Technology Data Exchange (ETDEWEB)

Miao, Zhu; Wang, Tao; Yang, Hairui; Zhang, Hai; Zhang, Zuyi [Tsinghua Univ., Beijing (China). Dept. of Thermal Engineering; Ministry of Education, Beijing (China). Key Lab. for Thermal Science and Power Engineering

2013-07-01

With emission control becomes more and more stringent, flue gas desulphurization (FGD) is commonly employed for desulfurization. However, the product of FGD, gypsum, causes the unexpected environmental problems. How to utilize the byproduct of FGD effectively and economically is a challenging task. This paper proposed the new technical process to produce SO{sub 2} and CaO by reducing the gypsum in multi-stage fluidized bed reactor with different atmosphere. In addition, some preliminary experiments were carried out in PTGA. The results show that CO concentration has little effect on the initial decomposing temperature, but affect the decomposing rate of phosphogypsum obviously. The decomposing product composed of CaS and CaO simultaneously. The ratio of the two products was determined by CO concentration. Lower CO content benefits to produce more CO product and more SO{sub 2}. The decomposition reaction of phosphogypsum in reducing atmosphere is parallel competition reaction. Therefore, it is necessary to eliminate the effect of CaS and other byproduct efficiently by the new technology, which utilize multi-atmosphere in multistage fluidized bed reactors.

Improvement of Biodesulfurization Rate of Alginate Immobilized Rhodococcus erythropolis R1

Science.gov (United States)

Derikvand, Peyman; Etemadifar, Zahra

2014-01-01

Background: Sulfur oxides released from the burning of oil causes severe environmental pollution. The sulfur can be removed via the 4S pathway in biodesulfurization (BDS). Immobilization approaches have been developed to prevent cell contamination of oil during the BDS process. Objectives: The encapsulation of Rhodococcus erythropolis R1 in calcium alginate beads was studied in order to enhance conversion of dibenzothiophene (DBT) to 2-hydroxy biphenyl (2-HBP) as the final product. Also the effect of different factors on the BDS process was investigated. Materials and Methods: Calcium alginate capsules were prepared using peristaltic pumps with different needle sizes to control the beads sizes. Scanning electron microscopy and flow cytometry methods were used to study the distribution and viability of encapsulated cells, respectively. Two non-ionic surfactants and also nano Ƴ-Al2O3were used with the ratio of 0.5% (v/v) and 1:5 (v/v) respectively to investigate their BDS efficiency. In addition, the effect of different bead sizes and different concentrations of sodium alginate in BDS activity was studied. Results: The 2% (w/v) sodium alginate beads with 1.5mm size were found to be the optimum for beads stability and efficient 2-HBP production. The viability of encapsulated cells decreased by 12% after 20 h of desulfurization, compared to free cells. Adding the non-ionic surfactants markedly enhanced the rate of BDS, because of increasing mass transfer of DBT to the gel matrix. In addition, Span 80 was more effective than Tween 80. The nanoƳ-Al2O3 particles could increase BDS rate by up to two-folds greater than that of the control beads. Conclusions: The nano Ƴ-Al2O3 can improve the immobilized biocatalyst for excellent efficiency of DBT desulfurization. Also the BDS activity can be enhanced by setting the other explained factors at optimum levels. PMID:25147685

Removal of fine particles in wet flue gas desulfurization system by heterogeneous condensation

Energy Technology Data Exchange (ETDEWEB)

Yang, L.J.; Bao, J.J.; Yan, J.P.; Liu, J.H.; Song, S.J.; Fan, F.X. [Southeast University, Nanjing (China). School of Energy & Environment

2010-01-01

A novel process to remove fine particles with high efficiency by heterogeneous condensation in a wet flue gas desulfurization (WFGD) system is presented. A supersaturated vapor phase, necessary for condensational growth of fine particles, was achieved in the SO{sub 2} absorption zone and at the top of the wet FGD scrubber by adding steam in the gas inlet and above the scrubbing liquid inlet of the scrubber, respectively. The condensational grown droplets were then removed by the scrubbing liquid and a high-efficiency demister. The results show that the effectiveness of the WFGD system for removal of fine particles is related to the SO{sub 2} absorbent employed. When using CaCO{sub 3} and NH{sub 3} {center_dot} H{sub 2}O to remove SO{sub 2} from flue gas, the fine particle removal efficiencies are lower than those for Na2CO{sub 3} and water, and the morphology and elemental composition of fine particles are changed. This effect can be attributed to the formation of aerosol particles in the limestone and ammonia-based FGD processes. The performance of the WFGD system for removal of fine particles can be significantly improved for both steam addition cases, for which the removal efficiency increases with increasing amount of added steam. A high liquid to gas ratio is beneficial for efficient removal of fine particles by heterogeneous condensation of water vapor.

Marble waste characterization as a desulfurizing slag component for steel; Caracterizacao do residuo de marmore como componente de escorias dessulfurantes para aco

Energy Technology Data Exchange (ETDEWEB)

Coleti, J.L.; Grillo, F.F.; Tenorio, J.A.S. [Universidade de Sao Paulo (USP), SP (Brazil); De Oliveira, J.R. [Instituto Federal do Espirito Santo (IFES), ES (Brazil)

2014-07-01

The current steel market requires from steel plants better quality of its products. As a result, steel plants need to search for improvements and costs reduction in its process. Hence, the residue of marble containing significant quantities of calcium and magnesium carbonates, raw materials of steel refining slag, was characterized in order to replace the conventional lime used. Therefore, it will be possible to reduce the cost and volume of waste produced by the ornamental rock industry. The following methods were applied to test the waste potential: SEM with EDS, x-ray diffraction, x-ray fluorescence (EDX), Thermogravimetry (TG) and analysis of surface area and particle size by the BET method using dispersion leisure. The results indicated the feasibility of waste as raw material in the composition of desulfurizing slags. (author)

Research report of FY 1997 on the environmentally acceptable coal utilization system introduction support project. Demonstration project on simplified desulfurizers; 1997 nendo seika hokokusho. Kankyo chowagata sekitan riyo system donyu shien jigyo (kan`i datsuryu setsubi ni kakawaru jissho jigyo)

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-03-01

To reduce SOx with coal utilization, a desulfurizer is introduced in Thailand as diffusion activities in the demonstration program. The purpose is to reduce the environmental pollutants. For this desulfurizer, lime mud mainly composed of lime stone is used as an absorber. SO2 in the flue gas is absorbed by the slurry of lime mud, to form calcium sulfite. The calcium sulfite blown in the bottom of recycling tank is oxidized by oxygen in the air, to form gypsum. The gypsum is recovered as a by-product. In this fiscal year, a feeder of lime stone, spray nozzles, and various analysis apparatuses were supplied. Supervisors for electric instrumentation/control were also dispatched as well as for main body construction, to carry out the instrumentation setting works, check of sequences, and adjustment of apparatuses. After the test operation, supervisors for the demonstration operation were dispatched up to March 1998, to conduct the cooperation works between Japan and Thailand sides. Thus, successful and successive demonstration operation was confirmed. 21 figs., 6 tabs.

ENHANCED CONTROL OF MERCURY BY WET FLUE GAS DESULFURIZATION SYSTEMS; FINAL

International Nuclear Information System (INIS)

Unknown

2001-01-01

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

Investigation of the effects of various water mediums on desulfurization and deashing of a coal sample by flotation

Energy Technology Data Exchange (ETDEWEB)

Ayhan, F.D. [Dicle University, Diyarbakir (Turkey)

2009-08-15

The aim of this study was to investigate the effects of various water mediums on desulfurization and deashing of a coal sample using flotation. For this purpose, experimental studies were conducted on a coal sample containing high ash and sulfur contents. The effects of pH, solid concentration, collector amount and frother amount on the flotation were investigated separately in Mediterranean Sea water, Cermik thermal spring water, snow water and tap water. Flotation, results indicated that, when comparing the various water mediums, the following order for the ash content was obtained: snow water < Cermik thermal spring water < tap water < the Mediterranean Sea water. For the reduction of total sulfur, the following order was obtained: snow water > Cermik thermal spring water > Mediterranean Sea water > tap water. When snow water was used as a flotation medium, it was found that a concentrate containing 3.01% total sulfur and 27.64% ash with a total sulfur reduction of 57.06% was obtained from a feed containing 7.01% total sulfur and 4.1.17% ash.

Flue gas desulfurization under simulated oxyfiring fluidized bed combustion conditions: The influence of limestone attrition and fragmentation

Energy Technology Data Exchange (ETDEWEB)

Scala, F.; Salatino, P. [CNR, Naples (Italy)

2010-01-01

Flue gas desulfurization by means of limestone injection under simulated fluidized bed oxyfiring conditions was investigated, with a particular focus on particle attrition and fragmentation phenomena. An experimental protocol was applied, based on the use of complementary techniques that had been previously developed for the characterization of attrition of sorbents in air-blown atmospheric fluidized bed combustors. The extent and pattern of limestone attrition by surface wear in the dense phase of a fluidized bed were assessed in bench scale fluidized bed experiments under simulated oxyfiring conditions. Sorbent samples generated during the oxyfiring tests were further characterized from the standpoint of fragmentation upon high velocity impact by means of a particle impactor. The experimental results were compared with those previously obtained with the same limestone under air-blown atmospheric fluidized bed combustion conditions. The profound differences in the attrition and fragmentation extents and patterns associated with oxyfiring as compared to air-blown atmospheric combustion and the role played by the different attrition/fragmentation paths were highlighted. In particular, it was noted that attrition could effectively enhance particle sulfation under oxyfiring conditions by continuously disclosing unconverted calcium to the sulfur-bearing atmosphere.

Molecular dynamics simulations on desulfurization of n-octane/thiophene mixture using silica filled polydimethylsiloxane nanocomposite membranes

International Nuclear Information System (INIS)

Shariatinia, Zahra; Jalali, Azin Mazloom; Taromi, Faramarz Afshar

2016-01-01

Molecular dynamics (MD) simulations were performed at 298.15 K and 1 atm in order to study microstructure and transport behaviors of polydimethylsiloxane (PDMS) membranes containing 0%–8% SiO 2 nanoparticles used for the separation of thiophene from n-octane. It was found that the fractional free volume (FFV) of 0% SiO 2 was the highest (47.24%) among five nanocomposite membranes and addition of 2%–8% silica nanoparticles led to dramatic decrease in the FFV of the cells. The x-ray diffraction (XRD) patterns of all membranes showed that they had a semi-crystalline structure containing a broad peak around 15°–18°. The radial distribution function (RDF) analysis proved that the smallest C(CH 2 -octane)–O(SiO 2 ), C(PDMS)–O(SiO 2 ) and H(thiophene)–O(SiO 2 ) distances were present in 4% SiO 2 membrane reflecting the silica–octane, silica–polymer and silica–thiophene interactions were the strongest in this membrane. The mean squared displacement (MSD) and diffusion coefficients of n-octane were both small in the 6% silica membrane but they were high for thiophene suggesting this membrane was the most suitable for the desulfurization process and separation of thiophene from n-octane. (paper)

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

Energy Technology Data Exchange (ETDEWEB)

Sublette, K.L.

1993-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1999-01-31

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

Evaluación de la actividad desulfurizadora de aislados nativos de Pseudomonas spp. en presencia de hidrocarburo Desulfurization activity evaluation of native strains of Pseudomonas spp. in the presence of hydrocarbon

Directory of Open Access Journals (Sweden)

Alméciga-Díaz Carlos Javier

2005-07-01

Full Text Available El principal inconveniente en la combustión de los hidrocarburos es la conversión del azufre y el nitrógeno a sus respectivos óxidos, los cuales participan en la formación de lluvia acida y deterioran el medio ambiente e infraestructuras. La remoción de azufre a partir de compuestos órgano-azufrados mediante el uso de microorganismos ha surgido como una alternativa frente al proceso catalítico de hidrodesulfurización (HDS. En el presente trabajo se evaluó la actividad desulfurizadora de veintitrés aislados nativos de Pseudomonas spp. sobre dibenzotiofeno (DBT, usando un sistema de fermentación con igual proporción de fase acuosa y orgánica (n-hexano en presencia de oleato de etanolamina. Los aislados 02,05 y 06 conservaron su viabilidad en este medio y presentaron una remoción de azufre entre 6,0 y 9,4%, generando los metabolitos DBT-sulfona, DBT-sulfóxido, 2-hidroxibifenilo (2-HBP y sulfato presentes en la ruta metabólica 4S. Con estos aislados se evaluó la actividad desulfurizadora sobre keroseno y se observó una remoción de azufre entre 19,9 y 62,6% y una disminución del poder calorífico entre 0,45 y 5,55%. Palabras clave: dibenzotiofeno, desulfurización, Pseudomonas spp., keroseno.The main difficulty with fossil fuel combustión lies in sulphur and nitrogen becoming converted to their respective oxides, forming part of the acid rain which deteriorates the environment and infrastructure. Removing sulphur from organo-sulfur compounds by using micro-organisms has become an alternative to hydrodesulphurisation (HDS. Twenty-three Pseudomonas spp. native strains' desulphurisation activity on dibenzothiophene (DBT was evaluated by using a fermentation system having equal proportions of aqueous and organic (n-hexane phases in the presence of ethanolamine oléate. The 02, 05 and 06 strains maintained their viability in this médium, presenting 6,0% to 9,4% sulphur removal, producing DBT-sulphone, DBT-sulphoxide, 2

Microbial reduction of SO{sub 2} and NO{sub x} as a means of by-product recovery/disposal from regenerable processes for the desulfurization of flue gas. Technical progress report, December 11, 1992--March 11, 1993

Energy Technology Data Exchange (ETDEWEB)

Sublette, K.L.

1993-12-31

This report describes the potential of sulfate reducing bacteria to fix sulfur derived from flue gas desulfurization. The first section reviews the problem, the second section reviews progress of this study to use desulfovibrio desulfuricans for this purpose. The final section related progress during the current reporting period. This latter section describes studies to immobilize the bacteria in co-culture with floc-forming anaerobes, use of sewage sludges in the culture media, and sulfate production from sulfur dioxide.

Dry flue gas desulfurization byproducts as amendments for reclamation of acid mine spoil

International Nuclear Information System (INIS)

Dick, W.A.; Stehouwer, R.C.; Beeghly, J.H.; Bigham, J.M.; Lal, R.

1994-01-01

Development of beneficial reuses of highly alkaline, dry flue gas desulfurization (FGD) byproducts can impact the economics of adopting these FGD technologies for retrofit on existing powerplants. Greenhouse studies were conducted to evaluate the use of two dry FGD byproducts for reclamation of acid mine spoil (pH, 3.1 to 5.8). Treatment rates of FGD ranges from 0% to 32% by dry weight and most treatments also included 6% by dry weight of sewage sludge. Fescue (Festuca arundinacea Schreb.) was harvested monthly for a total of six harvests. Plant tissue composition and root growth were determined after the sixth harvest. Leachate analyses and pH determination of mixes were done at the beginning and end of the experiments. Both FGD byproducts were effective in raising the spoil pH and in improving fescue growth. At the highest FGD application rate, fescue growth decreased from the optimum due to high pH and reduced rooting volume caused by cementation reactions between the FGD and spoil. Trace elements, with the exception of B, were decreased in the fescue tissue when FGD was applied. Leachate pH, electrical conductivity, dissolved organic carbon, Ca, Mg, and S tended to increase with increased FGD application rate; Al, Fe, Mn, and Zn decreased. pH was the most important variable controlling the concentrations of these elements in the leachate. Concentrations of elements of environmental concern were near or below drinking water standard levels. These results indicate that FGD applied at rates equivalent to spoil neutralization needs can aid in the revegetation of acid spoil revegetation with little potential for introduction of toxic elements into the leachate water or into the food chain

Investigation on application of coal ash, lime and gypsum-based compositions. ; Development of technology to utilize and dispose of used desulfurizing agnet. Sekitanbaiter dot sekkaiter dot sekkokei soseibutsu no oyo ni kansuru chosa. ; Shiyozumi datsuryu zai no riyo shori gijutsu no kaihatsu

Energy Technology Data Exchange (ETDEWEB)

Mori, K. (The Hokkaido Electric Power Co. Inc., Sapporo (Japan))

1991-11-20

This paper describes the result of an investigation by testing on re-utilizing the used desulfurizing agent discharged from a thermal power plant as a sludge disposer and a deodorant. The used desulfurizing agent used in the test is a nearly neutral substance composed mainly of SiO{sub 2} and CaSO{sub 4}. The paper describes that the tested agent has a character to solidify when added with water, and the solidified substance made from the agent added into a sludge is nearly neutral and usable in the similar manner as in the commercially available sludge solidifying materials. The paper also reports that in a field test for applying this tested agent to cover the sludge surface, a marked effect of improving water quality was recognized, including the increased water transparency. It also states that the tested agent absorbs ammonia actively, and that as a result of investigating its applicability as a deodorant for pet excreta odors, the agent can be handled more easily than the commercially available deodorants and has a deodorizing effect equivalent to or better than them. 4 refs., 7 figs., 6 tabs.

Remediation of saline-sodic soil with flue gas desulfurization gypsum in a reclaimed tidal flat of southeast China.

Science.gov (United States)

Mao, Yumei; Li, Xiaping; Dick, Warren A; Chen, Liming

2016-07-01

Salinization and sodicity are obstacles for vegetation reconstruction of coastal tidal flat soils. A study was conducted with flue gas desulfurization (FGD)-gypsum applied at rates of 0, 15, 30, 45 and 60Mg/ha to remediate tidal flat soils of the Yangtze River estuary. Exchangeable sodium percentage (ESP), exchangeable sodium (ExNa), pH, soluble salt concentration, and composition of soluble salts were measured in 10cm increments from the surface to 30cm depth after 6 and 18months. The results indicated that the effect of FGD-gypsum is greatest in the 0-10cm mixing soil layer and 60Mg/ha was the optimal rate that can reduce the ESP to below 6% and decrease soil pH to neutral (7.0). The improvement effect was reached after 6months, and remained after 18months. The composition of soluble salts was transformed from sodic salt ions mainly containing Na(+), HCO3(-)+CO3(2-) and Cl(-) to neutral salt ions mainly containing Ca(2+) and SO4(2-). Non-halophyte plants were survived at 90%. The study demonstrates that the use of FGD-gypsum for remediating tidal flat soils is promising. Copyright © 2016. Published by Elsevier B.V.

Comparison of Corrosion Behavior of Low-Alloy Steel Containing Copper and Antimony with 409L Stainless Steel for a Flue Gas Desulfurization System

Energy Technology Data Exchange (ETDEWEB)

Park, Sun-Ah; Shin, Su-Bin; Kim, Jung-Gu [Sungkyunkwan University, Suwon (Korea, Republic of)

2016-07-15

The corrosion behavior of low alloy steel containing Cu, Sb and 409L stainless steel was investigated for application in the low-temperature section of a flue gas desulfurization (FGD) system. The electrochemical properties were evaluated by potentiodynamic polarization testing and electrochemical impedance spectroscopy (EIS) in 16.9 vol% H{sub 2}SO{sub 4} + 0.35 vol% HCl at 60 ℃. The inclusions in these steels ere identified by electron probe microanalyzer (EPMA). The corrosion products of the steels were analyzed using scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The corrosion rate of the low alloy steel containing Cu, Sb was about 100 times lower than that of 409L stainless steel. For stainless steel without passivation, active corrosion behavior was shown. In contrast, in the low alloy steel, the Cu, Sb compounds accumulated on the surface improved the corrosion resistance by suppressing the anodic dissolution reaction.

Mineral concentrations of forage legumes and grasses grown in acidic soil amended with flue gas desulfurization products

Energy Technology Data Exchange (ETDEWEB)

Clark, R.B.; Baligar, V.C. [USDA ARS, Beltsville, MD (USA). Beltsville Agricultural Research Center West

2003-07-01

Considerable quantities of flue gas desulfurization products (FGDs) are generated when coal is burned for production of electricity, and these products have the potential to be reused rather than discarded. Use of FGDs as soil amendments could be important in overall management of these products, especially on acidic soils. Glasshouse studies were conducted to determine shoot concentrations of calcium (Ca), sulfur (S), potassium (K), magnesium (Mg), phosphorus (P), boron (B), zinc (Zn), copper (Cu), manganese (Mn), iron (Fe), aluminum (Al), sodium (Na), molybdenum (Mo), nickel (Ni), cadmium (Cd), chromium (Cr), and lead (Pb) in alfalfa (Medicago sativa), white clover (Trifolium repens), orchardgrass (Dacrylis glomerata), tall fescue (Festuca arundinacea), switchgrass (Panicum virgatum), and eastern gamagrass (Tripsacum dactyloides) grown in acidic (pH 4) soil (Typic Hapludult) amended with various levels of three FGDs and the control compounds CaCO{sub 3}, CaSO{sub 3}, and CaSO{sub 4}. Shoot concentrations of Ca, S, Mg, and B generally increased as levels of soil applied FGD increased. Concentrations of Mn, Fe, Zn, Cu were lower in shoots, especially when soil pH was high ({gt}7). Shoot concentrations of the trace elements Mo, Ni, Cd, Cr, and Pb were not above those reported as normal for foliage. Overall concentrations of most minerals remained near normal for shoots when plants were grown in FGD amended acidic soil.

Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils

Science.gov (United States)

Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

2015-01-01

Abstract Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline–alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation. PMID:26064038

Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils.

Science.gov (United States)

Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

2015-06-01

Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline-alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation.

FY1995 development of economical and high efficient desulfurization process using low rank coal; 1995 nendo teitankadotan wo mochiita ankana kokoritsu datsuryuho no kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

The objective of this study is to develop a new efficient desulfurization technique using a Ca ion-exchanged coal prepared from low rank coal and calcium raw material as a SO{sub 2} sorbent. Ion-exchange of calcium was carried out by soaking and mixing brown coal particles in milk of lime or slurry of industrial waste from concrete manufacture process. About 10wt% of Ca was easily incorporated into Yallourn coal. The ion-exchanged Ca was transformed to ultra-fine CaO particles upon pyrolysis of coal. The reactivity of CaO produced from Ca-exchanged coal to SO{sub 2} was extraordinary high and the CaO utilization of above 90% was easily achieved, while the conversion of natural limestone was less than 30% under the similar experimental conditions. High activity of Ca-exchanged coal was appreciably observed in a pressurized fluidized bed combustor. Ca-exchanged coal was quite effective for the removal of hydrogen sulfide. (NEDO)

Microbial reduction of SO{sub 2} and NO{sub x} as a means of by-product recovery/disposal from regenerable processes for the desulfurization of flue gas. Final report

Energy Technology Data Exchange (ETDEWEB)

Sublette, K.L.

1994-03-01

The main objective of this research was to investigate microorganisms capable of fossil fuel flue gas desulfurization and denitrification. The study used municipal sewage sludge as a carbon and energy source for SO{sub 2}-reducing cultures. The individual tasks developed a consortium of sulfate-reducing bacteria, investigated the design parameters for a continuous process, preformed a cost analysis, and screened sulfate-reducing bacteria. In the investigation of microbial reduction of NO{sub x} to nitrogen, tasks included screening denitrifying bacteria for NO and NO{sub 2} activity, developing optimum NO-reducing cultures, and investigating design parameters for a continuous system. This final report reviews the work previous to the current project, describes project objectives and the specific work plan, and reports results from the work completed during the previous reporting periods.

Safe, reliable desulfurization of high and very high H{sub 2}S loadings by UgnCleanTubes {sup registered}; Sichere, zuverlaessige Entschwefelung hoher und sehr hoher H{sub 2}S-Beladungen durch UgnCleanTubes {sup registered}

Energy Technology Data Exchange (ETDEWEB)

Zoelsmann, Herbert [UGN-Umwelttechnik GmbH, Gera (Germany); Hilgert, Walter [Rietzler-Gruppe GmbH, Nuernberg (Germany)

2016-08-01

UgnCleanPellets {sup registered} S 3.5 for complete, safe desulfurization of biogas/biogenic fuel gases (hydrolysis and pyrolysis gas, landfill gas, sewage gas,..), natural gas and associated petroleum gases and industrial production exhaust gases are market introduced and tested worldwide. In particular, the complete surrender of gas cooling, gas drying and gas reheating, the H{sub 2}S removal to zero level and proven in practice loading capacity of up to % 80 percent characterize the UgnCleanPellets {sup registered} S 3.5 external as a cost-effective, efficient and sustainable desulfurization medium. The further development of the pellets to the UgnCleanTubes {sup registered} S 3.5 - that is, to internally hollow pellets with correspondingly enlarged, outer surface - is the next logical step to further improve performance whilst fully retaining the advantages of pellets. [German] UgnCleanPellets {sup registered} S 3.5 zur vollstaendigen, sicheren Entschwefelung von Biogas/biogenen Brenngasen (Hydrolyse- und Pyrolysegas, Deponiegas, Klaergas,...), Erdgas und Erdoelbegleitgasen sowie industriellen Produktionsabgasen sind markteingefuehrt und weltweit erprobt. Insbesondere der vollstaendige Verzicht auf Gaskuehlung, Gastrocknung und Gaswiederaufheizung, die H{sub 2}S-Entfernung auf Nullniveau sowie die in der Praxis nachgewiesene Beladungskapazitaet von bis zu 80-Gew% zeichnen die UgnCleanPellets {sup registered} S 3.5 als ein kostenguenstiges, effizientes und nachhaltiges externes Entschwefelungsmedium aus. Die Weiterentwicklung der Pellets zu den UgnCleanTubes {sup registered} S 3.5 - d.h. zu innen hohlen Pellets mit entsprechend vergroesserter, aeusserer Oberflaeche - ist der naechste konsequente Schritt zur weiteren Leistungssteigerung bei vollstaendiger Beibehaltung der Vorteile der Pellets.

Testing CO2 Sequestration in an Alkaline Soil Treated with Flue Gas Desulfurization Gypsum (FGDG)

Science.gov (United States)

Han, Y.; Tokunaga, T. K.

2012-12-01

Identifying effective and economical methods for increasing carbon storage in soils is of interest for reducing soil CO2 fluxes to the atmosphere in order to partially offset anthropogenic CO2 contributions to climate change This study investigates an alternative strategy for increasing carbon retention in soils by accelerating calcite (CaCO3) precipitation and promoting soil organic carbon (SOC) complexation on mineral surfaces. The addition of calcium ion to soils with pH > 8, often found in arid and semi-arid regions, may accelerate the slow process of calcite precipitation. Increased ionic strength from addition of a soluble Ca source also suppresses microbial activity which oxidizes SOC to gaseous CO2. Through obtaining C mass balances in soil profiles, this study is quantifying the efficiency of gypsum amendments for mitigating C losses to the atmosphere. The objective of this study is to identify conditions in which inorganic and organic C sequestration is practical in semi-arid and arid soils by gypsum treatment. As an inexpensive calcium source, we proposed to use flue gas desulfurization gypsum (FGDG), a byproduct of fossil fuel burning electric power plants. To test the hypothesis, laboratory column experiments have been conducted in calcite-buffered soil with addition of gypsum and FGDG. The results of several months of column monitoring are demonstrating that gypsum-treated soil have lowered amounts of soil organic carbon loss and increased inorganic carbon (calcite) production. The excess generation of FGDG relative to industrial and agricultural needs, FGDG, is currently regarded as waste. Thus application of FGDG application in some soils may be an effective and economical means for fixing CO2 in soil organic and inorganic carbon forms.Soil carbon cycle, with proposed increased C retention by calcite precipitation and by SOC binding onto soil mineral surfaces, with both processes driven by calcium released from gypsum dissolution.

Dry flue gas desulfurization by-product application effects on plant uptake and soil storage changes in a managed grassland.

Science.gov (United States)

Burgess-Conforti, Jason R; Brye, Kristofor R; Miller, David M; Pollock, Erik D; Wood, Lisa S

2018-02-01

Environmental regulations mandate that sulfur dioxide (SO 2 ) be removed from the flue gases of coal-fired power plants, which results in the generation of flue gas desulfurization (FGD) by-products. These FGD by-products may be a viable soil amendment, but the large amounts of trace elements contained in FGD by-products are potentially concerning. The objective of this study was to evaluate the effects of land application of a high-Ca dry FGD (DFGD) by-product on trace elements in aboveground biomass and soil. A high-Ca DFGD by-product was applied once at a rate of 9 Mg ha -1 on May 18, 2015 to small plots with mixed-grass vegetation. Soil and biomass were sampled prior to application and several times thereafter. Aboveground dry matter and tissue As, Co, Cr, Hg, Se, U, and V concentrations increased (P  0.05) from pre-application levels or the unamended control within 3 to 6 months of application. Soil pH in the amended treatment 6 months after application was greater (P by-product application compared to the unamended control. High-Ca DFGD by-products appear to be useful as a soil amendment, but cause at least a temporary increase in tissue concentrations of trace elements, which may be problematic for animal grazing situations.

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

Science.gov (United States)

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.

Controllable Synthesis of Lindqvist Alkoxopolyoxovanadate Clusters as Heterogeneous Catalysts for Sulfoxidation of Sulfides.

Science.gov (United States)

Li, Ji-Kun; Dong, Jing; Wei, Chuan-Ping; Yang, Song; Chi, Ying-Nan; Xu, Yan-Qing; Hu, Chang-Wen

2017-05-15

Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H 2 O)] 2 [V 6 O 13 (OMe) 6 ] (1), [Cu(phen)(acac)(MeOH)] 2 [V 6 O 13 (OMe) 6 ] (2), [Co(dpa)(acac) 2 ] 2 [V 6 O 13 (OMe) 6 ]·2MeOH (3), [Co(phen)(acac) 2 ] 2 [V 6 O 13 (OMe) 6 ] (4), [Cu(dpa)(acac)] 2 [V IV 2 V V 4 O 12 (OMe) 7 ] (5), and [Cu(dpa)(acac)(MeOH)] 2 [V IV 2 V V 4 O 11 (OMe) 8 ] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In compounds 1-4 and 6, Cu or Co complexes and alkoxohexavanadate anions are assembled through electrostatic interactions. Differently, in compound 5, seven-methoxo-substituted Lindqvist-type [V 6 O 12 (OMe) 7 ] 2- are bridged to Cu complex via terminal O atoms by coordination bonds. All compounds 1-6 exhibit excellent heterogeneous catalytic performance in oxidative desulfurization and CEES ((2-chloroethyl) ethyl sulfide, a sulfur mustard simulant) abatement with H 2 O 2 as oxidant. Among them, the catalytic activity of 6 [conv. of DBT (dibenzothiophene) up to 100% in 6 h; conv. of CEES reached 100% and selectivity of CEESO ((2-chloroethyl) ethyl sulfoxide) up to 85% after 4 h] outperforms others and can be reused without losing its activity.

Simultaneous removal of Ni(II and fluoride from a real flue gas desulfurization wastewater by electrocoagulation using Fe/C/Al electrode

Directory of Open Access Journals (Sweden)

Shinian Liu

2017-09-01

Full Text Available Large amounts of anions and heavy metals coexist in flue gas desulfurization (FGD wastewater originating from coal-fired power plants, which cause serious environmental pollution. Electrocoagulation (EC with Fe/C/Al hybrid electrodes was investigated for the separation of fluoride and nickel ions from a FGD wastewater. The study mainly focused on the technology parameters including anode electrode type, time, inter-electrode distance (5–40 mm, current density (1.88–6.25 mA/cm2 and initial pH (4–10. The results showed that favorable nickel and fluoride removal were obtained by increasing the time and current density, but this led to an increase in energy consumption. Eighty-six percent of fluoride and 98% of Ni(II were removed by conducting the Fe/C/Al EC with a current density of 5.00 mA/cm2 and inter-electrode distance of 5 mm at pH 4 for 25 min and energy consumption was 1.33 kWh/m3. Concomitant pollutants also achieved excellent treatment efficiency. The Hg, Mn, Pb, Cd, Cu, SS and chemical oxygen demand were reduced by 90%, 89%, 92%, 88%, 98%, 99.9% and 89%, respectively, which met stringent environmental regulations.

Stack gas desulfurization using adsorbent materials based on copper oxide; Desulfuracion de gases de combustion usando materiales adsorbentes basados en oxido de cobre

Energy Technology Data Exchange (ETDEWEB)

Flores Velazquez, Roberto; Rodas Grapain, Arturo [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

2008-07-01

One of main fossil fuels used to date in Mexico for power generation is the fuel oil, with a total participation of 32%. The Mexican fuel oil is constituted in average by 84% in weight of carbon, 11% hydrogen, 0.4% nitrogen, 0.2% oxygen, 4% sulfur and the remaining is assumed to be metals such as vanadium, nickel, calcium, magnesium among others. The purpose of the present paper is to show a new route of preparation of materials impregnated through the application of ultrasonic energy and to evaluate its performance in the stack gas desulfurization. [Spanish] Uno de los principales combustibles fosiles empleados actualmente en Mexico para la generacion de energia electrica es el combustoleo, con una participacion total del 32%. El combustoleo mexicano esta constituido en promedio por 84% en peso de carbono, 11% de hidrogeno, 0.4% de nitrogeno, 0.2% de oxigeno, 4% de azufre y el resto se asume a metales como vanadio, niquel, calcio, magnesio entre otros. El proposito del presente trabajo es mostrar una nueva ruta de preparacion de materiales impregnados a traves de la aplicacion de energia ultrasonica y evaluar su desempeno en la desulfuracion de gases de combustion.

Fabrication of magnetically responsive HKUST-1/Fe3O4 composites by dry gel conversion for deep desulfurization and denitrogenation.

Science.gov (United States)

Tan, Peng; Xie, Xiao-Yan; Liu, Xiao-Qin; Pan, Ting; Gu, Chen; Chen, Peng-Fei; Zhou, Jia-Yu; Pan, Yichang; Sun, Lin-Bing

2017-01-05

Selective adsorption by use of metal-organic frameworks (MOFs) is an effective method for purification of hydrocarbon fuels. In consideration that the adsorption processes proceed in liquid phases, separation and recycling of adsorbents should be greatly facilitated if MOFs were endowed with magnetism. In the present study, we reported for the first time a dry gel conversion (DGC) strategy to fabricate magnetically responsive MOFs as adsorbents for deep desulfurization and denitrogenation. The solvent is separated from the solid materials in the DGC strategy, and vapor is generated at elevated temperatures to induce the growth of MOFs around magnetic Fe 3 O 4 nanoparticles. This strategy can greatly simplify the complicated procedures of the well-known layer-by-layer method and avoid the blockage of pores confronted by introducing magnetic Fe 3 O 4 nanoparticles to the pores of MOFs. Our results show that the adsorbents are capable of efficiently removing aromatic sulfur and nitrogen compounds from model fuels, for example removing 0.62mmolg -1 S and 0.89mmolg -1 N of thiophene and indole, respectively. In addition, the adsorbents are facile to separate from liquid phases by use of an external field. After 6 cycles, the adsorbents still show a good adsorption capacity that is comparable to the fresh one. Copyright © 2016 Elsevier B.V. All rights reserved.

A Green Desulfurization Technique: Utilization of Flue Gas SO2 to Produce H2 via a Photoelectrochemical Process Based on Mo-Doped BiVO4

Directory of Open Access Journals (Sweden)

Jin Han

2017-12-01

Full Text Available A green photoelectrochemical (PEC process with simultaneous SO2 removal and H2 production has attracted an increasing attention. The proposed process uses flue gas SO2 to improve H2 production. The improvement of the efficiency of this process is necessary before it can become industrial viable. Herein, we reported a Mo modified BiVO4 photocatalysts for a simultaneous SO2 removal and H2 production. And the PEC performance could be significantly improved with doping and flue gas removal. The evolution rate of H2 and removal of SO2 could be enhanced by almost three times after Mo doping as compared with pristine BiVO4. The enhanced H2 production and SO2 removal is attributed to the improved bulk charge carrier transportation after Mo doping, and greatly enhanced oxidation reaction kinetics on the photoanode due to the formation of SO32− after SO2 absorption by the electrolyte. Due to the utilization of SO2 to improve the production of H2, the proposed PEC process may become a profitable desulfurization technique.

A green desulfurization technique: utilization of flue gas SO2 to produce H2 via a photoelectrochemical process based on Mo-doped BiVO4

Science.gov (United States)

Han, Jin; Li, Kejian; Cheng, Hanyun; Zhang, Liwu

2017-12-01

A green photoelectrochemical (PEC) process with simultaneous SO2 removal and H2 production has attracted an increasing attention. The proposed process uses flue gas SO2 to improve H2 production. The improvement of the efficiency of this process is necessary before it can become industrial viable. Herein, we reported a Mo modified BiVO4 photocatalysts for a simultaneous SO2 removal and H2 production. And the PEC performance could be significantly improved with doping and flue gas removal. The evolution rate of H2 and removal of SO2 could be enhanced by almost 3 times after Mo doping as compared with pristine BiVO4. The enhanced H2 production and SO2 removal is attributed to the improved bulk charge carrier transportation after Mo doping, and greatly enhanced oxidation reaction kinetics on the photoanode due to the formation of SO32- after SO2 absorption by the electrolyte. Due to the utilization of SO2 to improve the production of H2, the proposed PEC process may become a profitable desulfurization technique.

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

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-04-30

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

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations.

Science.gov (United States)

Niksa, Stephen; Fujiwara, Naoki

2005-07-01

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.

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

International Nuclear Information System (INIS)

Bolinsky, F.T.; Ross, J.; Dennis, D.S.

1991-01-01

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

Factors affecting the precipitation of pure calcium carbonate during the direct aqueous carbonation of flue gas desulfurization gypsum

International Nuclear Information System (INIS)

Song, Kyungsun; Jang, Young-Nam; Kim, Wonbaek; Lee, Myung Gyu; Shin, Dongbok; Bang, Jun-Hwan; Jeon, Chi Wan; Chae, Soo Chun

2014-01-01

The mineral carbonation of FGD (flue gas desulfurization) gypsum was carried out through CO 2 sorption into ammonia solution containing FGD gypsum. High-purity calcium carbonate was precipitated from DCC (dissolved calcium carbonate) solution which was extracted during the induction period. The factors affecting the preparation of pure calcium carbonate were examined under the following conditions: CO 2 flow rate (1–3 L/min), ammonia content (4–12%), and S/L (solid-to-liquid) ratio (5–300 g/L). X-Ray diffraction study revealed that the PCC (precipitated calcium carbonate) was round-shaped vaterite. The induction time for PCC decreased as the CO 2 flow rate increased. The maximum formation efficiency for pure PCC was seen to increase linearly with the ammonia content. The formation efficiency for pure PCC was the highest (90%) for S/L ratio of 5 g/L but it decreased as S/L ratio increased. On the other hand, S/L ratio didn't affect the maximum solubility limit of DCC. It is believed that the pure PCC would add an economic value to the FGD gypsum carbonation for industrial CO 2 sequestration. - Highlights: • Pure and white CaCO 3 was synthesized using induction period during direct carbonation of FGD gypsum. • Its formation efficiency was increased with ammonia content but decreased with solid-to-liquid ratio. • This method is expected to extend to other industrial CO 2 sequestration for the enhanced economic value of precipitated CaCO 3

Selective catalytic oxidation: a new catalytic approach to the desulfurization of natural gas and liquid petroleum gas for fuel cell reformer applications

Science.gov (United States)

Lampert, J.

In both natural gas and liquid petroleum gas (LPG), sulfur degrades the performance of the catalysts used in fuel reformers and fuel cells. In order to improve system performance, the sulfur must be removed to concentrations of less than 200 ppbv (in many applications to less than 20 ppbv) before the fuel reforming operation. Engelhard Corporation presents a unique approach to the desulfurization of natural gas and LPG. This new method catalytically converts the organic and inorganic sulfur species to sulfur oxides. The sulfur oxides are then adsorbed on a high capacity adsorbent. The sulfur compounds in the fuel are converted to sulfur oxides by combining the fuel with a small amount of air. The mixture is then heated from 250 to 270 °C, and contacted with a monolith supported sulfur tolerant catalyst at atmospheric pressure. When Engelhard Corporation demonstrated this catalytic approach in the laboratory, the result showed sulfur breakthrough to be less than 10 ppbv in the case of natural gas, and less than 150 ppbv for LPG. We used a simulated natural gas and LPG mixture, doped with a 50-170 ppmv sulfur compound containing equal concentrations of COS, ethylmercaptan, dimethylsulfide, methylethylsulfide and tetrahydrothiophene. There is no need for recycled H 2 as in the case for hydrodesulfurization.

Integration of non linearities in the economic refining model. Case of the hydro-desulfurization unit; Prise en compte de non-linearites dans la modelisation economique du raffinage. Cas de l`unite d`hydrodesulfuration

Energy Technology Data Exchange (ETDEWEB)

Baudouin, C.

1998-12-08

In recent years, the modifications in oil products demand and the increased quality requirements of European specifications have driven the oil industry towards more and more complex refining schemes. This situation should become even more pronounced in the future. Under these conditions, a technical analysis of the units operation must be carried out and combined with an economic approach. The research undertaken is divided into two parts. The first part is dedicated to the study of the European refining industry and its representation by the classic linear programming model. In these models, the units` operation is represented by typical running. The technical parameters are not explicitly taken into account. Therefore, in order to meet future requirements and to represent this activity in the best way, the current model must be improved. The second part relates to an analysis with forecasts future developments in the European refining sector up to 2010 and how linear programming models themselves will be adapted. Thus, the straight run gas oil hydro-desulfurization unit is completely redefined. The operating conditions and the design parameters of this unit are introduced into the model. Depending on the feed, they determine the performances and the material balance of the unit. Some of these operating conditions are new variables and appear in non linear equations. Therefore, we need non linear programming (the augmented Lagrangians method) to solve this detailed model. The results of the second part confirm those determined by the first part. They also provide us with a better representation of the hydro-desulfurization unit (taking the optimisation of the operating conditions into account). Using these models and the analysis described above, we can develop an outline plan of the future European refining industry. This shows that sizeable investments in both conventional and deep conversion capacity will be required to meet the requirements of changes in

Effect of Substituents on the Electronic Structure and Degradation Process in Carbazole Derivatives for Blue OLED Host Materials

KAUST Repository

Hong, Minki

2016-07-25

We investigate the dissociation mechanism of the C-N bond between carbazole and dibenzothiophene in carbazole-dibenzothiophene (Cz-DBT) positional isomers, selected as representative systems for blue host materials in organic light-emitting diodes (OLEDs). The C-N bond dissociation energies, calculated at the density functional theory level, are found to depend strongly on the charge states of the parental molecules. In particular, the anionic C-N bond dissociations resulting in a carbazole anion can have low dissociation energies (∼1.6 eV) with respect to blue emission energy. These low values are attributed to the large electron affinity of the carbazole radical, a feature that importantly can be modulated via substitution. Substitution also impacts the energies of the first excited electronic states of the Cz-DBT molecules since these states have an intramolecular charge-transfer nature due to the spatially localized character of the frontier molecular orbitals within the carbazole moiety (for the HOMO) and the dibenzothiophene moiety (for the LUMO). The implications of these results must be considered when designing blue OLED hosts since these materials must combine chemical stability and high triplet energy. © 2016 American Chemical Society.

Combined method for reducing emission of sulfur dioxide and nitrogen oxides from thermal power plants

Energy Technology Data Exchange (ETDEWEB)

Kotler, V.R.; Grachev, S.P.

1991-11-01

Discusses the method developed by the Fossil Energy Research Corp. in the USA for combined desulfurization and denitrification of flue gases from coal-fired power plants. The method combines two methods tested on a commercial scale: the dry additive method for suppression of sulfur dioxide and the selective noncatalytic reduction of nitrogen oxides using urea (the NOXOUT process). The following aspects of joint flue gas desulfurization and denitrification are analyzed: flowsheets of the system, chemical reactions and reaction products, laboratory tests of the method and its efficiency, temperature effects on desulfurization and denitrification of flue gases, effects of reagent consumption rates, operating cost, efficiency of the combined method compared to other conventional methods of separate flue gas desulfurization and denitrification, economic aspects of flue gas denitrification and desulfurization. 4 refs.

Utilisation des écumes de sucrerie pour la désulfuration des fumées Using Sugar Factory Carbonatation Lime for Flue-Gas Desulfurization

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Dolignier J. C.

2006-12-01

Full Text Available Des études ont été réalisées par l'Institut français du pétrole et Babcock Entreprise pour montrer que l'écume de sucrerie pouvait être utilisée comme agent de désulfuration dans la chaudière Aude, un nouvel équipement de combustion permettant l'emploi de combustibles à haute teneur en soufre. Les tests ont été effectués en laboratoire et sur une chaudière semi-industrielle de 10 MW. L'écume de sucrerie donne des rendements de désulfuration supérieurs à ceux obtenus avec des calcaires naturels finement broyés. De plus, l'azote contenu dans l'écume permet de réduire les émissions de NOx selon le mécanisme de la réduction sélective non catalytique. Les utilisateurs de combustibles à haute teneur en soufre, qui devront faire face à une législation de plus en plus sévère, pourraient réduire leur coût annuel d'absorbants en utilisant l'écume de sucrerie. Par ailleurs, les producteurs de sucre auraient l'opportunité de mettre en place une nouvelle filière de valorisation pour leurs écumes. La teneur en eau élevée de l'écume n'autorise pas un transport sur de longues distances et des calculs ont été effectués pour définir la distance à partir de laquelle l'écume devient moins rentable que le calcaire. Studies have been carried out by the Institut français du pétrole and Babcock Entreprise to demonstrate that sugar factory carbonatation lime can be used as a desulfurization agent in the Aude boiler, which is a new combustion apparatus designed to use high sulfur fuels. Tests have been conducted both in the laboratory and on a near-industrial-scale 10 MW boiler. Sugar factory carbonatation lime provides greater desulfurization efficiency than that obtained using finely crushed natural limestone. Furthermore, the nitrogen contained in the carbonatation lime reduces NOx, emissions through selective non-catalytic reduction. Those who use high sulfur content fuels, and who are faced with increasingly

Démonstration du procédé IFP de désulfuration des fumées de centrales Demonstration of the Ifp Stack-Gas Desulfurization Process

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Busson C.

2006-11-01

Full Text Available Les produits pétroliers et le charbon continueront à couvrir les besoins énergétiques pendant plusieurs décennies. La pollution par le SOZ, provenant de la combustion de ces combustibles fossiles, devient une préoccupation pour la population et les Pouvoirs publics. La désulfuration des fumées de combustion devrait, à plus ou moins longue échéance, se développer. L'Institut Français du Pétrole (IFP, mettant à profit ses travaux dans le domaine de la désulfuration, a développé un procédé de traitement des fumées. L'IFP, en collaboration avec Électricité de France (EDF, a effectué en 1976 une opération de démonstration à une échelle pilote (30 MW dans la Centrale de Champagne-sur-Oise. Le procédé consiste à éliminer le S02 des fumées par lavage avec une solution ammoniacale, à produire du soufre à partir de la liqueur obtenue et à recycler l'ammoniaque dans l'étape de lavage. Après quelques modifications d'ordre technologique, l'unité de démonstration a fonctionné d'une manière continue pendant une période de trois mois, correspondant à l'objectif fixé. Les résultats obtenus permettent, actuellement, d'envisager une application de cette technique à une échelle de 250 MW. Oil and coal productswill continue to fulfill energy needs for several more decades. Pollution by SO2 coming from the combustion of such fossil fuels is becoming a preoccupation for the population and the public authorities. The desulfurization of combustion fumes should continue ta develop in the more or less long run. Institut Français du Pétrole (IFP has taken advantage of its research in the fixed of desulfurization to develop a stock-gas treating process. In collaboration with Électricite de Fronce (EDF, IFP carried out a demonsiration operation in 1976 on a pilot-plant scale (30MW in a power plant at Champagne-sur-Oise. The process consists in removing S02 from stock gases by scrubbing them with an ammonia solution

Effect of Prussian blue on organic sulfur of coal in aqueous medium

Energy Technology Data Exchange (ETDEWEB)

Demirbas, A. [Selcuk University, Konya (Turkey). Dept. of Chemical Engineering

2007-01-15

This study is an attempt to desulfurize organic sulfur from coal samples with ferric hexacyanoferrate (II), Fe{sub 4} (Fe(CN){sub 6}), as the desulfurization agent. Effect of temperature, particle size and concentration of ferrocyanide ion on desulfurization from the coal samples has been investigated. The temperature and stirring time are the most important parameters for the level of desulfurization of organic sulfur. Removal of organic sulfur content increased continuously with increasing temperature from 298 to 368 K. The organic sulfur removal rate sharply increases from 10 min to 30 min stirring time. After 30 min, it reaches a value of plateau. Particle size between -100 mesh and -200 mesh slightly affects the amount of organic sulfur removal. Gradual increase in the concentration of ferric hexacyanoferrate (II) raised the magnitude of desulfurization, but at higher concentration, the variation is not significant.