Conversion of sulfur dioxide to sulfate and hydrogen sulfide by Desulfotomaculum orientis

The autotrophic, sulfate-reducing bacterium, Desulfotomaculum orientis, grew in batch culture with molecular hydrogen (H₂) as an energy source, carbon dioxide (CO₂) as a carbon source and sulfur dioxide (SO₂) as the terminal electron acceptor. At high H₂ partial pressure, SO₂ was stoichiometrically reduced to hydrogen sulfide (H₂S). At low partial pressures of hydrogen (< 0.025 atm), SO₂ was both oxidized to sulfate and reduced to hydrogen sulfide. These results indicated a new mode of sulfur metabolism for D. orientis.     

Microbial reduction of sulfur dioxide and nitric oxide

Two process concepts have been developed for a microbial contribution to the problem of flue gas desulfurization and NO_x removal. We have demonstrated that the sulfate-reducing bacterium Desulfovibrio desulfuricans can be grown in a mixed culture with fermentative heterotrophs in a medium in which glucose served as the only carbon source. Beneficial cross-feeding resulted in vigorous growth of D. desulfuricans, which used SO₂(g) as a terminal electron acceptor, with complete reduction of SO₂ to H₂S in 1–2 s of contact time. We have proposed that the concentrated SO₂ stream, obtained from regeneration of the sorbent in regenerable processes for flue gas desulfurization, could be split with two-thirds of the SO₂ reduced to H₂S by contact with a culture of sulfate-reducing bacteria. The resulting H₂S could then be combined with the remaining SO₂ and used as feed to a Claus reactor to produce elemental sulfur. However, the use of glucose as an electron donor in microbial SO₂ reducing cultures would be prohibitively expensive. Therefore, if microbial reduction of SO₂ is to be economically viable, less expensive electron donors must be found. Consequently, we have evaluated the use of municipal sewage sludge and elemental hydrogen as carbon and/or energy sources for SO₂ reducing cultures. Heat and alkali pretreated sewage sludge has been successfully used as a carbon and energy source to support SO₂ reduction in a continuous, anaerobic mixed culture containing D. desulfuricans. The culture operated for nine months with complete reduction of SO₂ and H₂S. Another sulfate-reducing bacterium, Desulfotomaculum orientis, has also been grown in batch cultures on a feed of SO₂, H₂ and CO₂. Complete reduction of SO₂ to H₂S was observed with gas-liquid contact times of 1–2 s. We have also demonstrated that the facultative anaerobe and chemoautotroph, Thiobacillus denitrificans, can be cultured anoxically in batch reactors using NO(g) as a terminal electron acceptor with reduction to elemental nitrogen. We have proposed that the concentrated stream of NO_x, as obtained from certain regenerable processes for flue gas desulfurization and NO_x removal, could be converted to elemental nitrogen for disposal by contact with a culture T. denitrificans. Two heterotrophic bacteria have also been identified which may be grown in batch cultures with succinate or heat and alkali pretreated sewage sludge as carbon and energy sources and NO as a terminal electron acceptor. These are Paracoccus denitrificans and Pseudomonas denitrificans.     

(NH4)2S吸收净化冶炼烟气中SO2回收硫资源的方法

采用(NH₄)₂S溶液吸收净化高浓度SO₂烟气,得到(NH₄)₂S₂O₃和NH₄HSO₃的混合溶液并转移至高压反应釜中,控制反应条件,两种物质发生自氧化还原反应,生成硫磺和(NH₄)₂SO₄.实验考察了吸收SO₂过程和自氧化还原过程的影响条件,结果表明:在pH=3～7,SO₂气体流速300 ml·min^-1,(NH₄)₂S浓度为0.2～1.2 mol·L^-1,常温条件下,烟气中二氧化硫的吸收率达到99.8%以上,且无H₂S生成;在pH=2.5～3.0,温度为130℃条件下,反应进行1 h,硫磺收率达到95%以上,溶液经过蒸发结晶得到(NH₄)₂SO₄.用X射线衍射(XRD)和X射线荧光光谱(XRF)对硫磺和硫酸铵进行表征分析,结果表明:硫磺的纯度为99.14%,硫酸铵中氮元素含量为23.6%.     

双反应器选择性氧化硫回收工艺改进与优化

陕西某天然气净化厂采用干法双反应器选择性氧化硫回收工艺,该硫磺回收装置自2016年1月投产以来,存在等温反应器床层热点温度>300℃、硫磺夹带严重等问题,造成焚烧后φ（SO₂）偏高。通过对运行数据分析,结合实验室评价和模拟计算,确定汽包管路的不对称性分布为热点温度高的主因,硫分离器内流速低于设计值为硫磺夹带的主因,并提出汽包管路均布、降低硫分离器内件流通面积及增加在线仪表蒸汽吹扫等改进措施,使得装置运行平稳,热点温度降低至300℃以下,硫磺收率增加,外排SO₂降低至4 000 mg/m³（标准状态,下同）以下。     

Selective removal of H2S from coke oven gas

The catalytic performance of some metal oxides in the selective oxidation of H₂S in the stream containing water vapor and ammonia was investigated in this study. Among the catalysts tested, V₂O₅/SiO₂ and Fe₂O₃/SiO₂ catalyst showed good conversion of H₂S with very low selectivity to undesired SO₂. Hydrogen sulfide could be recovered as harmless solid products (elemental sulfur and various ammonium salts), and distribution of solid products was varied with types of catalyst and compositions of reactant. XRD and FT-IR analysis revealed that the salt was mixture of ammonium–sulfur–oxygen compounds. It was noteworthy that V₂O₅/SiO₂ catalyst produced elemental sulfur and ammonium thiosulfate, and that elemental sulfur was principal product on Fe₂O₃/SiO₂ catalyst. Small amount of ammonium sulfate was obtained with the Fe₂O₃/SiO₂ catalyst. In order to elucidate the reaction path, the effects of O₂/H₂S ratio and concentration of NH₃ and H₂O are also studied with the V₂O₅/SiO₂ catalyst.     

Claus Catalysis and H2S Selective Oxidation

This review article deals with the development of sulfur recovery from the Claus process to H₂S selective oxidation. Governments are constantly tightening regulations to limit the emission of sulfur compounds into the air. This makes it necessary to constantly enhance the level of sulfur recovery from natural, refinery, or coal gasification geses, and many improvements in the Claus process have been introduced to this end. In this review, emphasis has been put on the mechanism of reactions occurring in most of the sulfur recovery units, reactions between H₂S and SO₂ or O₂ and side reactions such as hydrolysis of COS and CS₂ or sulfation of the catalyst.     

煤化工烟道气毒性成分对Chlorella pyrenoidosa生长和细胞成分的影响

探究煤化工烟道气中毒性成分对微藻的影响是利用微藻固定煤化工烟道气CO₂实现减排的关键。本文利用不同浓度的NaHS、Na₂SO₃和NH₃·H₂O培养Chlorella pyrenoidosa（C. pyrenoidosa），以探究煤化工烟道气主要毒性成分H₂S、SO₂和NH₃气体水溶物的毒性。实验结果表明：NaHS、Na₂SO₃和NH₃·H₂O浓度分别低于1mmol/(L·d)、40mmol/(L·d)和7mmol/(L·d)时对C. pyrenoidosa生长无抑制作用，而且Na₂SO₃[＜40mmol/(L·d)]会显著促进 C. pyrenoidosa的生长；NaHS 添加4mmol/(L·d)时会在生长初期抑制C. pyrenoidosa的生长，NH₃·H₂O添加35mmol/(L·d)则会直接造成藻细胞的破碎死亡。与对照组相比，NaHS和Na₂SO₃浓度分别低于1mmol/(L·d)、10mmol/(L·d)时对C. pyrenoidosa的细胞成分无影响；NaHS添加4mmol/(L·d)使藻蛋白含量提高7.13%；Na₂SO₃添加40mmol/(L·d)使藻蛋白降低13.45%，总糖含量提高42.90%；NH₃·H₂O的添加会使藻蛋白含量降低，总糖含量提高。微藻生物质整体蛋白质含量较高，可作为蛋白饲料来源。研究结果表明，C. pyrenoidosa对煤化工烟道气中的主要毒性气体有较好的耐受性，利用煤化工烟道气培养微藻具有可行性。     

Selective catalytic reduction of sulfur dioxide with hydrogen to elemental sulfur over Co---Mo/Al2O3

The selective reduction of sulfur dioxide with hydrogen to elemental sulfur was studied over Co---Mo/Al₂O₃. When the feed conditions were properly optimized (SO₂/H₂ mole RATIO = 1:3), a sulfur yield of about 80% was achieved at temperatures around 300°C. The temperature is the lowest that has been reported so far for any catalyst for this reaction. The catalytic activity remained high and stable after presulfiding with 10% H₂S in hydrogen. Little influence on the catalytic activity was observed if the water content in the feed was kept below 11 vol.-%. The overall reaction consisted of two individual steps occurring on two different sites; sulfur dioxide was first hydrogenated to hydrogen sulfide on the metal sulfide phase, then followed by the Claus reaction of hydrogen sulfide with sulfur dioxide to produce elemental sulfur on the acidic sites of the alumina support.     

污泥深度脱水调理剂对污泥干化过程中含硫气体释放的影响

采用5种复合调理剂改善污泥脱水性能,制得深度脱水泥饼。通过检测N₂气氛下,不同干化温度（100℃、200℃）,停留时间（30 min、60 min）时,不同调理脱水污泥含水率的变化情况,以及含硫气体的种类和释放量,探讨不同调理剂对干化过程中含硫气体释放特性的影响。结果表明,提高温度、延长时间都可以有效降低污泥的含水率;原污泥干化过程释放的主要含硫气体为H₂S和SO₂,其总量占含硫气体的82.4%;FeCl₃+CaO和H₂SO₄+FeSO₄+H₂O₂+CaO复合调理剂调理脱水泥饼在干化过程中SO₂释放量占原污泥释放量的40.3%和40.6%,H₂S则基本没有释放;H₂SO₄+FeSO₄+H₂O₂+CaO调理脱水污泥在100℃和200℃干化过程中的总硫释放量分别占原污泥总释放量的75.0%和45.6%,该复合调理剂在有效提高污泥脱水性能的基础上,能最大限度地抑制含硫气体的释放。     

SULFUR RECOVERY WITH REDUCED EMISSIONS, LOW CAPITAL INVESTMENT AND HYDROGEN CO-PRODUCTION

The main disadvantage of the Claus process is that by introducing air as oxidant a large volume of tail gas is produced. This must be treated to reduce atmospheric emissions of sulfur-containing gases. The costs of the tail-gas unit are a significant fraction of the total capital and operating costs for sulfur recovery. A new process uses thermal decomposition of hydrogen sulfide in the presence of carbon dioxide instead of air oxidation. The products of this reaction are hydrogen, carbon monoxide, elemental sulfur, water vapor and carbonyl sulfide. Carbonyl sulfide is easily converted to H₂S and C0₂ by liquid- or vapor-phase hydrolysis. Unreacted H₂S and C0₂ are recovered by absorption and recycled to the reactor. Since no air is introduced, there is no tail gas and the tail-gas unit is eliminated, giving a substantial reduction in capital investment. The concentrations of sulfur-containing gases in the product streams depend only on the operation of the absorber and stripper units and can be controlled to very low levels by increasing stripper boil-up. Process operating costs depend on the level of sulfur recovery required and can also be much lower than those of the modified Claus Process.

The process chemistry depends on a shift in the equilibrium of H₂S decomposition caused by reaction of hydrogen with C0₂ by the reverse of the water-gas-shift reaction. Catalysts for this chemistry have been identified. Reactor conversion is further improved by rapid cooling of the reactor effluent gas. Other aspects of process design and operation confer further advantages with respect to the Claus process; however, the process equipment used is similar to that used in a Claus plant. Retrofit of existing plant to the new technology can therefore be considered.     

Resistance to sulfur poisoning of hot gas cleaning catalysts for the removal of tar from the pyrolysis of cedar wood

In the partial oxidation of tar derived from the pyrolysis of cedar wood, the effect of H₂S addition was investigated over non-catalyst, steam reforming Ni catalyst, and Rh/CeO₂/SiO₂ using a fluidized bed reactor. In the non-catalytic gasification, the product distribution was not influenced by the presence of H₂S. Steam reforming Ni catalyst was effective for the tar removal without H₂S addition, however, the addition of H₂S deactivated drastically. In contrast, Rh/CeO₂/SiO₂ exhibited higher and more stable activity than the Ni catalyst even under the presence of high concentration of H₂S (280 ppm). On the Ni catalyst, the adsorption of sulfur was observed by XPS and Ni species was oxidized during the partial oxidation of tar. In the case of Rh/CeO₂/SiO₂, the adsorption of sulfur was below the detection limit of XPS. This can be related to the self-cleaning of catalyst surface during the circulation in the fluidized bed reactor for the partial oxidation of tar derived from cedar pyrolysis.     

Microwave-assisted desulfurization of NOx storage-reduction catalyst

The activity of NO_x storage-reduction (NSR) catalysts is greatly reduced by sulfur poisoning, caused by the SO₂ present in the exhaust stream. Desorption of sulfur species from poisoned NSR catalysts occurs at temperatures in excess of 600 °C using reducing atmospheres and conventional heating. In this work, microwave (MW) heating has been used to promote desulfurization of poisoned NSR catalysts. The experiments were carried out by heating the catalyst with MW radiation and using hydrogen as the reducing gas. Desorption of H₂S at 200 °C was observed. Desorption at even lower temperatures (150 °C) was observed when water was introduced to the system. In the presence of water, sulfur species desorbed as both H₂S and SO₂. An overall reduction of sulfur species of about 60% was obtained. The use of MW heating proves to be an efficient way to achieve regeneration of poisoned NSR catalysts.     

10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

基于化学链气化技术依靠气固反应定向调控气化产物中H₂S和SO₂摩尔比为2的优势，将化学链气化与Claus工艺中的催化转化单元相结合，提出了高硫石油焦化学链气化制合成气和回收硫磺的新系统。针对系统核心单元，即化学链气化过程，基于Aspen Plus，开展热输入10 MW_th的高硫石油焦化学链气化过程模拟，以赤铁矿石为载氧体，水蒸气为气化介质，重点考察了氧碳比、气化温度对化学链气化过程及硫转化过程的影响。结果发现，氧碳比的增大导致合成气产率显著降低，但系统从需要外部提供能量逐渐转变为对外部放热，在氧碳比0.8669～0.9535区间内，系统可以达到热量自平衡。同时，气化温度的提高对合成气产率是有利的，在975℃时达到2.15 m³/kg，主要是由于CO体积分数随气化温度增加而增加。氧碳比和气化温度的提高都会导致H₂S浓度的降低和SO₂浓度的提高。并且研究了当H₂S和SO₂摩尔比为2的最佳工况时，氧碳比和气化温度为反相关，其中氧碳比为0.8669，气化温度为900℃时，冷煤气效率为64.09%。     

活性碳纤维负载型脱硫剂在矿井气体环境条件下的应用

H₂S作为煤炭开采过程中经常会出现的气体,对煤矿的生产安全造成不利影响,必须进行脱除工作。然而煤矿中还可能存在其他组分的气体,这些气体可能会一定程度上影响H₂S的脱除。本文选取活性碳纤维分别负载氢氧化钠及氧化铜,并选取两种材料的最佳负载量。之后,模拟煤矿实际条件,探讨复合脱硫剂在实际矿井气氛条件下的脱硫性能。结果表明,煤体在受热情况下会产生的多组分混合性气体,这些气体会对脱硫剂性能产生极大的影响,当煤体温度升高,其产生的CO、CO₂等气体呈指数增大,并且会产生少量的CH₄、C₂H₆、C₂H₄、C₂H₂等气体,随着这些气体生成量增大,脱硫剂脱硫性能开始下降。且在矿井气体氛条件下SO₂气体的产生受到了抑制,特别在煤气组分含量大的情况下,SO₂气体甚至晚于H₂S气体出现。此外通过测量脱硫剂失活后的表面pH,发现即便在一些气体氛围下脱硫剂的脱硫时间更短,其脱硫后产物的表面pH极为相近,说明煤体产生的酸性气体CO以及CO₂等可能也被吸附到脱硫剂的表面上生成酸性物质。     

A combined chemico-biological treatment of waste waters from coal depyritization with production of elemental sulphur

A combined chemico-biological process has been developed to remove sulphate and heavy metal ions from waste waters after microbial depyritization of coal. The waters are initially neutralized to a pH of about 3.5, diluted with pure water and then treated in an anaerobic bioreactor for microbial sulphate reduction in which nutrients are added to support the growth of bacteria. In the bioreactor the sulphate ions are reduced to hydrogen sulphide and the heavy metals are precipitated as the relevant insoluble sulphides. The process then involves H₂S stripping from the anaerobic bioreactor using nitrogen as a carrier gas, sulphur production from H₂S oxidation by bacterially produced ferric ions, aerobic solution polishing by microbial degradation of the organics, and secondary anaerobic processing. The product solution is rich in carbonate and may be recycled to the sulphate reduction stage or to the ferric ions production stage or may be discharged from the system.     

All-silica zeolites screening for capture of toxic gases from molecular simulation

The exhaust gases, including SO_2,NH_3, H_2S, NO_2, NO, and CO, are principal air pollutants due to their severe harms to the ecological environment.Zeolites have been considered as good absorbent candidates to capture the six exhaust gases.In this work, we performed grand canonical ensemble Monte Carlo(GCMC) simulations to examine the capability of 95 kinds of all-silica zeolites in the removal of the six toxic gases, and to predict the adsorption isotherms of the six gases on all the zeolites.The simulation results showed that, H_2S, NO, NO_2, CO and NH_3 are well-captured by zeolite structures with accessible surface area of 1600–1800 m~2·g~(-1) and pore diameter of 0.6–0.7 nm, such as AFY and PAU, while SO_2 is well-adsorbed by zeolites containing larger accessible surface area(1700–2700 m~2·g~(-1)) and pore diameter(0.7–1.4 nm) at room temperature and an atmospheric pressure.However, at saturated adsorption, zeolites RWY, IRR, JSR, TSC, and ITT are found to exhibit better abilities to capture these gases.Our study provides useful computational insights in choosing and designing zeolite structures with high performance to remove toxic gases for air purification, thereby facilitating the development and application of exhaust gas-processing technology in green industry.     

Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore

Manganese leaching during high concentration flue gas desulfurization process with semi-oxidized manganese ore was studied in this paper. It was found that there were different reaction pathways among which MnO_2,Mn_2O_3 and MnCO_3 in semi-oxidized manganese ore during flue gas desulphurization and manganese leaching.High SO_2 concentration facilitated redox reaction between MnO_2 and SO_2, and high concentration of H_2SO_4 accelerated MnCO_3/Mn_2O_3 leaching from semi-oxidized ore. Kinetics study showed that manganese leaching in flue gas desulfurization process with semi-oxidized ore was controlled by a mixed-control model, that is the surface chemical reaction and mass diffusion dominated both the oxidation of SO_2 and manganese leaching process. The apparent activation energy was 13.05 k J·mol~(-1) and the reaction orders with respect to SO_2 and H_2SO_4 concentration were 1.38 and 0.10, respectively. Finally, a semi-empirical rate equation based on shrinking core model was derived to describe the process.     

Activation of monolithic catalysts based on diatomaceous earth for sulfur dioxide oxidation

The formation of the active phases during the activation process of monolithic catalysts based on V₂O₅–K₂SO₄ supported on diatomaceous earth for SO₂ to SO₃ oxidation in flue gases, has been shown to be a crucial factor to achieve satisfactory catalytic performance. As the temperature is increased from room temperature to 470°C, SO₂ and SO₃ are taken up by the green catalyst and the precursors are transformed into the active species. The role of each component of the catalyst during the activation was analyzed by studying the behavior towards SO₂ adsorption of four materials, which contained: diatomaceous earth, diatomaceous earth + V, diatomaceous earth + K, and diatomaceous earth + V + K. The influence of the potassium sulfate accessibility in the green catalyst was studied by using two different preparation methods, which gave rise to differences in the catalysts SO₂ adsorption properties and catalytic performance. Furthermore, the influence of the activation atmosphere was studied using nitrogen, oxygen or a flue gas composition. It was shown that pyrosulfate species should be formed at temperatures below 400°C, to keep the vanadium in the active 5+ oxidation state.     

Selective oxidation of H2S to elemental sulfur over chromium oxide catalysts

CrO_x and CrO_x supported on SiO₂ have been found to be active for the selective oxidation of hydrogen sulfide to elemental sulfur. The catalysts show maximum sulfur yield at a stoichiometric ratio of O₂/H₂S, 0.5. Amorphous Cr₂O₃ exhibits higher yield of sulfur and has stronger resistance against water than supported Cr/SiO₂, especially at low temperatures. At high temperatures above 300°C, the sulfur yield over the supported catalyst becomes similar to amorphous Cr₂O₃ because the Claus reaction occurring on the silica support removes SO₂ to increase the sulfur yield. Active sites are the amorphous monochromate species that can be detected as a strong temperature programmed reduction (TPR) peak at 470°C. Catalytic activity can be correlated with the amount of labile lattice oxygen and the strength of Cr–O bonding. The reaction proceeds via the redox mechanism with participation of lattice oxygen.     

三聚氰胺与SO2反应及再生行为

以固体有机胺三聚氰胺（MN）为脱硫剂,对MN与SO₂反应及再生行为进行研究。结果表明,烟气组成0.35% SO₂+5% O₂+N₂,40℃、4% MN（质量分数）条件下,MN可维持140 min脱硫率>99%,穿透硫容（出口SO₂浓度200 mg/m³）0.33 g SO₂/（g MN）。MN脱硫及再生产物XRD、FTIR、SEM及TG-MS等表征分析表明,MN与SO₂反应首先生成三聚氰胺亚硫酸盐,随后被烟气中的氧气氧化为三聚氰胺硫酸盐,加入0.1%对苯二胺可有效抑制三聚氰胺亚硫酸盐氧化;三聚氰胺亚硫酸盐在75~150℃可加热再生,三聚氰胺硫酸盐不能加热再生。烟气含5% O₂条件下,加入0.1%对苯二胺,三聚氰胺亚硫酸盐氧化率由36%降低至13%,150℃下再生2 h,再生率由58%提高至94%,MN抗氧二次脱硫性能优良。