On the role of conserved proline residues in the structure and function of Clostridium pasteurianum 2[4Fe-4S] ferredoxin

The widespread occurrence of Pro residues adjacent to Cys ligandsin the sequences of [4Fe-4S] electron transfer proteins hasnot yet found a functional basis. The two such Pro of Clostridiumpasteurianum 2[4Fe-4S] ferredoxin have been probed by site-directedmutagenesis. Any one of them, but not both simultaneously, canbe substituted without impairing the proper folding of the protein.The reduction potentials of the ferredoxin variants fall ina narrow range of <20 mV above the potential of the nativeprotein. The biological activities with C.pasteurianum hydrogenaseand pyruvate-ferredoxin oxidoreductase do not change significantly,except when Lys replaces Pro. In these cases, the data suggestthat the two clusters of 2[4Fe-4S] ferredoxin may not alwaysbe equivalent in the interaction with the redox partners. Destabilizationof the structure has been observed as the consequence of theProl9 or Pro48 substitutions. Using 2-D NMR, this effect hasbeen associated with perturbations of both the hydrogen bondnetwork and one amino acid side chain around the [4Fe-4S] clusters.Thus, the conserved Pro found in the binding motif of [4Fe-4S]clusters in proteins strongly stabilizes the active site butdoes not play an essential role in the mechanism of electrontransfer.     

色谱法分析煤气总硫

铂丝还原滴定法在测量干法脱硫后硫化物含量时，测量数据偏离实际结果，容易造成触媒中毒。提出了用气相色谱火焰光度检测器测定的方法，使数据更可靠、准确。     

燃烧固硫反应的动力学和热力学及其影响固硫产物分解因素的研究

煤在高温条件下燃烧不利于固硫反应，并从热力学角度出发，得出了煤燃烧中钙基固硫剂反应自由能与温度的关系函数，由化学反应动力学得出院 硫酸钙分解反应的动力学方程及其相关参数，在还原性气氛中，从理论和实验上都证明了硫酸钙在较低温下会发生二次分解，理论分解温度与实际分解温度非常吻合，煤灰中氧化钙和三氧化二铝的存在，可以提高硫酸钙的分解温度同阳也给出了钙基固硫剂的应用条件。     

Combined XPS and TPR study of sulfur removal from a Pt/BaO/Al2O3 NO x storage reduction catalyst

Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts (1 wt% Pt, 10 wt%BaO) were sulfated under conditions simulating a real NSR catalyst operation. Comparative TPR and XPS studies of sulfur removal from Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts indicate that the sulfur removal from Al₂O₃ surface precedes reductive decomposition of BaSO₄ (250–400 °C). Barium sulfate decomposition started with further increase in desulfation temperature at the point of surface atomic ratio Ba:S = 1 (~450^o). Simultaneously, an intensive formation of sulfide species on the catalyst surface was observed. Thermodynamic analysis of the desulfation process allows us to hypothesize that barium sulfide formation may hinder sulfur removal under reducing conditions.     

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.     

Co－Mo／MgO－Al_2O_3一氧化碳耐硫变换催化剂失活原因的探讨

采用程序升温硫化（ＴＰＳ）技术，微反—色谱法（ＭＲＣ）、扫描电镜、透射电镜和其它分析测试手段，对工业应用前后的Ｃｏ－Ｍｏ系耐硫变换催化剂Ｋ８－１１进行了分析，从而对其失活原因进行了分析和讨论     

硫黄硫化聚氨酯橡胶的性能研究

研究了不饱和聚醚型聚氨酯橡胶（PUR）的硫黄硫化体系，以及硫化剂硫黄和促进剂DM对胶料硫化特性、硫化胶的物理机械性能和耐热空气老化性能的影响。结果表明，硫黄对PUR性能影响明显，焦烧时间长，正硫化时间短，胶料有很好的操作安全性；硫化胶物理机械性能高，拉伸强度达到30MPa，耐热空气老化性能优异，100℃×72h后其拉仲强度保持率高达90％，硫黄用量以2～2．5份为佳；促进剂DM对PUR性能影响显著，有效提高其硫化反应速度，缩短正硫化时间，其用量以2～3份为宜。     

Influence of Carbon on SOx Emissions from Glass Processing

Carbon reacts with Na₂SO₄ in glass batches, influencing SO _x emissions. To study the role of carbon active surface area (ASA) in the decomposition phenomena, Na₂SO₄ is reacted with three carbons with a wide ASA range. The decomposition behavior was evaluated by thermogravimetric analysis (TGA) and evolved gas analysis via mass spectrometry and Fourier transform infrared spectrometry. Higher carbon ASA yields lower decomposition temperatures. SO _x emissions are realized at temperatures as low as 773 K. Isothermal Na₂SO₄–C decomposition initiates via the nucleation of Na₂S. The rate constants for the nucleation regime are normalized against ASA, yielding an activation energy of 275 kJ/mol for nucleation.     

微生物法处理含硫工业废气

指出了含硫工业废气传统处理方法的缺陷 ,介绍了微生物处理方法的优势所在 ;对微生物菌种的共同特征以及无机硫和有机硫脱除时菌种的选择依据进行了讨论 ,并对微生物法脱硫的机理进行了分析 ;评述了国内外生物滤池法、生物滴滤池法和生物吸收法等生物膜法脱硫的工艺及其工业化应用。指出了微生物法脱硫技术有待深入研究的问题、发展趋势和应用前景。     

三氧化硫磺化甲苯反应的工艺条件研究

采用稀释SO3磺化甲苯工艺，研究了磺化温度．SO3配气比，原料中水含量和二甲苯砜抑制剂等工艺因素对反应转化率，产物中甲苯磺酸异构体含量及副产物二甲苯砜含量的影响。在10℃．SO3浓度为6％（volume）的操作条件下，二甲苯砜为抑制剂，甲苯转化率达到35％（mass）．反应产物中没有新增二甲苯砜，对甲苯磺酸含量达到88．24％．间甲苯磺酸含量降低到0．97％。