羰基硫催化水解研究进展

综述了羰基硫水解催化剂载体和活性组分的选择，介绍了羰基硫水解反应机理和催化剂中毒失活的研究现状，并指出多组分混合或添加抗中毒助剂制备高活性、耐高氧羰基硫水解催化剂是未来这一领域的发展方向。     

羰基硫脱除技术

综述了羰基硫(COS)的性质和各种脱除方法包括胺法、加氢、水解、氧化等技术的原理与特点。胺法多用于处理H2S和COS同时存在的天然气和炼厂气,关键在于提高COS脱除率;加氢转化法将COS转化成H2S的转化率高,在石油炼制中应用较为广泛,但所用Co-Mo-Al2O3催化剂价格昂贵,操作温度较高,并存在一定的副反应。水解转化法反应温度低、不消耗氢源、副反应少,是目前十分活跃的研究领域,重点在于高活性催化剂的研制。指出开发配方优化和系列化的醇胺类溶剂吸收体系及催化剂性能优良的水解转化法有较好的发展前景。     

中低温羰基硫催化水解技术研究进展

对羰基硫水解催化剂、水解反应动力学和反应机理等研究现状进行了评述。指出添加抗中毒助剂制备高活性催化剂、将醇胺脱硫体系与水解法相结合以及采用水滑石吸附法同时脱除H₂S和COS是未来这一领域的研究热点。     

TGH-3Q型羰基硫常低温水解催化剂及应用

研究了太原理工大学开发的TGH－3Q型COS水解催化剂上的动力学行为。实验表明,这种改进型催化剂在温度40～180℃范围显示很高的催化活性和抗氧中毒能力。该催化剂已成功用于氨厂和甲醇厂的气体净化,使用寿命超过三年。根据用无梯度微型反应器和色谱仪获得的结果,其水解反应的本征速率可表达为：对于大颗粒催化剂,宏观速率可表示为该催化剂的耐毒害能力与其上沉积的硫／硫酸盐沉积学密切相关。在所提出的机理的基础上给出了催化剂因氧毒害而失活的动力学模型。     

羰基硫脱除技术研究现状及进展

论述了脱除羰基硫的各种方法,包括还原法、水解法、吸收法、吸附法、光解法及氧化法等,展望了COS脱除技术的研究趋势。指出ZrO2与TiO2、Al2O3混合制备新的多组分催化剂,以及引入铁一类助剂来降低催化剂表面的亲水性进而降低催化剂的失活程度是COS脱除技术研究可能的新方向。     

TGH-3Q型羰基硫常低温水解催化剂及其应用

系统介绍了TGH-3Q宽稳区羰基硫水解催化剂的性能及在常低温不同情况下的使用情况，该催化水解过程的本征及宏观动力学规律和氧中毒的动力学特征。指出，研究开发动力学软件对使用催化剂的重要性。     

羰基硫在氢氧化钠水溶液中的水解动力学

常压下、温度20～50℃,测定了鼓泡反应器中羰基硫(COS)在1.3130～4.4038mol/LNaOH水溶液中的水解速率,获得一级快速不可逆反应的水解速率表达式,其表观活化能为59.63kJ/mol.     

金属氧化物吸附剂脱硫过程中羰基硫的生成

金属氧化物脱硫剂脱硫过程中产生羰基硫的现象缩小了脱硫剂的使用范围。本文从气体中存在一氧化碳、二氧化碳、单质硫和硫化氢出发给出了均相、非均相生成羰基硫的途径,特别综述了生成羰基硫的催化作用。在总结氧化铁基、氧化锌基、氧化锰基及氧化铜基主流金属氧化物脱硫剂脱硫过程中产生羰基硫研究结果的基础上,发现吸附在金属硫化物表面上的一氧化碳与活性硫化物的相互作用是生成羰基硫的主要反应步骤,活性硫化物可能是硫化氢热解成蒸气硫或硫氢根离子及硫化氢与金属氧化物反应生成的金属硫化物。     

Kinetic modelling of the hydrolysis of carbonyl sulfide catalyzed by either titania or alumina

The reaction rates for the hydrolysis of COS on both alumina (Kaiser 201) and titania (CRS 31) were measured from 270 to 330°C using a laboratory Berty reactor over ranges of water concentration, 2-12 mol %, and COS concentrations, 0.5-2 mol %. Four mechanism-related model functions were tested in the search for the best fitting function by using nonlinear regression techniques. The results indicate that an Eley-Rideal model provides the best fitting rate function for the hydrolysis of COS for both alumina and titania, even though their catalytic activities are different. The Bates and Watt's (1980) curvature measure along with simulation studies were used in the nonlinear regression search for the best values of the model parameters. The kinetic parameters obtained confirm that CRS 31 appears to be the better of the two catalysts for COS hydrolysis. The adsorption of water vapor significantly retards the hydrolysis rate, more so for Kaiser 201.     

羰基硫催化水解气氛效应及动力学研究进展

羰基硫催化水解是从原料气中间接脱除羰基硫的主要过程,在合成原料气精脱硫技术中起重要作用。从合成原料气主要构成如CO、CO_2、H_2、O_2、水蒸汽、H_2S和羰基硫等对羰基硫催化水解活性的影响,揭示了羰基硫催化水解的气氛效应,并综述了羰基硫催化水解动力学。认为改进催化剂活性组成和孔隙结构以及复杂气氛下动力学是羰基硫催化水解研究的主要领域。     

The low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review

The impetus to reduce the emission of sulfur-containing compounds into the environment has become increasingly important in recent years. This paper reviews the progress made towards reaching this goal and highlights the significant contributions made towards developing effective catalysts for the removal of carbonyl sulfide and carbon disulfide. Novel promoter materials, new catalyst morphologies, new reactor designs and developments for the future are reviewed and discussed.     

Compensation effect in catalytic hydrolysis of carbonyl sulfide at lower temperature compensation effect in COS hydrolysis

A series of catalysts impregnated with alkali metal oxides and alkali earth metal oxides for COS hydrolysis reaction was prepared. The activities of catalysts in lower temperature range (45–100 ° C) were investigated by means of microreactor-chromatograph. It was shown that the catalytic activity is closely related to the oxide and its content. Further, it was also observed that a compensation effect exists by studying the reaction rate constant (k) at various temperatures. That is, the activation energy (E) increases along with the increase of the pre-exponential factor (A).Both compensation effect parameter (K ₀) and energy distribution exponential factor (1/b) are closely related to the metal ionic radius (d _m).K ₀ = 11.437-6.5189d _m, ln(1/b) = ln 2.6382+0.039577 lnK ₀. The isokinetic temperatures (T _s) of all prepared catalysts were obtained. A possible explanation for the compensation effect in COS hydrolysis was given.     

羰基硫水解催化剂失活研究的现状与进展

介绍目前国内外对羰基硫水解催化剂机理及催化剂失活原因的研究进展与发展趋势。     

NHD/MDEA/H2O复合脱硫液催化水解羰基硫

为解决传统湿法脱硫工艺中有机硫脱除效率低、副产物多等问题,依托配方型溶剂脱硫工艺,以聚乙二醇二甲醚（NHD）、N-甲基二乙醇胺（MDEA）和水为原料构建新型湿法催化水解羰基硫（COS）脱硫体系。优化复配溶剂组成比例,确立配方溶剂组成为25% MDEA/15% H₂O/60% NHD,考察了脱硫操作参数、反应温度、气体浓度、气体流量等因素对脱硫的影响,使用气相色谱和离子色谱分析探究脱硫过程及反应动力学。结果表明,在低温（298.15~343.15 K）、常压条件下对COS的脱除效率达80%以上;复配溶液将吸收后的COS催化水解为H₂S和CO₂,吸收过程符合准一级反应动力学。该脱硫液中有机溶剂含量占85%以上,可解决脱硫副产物产生多和碱耗大的问题,是一种新型有机介质脱硫工艺。