柠檬酸钠溶液循环吸收工艺在制硫尾气脱硫中的工业应用

阐述了利用柠檬酸钠溶液循环脱硫工艺对克劳斯制硫尾气进行脱硫处理的效果。工业试验结果表明,把克劳斯制硫尾气焚烧、洗涤降温后,用柠檬酸钠溶液循环吸收脱硫,脱硫效果好,排烟中二氧化硫体积质量低于50 mg/m3。该工艺将脱硫过程中回收的二氧化硫再返回克劳斯制硫装置回收硫黄。脱硫系统工程投资小,运行费用低,脱除二氧化硫的成本为1 172.5 RMB$/t,工艺简单,操作方便,排放的废液量少。     

A study on the reactivity of Ce-based Claus catalysts and the mechanism of its catalysis for removal of H2S contained in coal gas

In this study, Claus reaction was applied for the selective removal of H₂S contained in the gasified coal gas, and the characteristics of Claus reaction over the Ce-based catalysts were investigated to propose the reaction mechanism. The Ce-based catalysts showed a high activity on Claus reaction. Specially, Ce_0.8Zr_0.2O₂ catalyst had a higher activity than CeO. On the basis of our experimental results, it was proposed that the selective oxidation of H₂S was carried out by the lattice oxygen in the Ce-based catalysts and that the reduction of SO₂ was performed by the lattice oxygen vacancy in the reduced catalyst. Since the mobility of the lattice oxygen in Ce_0.8Zr_0.2O₂ composite catalyst was better than the one in CeO₂, Ce_0.8Zr_0.2O₂ provided more lattice oxygen for the selective oxidation of H₂S. It was presumed that the reaction mechanism to convert H₂S and SO₂ into elemental sulphur over our prepared catalysts was different from the mechanism over the solid-acid catalysts. It is believed that Claus reaction over the Ce-based catalysts was carried out by the redox mechanism. Since the moisture was contained in the major components, CO and H, of the gasified fuel gas, the effects of CO and H₂O on the catalytic reaction were investigated over a Ce-based catalyst. The conversion of H₂S and SO₂ was decreased in Claus reaction over the Ce-based catalysts as the concentration of either H₂O or CO in the gasified coal gas was increased. Under the circumstances of the coexistence of both moisture and CO, however, the conversion was increased as the concentration of CO was increased. The reactivity of Claus reaction was varied in terms of the concentration ratio of CO to H₂O. The maximum conversion of H₂S and SO₂ was achieved in the condition of that the concentration of CO contained in the reacting gas was higher than the one of H₂O. The conversions of H₂S and SO₂ did not match to the stoichiometric ratios of Claus reaction. The higher conversion of H₂S was obtained in the higher concentration of H₂O, while the higher conversion of SO₂ was achieved in the higher concentration of CO. It was another evidence to indicate that the Claus reaction over the Ce-based catalysts was carried out by the redox mechanism.     

硫回收系统运行及改造措施

介绍改良的Claus工艺加Clinsulf工艺的硫回收系统的工艺流程,总结系统的运行状况,分析系统运行不正常的原因,提出改造措施,经过改造后系统运行效果良好.     

BYSR硫黄回收工艺在促进剂M酸性废气处理中的应用

介绍BYSR硫黄回收工艺的技术特点、工艺流程及其在促进剂M酸性废气处理中的应用。结果表明：BYSR硫黄回收工艺的二级克劳斯工艺,总硫回收率为95．0％～97．0％,二级克劳斯工艺＋低温克劳斯工艺,总硫回收率为99．0％～99．5％;尾气中二氧化硫排放量达到国标要求;回收硫黄的纯度不小于99．90％;装置的工艺适应性和针对性更高,操作弹性大,有助于降低促进剂生产企业的投资和运营成本。     

对降低尾气处理装置SO_2排放的认识与建议

针对将硫磺回收装置排放尾气中SO2质量浓度从960mg/m3降至500mg/m3以下的技术方案,提出通过降低贫液进入SCOT工艺选吸塔的温度及贫液中H2S浓度,可有效地将总硫回收率提高至99.9%以上;若再辅以配方型溶剂的应用,则有望进一步改善选吸效果与总硫回收率。但现有工业数据表明,目前,属于氧化-吸收型的Cansolv总硫回收率低于常规SCOT工艺。因此,对采用Cansolv工艺处理Claus硫磺回收装置尾气的方案宜采取慎重态度。     

Modifying effects of hydrogen sulfide on the rheometric properties of liquid elemental sulfur

Handling molten sulfur is inherently difficult due to liquid sulfur's extreme rheological behavior. Upon melting at 115°C, sulfur's viscosity remains low until reaching 160°C, the λ-transition region, where the viscosity increases to a maximum of 93,000 × 10⁻³ Pa s at 187°C. Within this study, our previous viscosity measurements for pure liquid elemental sulfur have been discussed along with new measurements on sulfur containing physically and chemically dissolved hydrogen sulfide (H₂S). H₂S is always incorporated into industrial sulfur which has been recovered through the modified Claus process in gas plants and oil refineries. Using the experimental data from this study, a semi-empirical correlation model was reported based on the reptation model of Cates to estimate the impact of H₂S on liquid sulfur's viscosity as a function of temperature. The equation can be applied to commercial sources of sulfur with 0–500 ppm of total dissolved H₂S.     

克劳斯尾气碱洗涤与生产硫酸的比较

为使克劳斯硫回收装置的硫回收率达到100%,讨论并比较了碱洗涤与生产硫酸这2种尾气处理技术。这2种技术都可用于满足最苛刻的排放要求,生产硫酸的成本略低。但除了成本之外,还应考虑炼油厂的总体布置、原油类型及硫和氮含量、产品酸的市场需求、所需公用工程的供应等因素。     

An investigation of reaction furnace temperatures and sulfur recovery

In a modern day sulfur recovery unit (SRU), hydrogen sulfide (H₂S) is converted to elemental sulfur using a modified Claus unit. A process simulator called TSWEET has been used to consider the Claus process. The effect of the H₂S concentration, the H₂S/CO₂ ratio, the input air flow rate, the acid gas flow of the acid gas (AG) splitter and the temperature of the acid gas feed at three different oxygen concentrations (in the air input) on the main burner temperature have been studied. Also the effects of the tail gas ratio and the catalytic bed type on the sulfur recovery were studied. The bed temperatures were optimized in order to enhance the sulfur recovery for a given acid gas feed and air input. Initially when the fraction of AG splitter flow to the main burner was increased, the temperature of the main burner increased to a maximum but then decreased sharply when the flow fraction was further increased; this was true for all three concentrations of oxygen. However, if three other parameters (the concentration of H₂S, the ratio H₂S/CO₂ and the flow rate of air) were increased, the temperature of the main burner increased monotonically. This increase had different slopes depending on the oxygen concentration in the input air. But, by increasing the temperature of the acid gas feed, the temperature of the main burner decreased. In general, the concentration of oxygen in the input air into the Claus unit had little effect on the temperature of the main burner (This is true for all parameters). The optimal catalytic bed temperature, tail gas ratio and type of catalytic bed were also determined and these conditions are a minimum temperature of 300°C, a ratio of 2.0 and a hydrolysing Claus bed.     

硫磺回收过程工艺研究进展

介绍了克劳斯硫回收工艺的基本原理、工艺方法及硫回收中影响操作的主要因素,介绍了国内外硫回收的进展和方向,提出改善我国硫回收状况的建议。     

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采用自行研制的4条气路、双高灵敏热导检测器、五柱管专用气相色谱仪,对川西北净化厂引进的三级转化MCRC硫回收装置进行考核分析。用这台仪器检出该工艺过程涉及的15个组分的控制分析,由分析数据所得的考核值与工艺模拟电算程序的结果吻合。本文介绍的分析技术快速、可靠,适用于天然气净化厂硫磺回收及尾气处理工艺装置的控制分析和考核分析。