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。     

活性炭负载磷钨酸催化剂的制备及其催化氧化脱硫性能

以活性炭(AC)为载体,磷钨酸(HPW)为活性组分,通过等体积浸渍法制备HPW/AC催化剂,并以二苯并噻吩(DBT)的正十二烷溶液为模拟油(硫含量为800μg/g),H_2O_2为氧化剂,探究催化剂的催化氧化脱硫性能。采用BET、SEM和XRD表征手段对催化剂的结构进行分析。考察了反应温度、反应时间、H_2O_2用量、催化剂用量、乳化剂用量以及模拟油的组成对催化剂催化氧化脱硫效果的影响,最后考察了催化剂的循环使用性能。结果表明,AC经质量分数45%硝酸溶液80℃下活化2h,活性组分HPW的负载质量分数为30%时,所制备的HPW/AC催化剂的氧化脱硫性能最好;最佳反应条件为反应温度80℃,反应时间80min,氧化剂/硫摩尔比n(H_2O_2)/n(S)=12,催化剂用量0.05g/m L,乳化剂用量0.004g/m L。该反应条件下DBT被氧化为二苯并噻吩砜(DBTO_2),用N-甲基吡咯烷酮(NMP)进行萃取,萃取比为1,模拟油的氧化脱硫率达到90.4%。芳香族化合物和烯烃对氧化脱硫效果起到抑制作用,烯烃的影响最为显著,并且催化剂具有良好的稳定性。     

Pd/AC催化剂制备及其催化完全氧化邻-二甲苯性能

制备了一系列活性炭(AC)负载的贵金属催化剂,并考察了其对邻-二甲苯的完全催化氧化性能,发现Pd/AC是其中活性最高的催化剂。重点研究了制备溶剂、预处理、负载量以及反应空速对Pd/AC催化剂催化氧化邻-二甲苯性能的影响。利用比表面积(BET)、热重差热(TG-DTA)、X射线光电子能谱(XPS)和X射线衍射(XRD)等表征手段,研究了Pd/AC催化剂的物性结构与催化氧化邻-二甲苯性能之间的关系。结果表明,还原态的Pd既是Pd/AC上主要的存在状态,又是催化氧化邻-二甲苯的活性物种。同时,结合气相色谱-质谱仪(GC/MS)对反应产物的检测结果,讨论了邻-二甲苯在Pd/AC催化剂上可能的催化氧化反应机理。     

888脱硫催化剂及在中氮厂应用技术的新进展

众所周知，湿式氧化法脱硫是在液相进行催化氧化反应的脱硫过程。即气相中的H2S首先被脱硫液所吸收并电离，通过催化氧化作用使HS-变成单质硫。在液相将HS-氧化成单质硫是借助于脱硫液中的催化剂来实现的。催化剂在很大程度上决定着     

活性炭脱除煤气中H_2S的气氛影响及动力学研究

用活性炭对模拟煤气中的H2S进行催化氧化脱除,考察了反应温度、氧硫比以及煤气气氛组成对活性炭催化氧化脱除H2S行为的影响.结果表明,最佳催化脱硫温度约为180℃,氧硫比为1∶2.煤气气氛中,CO,CO2和H2含量的增加降低了活性炭的硫容,而水蒸气含量的提高则有利于脱硫反应的进行,提高了反应的脱硫效率和活性炭的硫容.对其动力学行为进行研究,结果表明,脱硫反应过程属于表面反应控制过程,给出了脱硫反应动力学方程及动力学参数.     

载铁酚醛树脂基活性炭的制备及H2S脱除性能

通过共溶法在水溶性酚醛树脂中加入硝酸铁,经高温炭化和二氧化碳活化,制备出载铁酚醛树脂基活性炭.使用X-射线衍射(XRD)、热重(TGA)、红外光谱(FTIR)、扫描电镜(SEM)和液氮物理吸附对产品进行了物理性质表征.BET测试表明,活性炭比表面积为258.11 m3/g,平均孔径为3.2 nm.考察了载铁活性炭常温含氧气氛下对硫化氢的催化氧化性能,结果表明,载铁酚醛树脂基活性炭具有较高的脱硫活性,其中含铁组分对氧化硫化氢有强的催化作用.     

栲胶脱硫过程中单质硫生成机理

采用循环伏安法研究了栲胶脱硫过程中HS-和V5＋之间的氧化还原反应。实验结果表明：在栲胶脱硫过程中,HS-和V5＋之间的反应有多硫离子Sx2-生成,多硫离子是反应过程中的活性中间产物,其进一步转化可生成单质硫S8。随着反应物V5＋浓度的增加,单质硫的生成速率增加。最后,提出了一种硫氢根HS-和V5＋反应生成单质硫S8的自由基机理。     

炭载体对Pt-C复合物非碱性条件下催化甘油氧化性能的影响

采用等量浸渍法制备了具有相似平均粒径的活性炭(AC)和碳纳米管(CNTs)负载的Pt催化剂,并比较研究了非碱性条件下两种催化剂催化甘油氧化反应的性能。结果表明,炭载体对Pt-C复合物催化甘油氧化反应的活性、选择性和稳定性有重要影响。相对于Pt/CNTs催化剂,Pt/AC催化剂中Pt 4f结合能较低,导致其表面氧的覆盖度相对较高,因而抑制了甘油的吸附,降低了甘油氧化反应的初始活性;Pt/AC催化剂会促进甘油醛进一步氧化成甘油酸以及C3产物的氧化断键;Pt/AC催化剂失活的主要原因是氧中毒和中间产物的吸附,而Pt/CNTs催化剂的失活主要是由于甘油酸的吸附堵塞Pt表面的活性位造成的。     

催化裂化汽油氧化-萃取脱硫

采用催化裂化(FCC)汽油氧化-萃取深度脱硫工艺,考察了氧化反应条件、萃取剂的种类、萃取剂中的含水量以及剂油比对萃取脱硫效果的影响,并对氧化-萃取前后硫含量及类型硫进行了分析。结果表明:杂多酸/相转移剂/H2O2催化氧化体系是非常有效的氧化脱硫体系;随着油剂比、萃取剂含水量的增加,汽油的脱硫率下降,收率增加,在剂油比1∶1、溶剂的含水量10%条件下,汽油的脱硫率达到80%以上,收率97.5%以上;杂多酸/相转移剂/H2O2催化氧化体系对噻吩环被破坏电子效应强的苯并噻吩及甲基苯并噻吩类硫化合物有很好的反应活性,对电子效应弱的噻吩类硫化合物反应活性较低。     

焦炉荒煤气脱硫化氢技术开发与应用

河钢宣钢焦化厂研究了开发新型非水相离子液焦炉煤气脱硫工艺。此工艺利用专有的铁基非水相离子脱硫剂,在脱硫塔内与煤气硫化氢接触反应,使硫化氢氧化成单质硫,单质硫进入脱硫液中形成脱硫富液,富液经富液泵打入再生塔中氧化,形成脱硫贫液,贫液经贫液泵打入脱硫塔脱硫,循环使用。脱下的硫经板框压滤机分离入熔硫釜熔化成硫黄液体,冷却后变成硫黄。没有废液外排,脱硫剂和催化剂为无毒无害,所产生的硫膏没有气味,为绿色处理工艺。从运行过程中看,可将硫化氢含量降低到20mg/m~3以下,该技术工艺具有投资适中,运行效果好,不产生二次污染,综合运行成本低等特点。     

A continuous process for recovery of sulfur from natural gas containing low concentrations of hydrogen sulfide

A continuous catalytic process was developed to remove hydrogen sulfide from a natural gas stream using activated carbon as catalyst. The concentration range of hydrogen sulfide in the gas stream studied was 300–3000 ppmv (0.0126–0.126 moles/m³). Virtually 100 percent conversion of hydrogen sulfide was achieved by the combination of various parameters. The “field gas” employed in this study exhibited cracking of some heavier hydrocarbons and made the product sulfur slightly brown. These hydrocarbons should therefore be separated from the gas stream prior to the oxidation reaction. No carbon monoxide or carbon dioxide was produced during the oxidation of hydrogen sulfide. It is concluded that the process described herein has the potential for the removal of hydrogen sulfide as sulfur from a sour natural gas stream on a continuous basis and could therefore eliminate an environmental problem which now exists.     

Reactivity of Metal Oxide Sorbents for Removal of Sulfur Compounds from Coal Gases at High Temperature and Pressure

Abstract

Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated to effectively remove hydrogen sulfide with various metal oxide sorbents at high temperatures and pressures. Metal oxide sorbents such as zinc titanate oxide, zinc ferrite oxide, copper oxide, manganese oxide, and calcium oxide were found to be promising sorbents in comparison with other removal methods such as membrane separation and reactive membrane separation. The removal reaction of H₂S from coal gas mixtures with zinc titanate oxide sorbents was conducted in a batch reactor. The main objectives of this research are to formulate promising metal oxide sorbents for removal of hydrogen sulfide from coal gas mixtures, to compare reactivity of a formulated sorbent with a sorbent supplied by the Research Triangle Institute at high temperatures and pressures, and to determine effects of concentrations of moisture contained in coal gas mixtures, and to determine effects of concentrations of moisture contained in coal gas mixtures on equilibrium absorption of H₂S into metal oxide sorbents. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures.     

活性炭的改性条件及其对硫化氢吸附性能的影响

以工业活性炭为载体制备改性活性炭,对比研究了未改性活性炭,NaOH、Na2CO3、Fe(NO3)3、Cu(Ac)2改性活性炭及挂膜硫氧化细菌后活性炭在相同条件下对硫化氢穿透时间及吸附容量的影响。结果表明：在相同控制条件下,NaOH改性活性炭明显优于其它改性剂;不同梯度改性剂条件下,20% NaOH改性活性炭对硫化氢的吸附效果最好,吸附穿透容量为78.25 mg/g,穿透时间可以达到2000 min以上;不同改性剂挂膜硫氧化细菌后对硫化氢均有一定的处理效果,其中对已达到饱和吸附的NaOH改性活性炭挂膜后的再生效果可以达到100%以上,说明挂膜硫氧化细菌活性炭对硫化氢的处理具有很好的效果。     

Desulfurization of digester gas: prediction of activated carbon bed performance at low concentrations of hydrogen sulfide

Three chemically modified/impregnated activated carbons (supplied by manufactures) were used for adsorption–catalytic removal of hydrogen sulfide from digester gas. The performance of samples was studied in dynamic conditions at 1000, 2000 and 5000 ppm of H₂S in digester gas. The results showed differences in the H₂S removal capacities related to the type of carbon and conditions of the experiment. A decrease in H₂S concentration resulted in an increase in a breakthrough capacity, which is linked to slow kinetics of oxidation process. No significant changes were observed when the oxygen content increased from 1 to 2% and the temperature from 38 to 60 °C. On the surface of carbons studied hydrogen sulfide was oxidized predominantly to sulfur, which was deposited in micropores, either on the walls or at the pore entrances. The capacities at low concentrations, 50 and 100 ppm, of H₂S were determined using an approach based on known theoretical solution of a dynamic model where the parameters of the model were determined from the experimental data at a high concentration of an adsorbate.     

Hydrogen sulphide emission control by combined adsorption and catalytic combustion

The removal of low concentrations of hydrogen sulfide by adsorption and catalytic combustion has been studied. Concentration of hydrogen sulfide by adsorption from waste-gas streams is best effected by molecular sieve 13X, if the stream is dry, and by activated carbon, if the gas stream is moist.

Low-temperature catalytic oxidation of hydrogen sulphide in moist gas streams can be effected over activated carbon. The reaction appears to involve ionized hydrogen sulfide, dissolved in water condensed in the pores of the carbon.

At high temperatures, both supported platinum and palladium catalysts are found to be oxidation catalysts. Palladium is the best catalyst for methane oxidation but is partially deactivated in the presence of sulfur-containing gases. In contrast, platinum was more active for the same reaction in the presence of sulfur-containing gases.

Both metals were found to promote the oxidation of hydrogen sulfide above ca. 150°C. The power rate laws describing the kinetics of reaction were determined.     

硅胶催化双氧水甲酸氧化噻吩类化合物的研究

1 INTRODUCTION Due to growing environmental concern to impact of sulfur oxides contained in engine exhaust emissions, sulfur content specifications in light oils are becoming more and more stringent worldwide[1,2]. The necessity of producing low sulfur fuels to meet new regulation mandates requires new desulfurization techniques. As for the current hydrodesulfurization (HDS) technology, higher temperature, higher pressure, larger reactor volume, and more active catalysts are unavoidable,…     

国外高温煤气脱硫剂研究进展

本文评述了国外高温煤气脱硫剂的研究进展，讨论了热力学和动力学研究结果，将脱硫剂归纳为含单一，双1混合金属氧化物及其它4类，最后简介工业化试验情况并提出我国开展该研究的几点建议。     

催化臭氧氧化处理渗滤液RO浓液的氧化特性及光谱分析

腐殖质的去除效率是催化臭氧氧化降解垃圾渗滤液RO浓液中有机物的关键,活性炭负载金属铈催化剂（Ce-AC）催化臭氧氧化可有效提高腐殖质的去除效率。本文通过XRD、SEM和EDS等手段对Ce-AC催化剂进行表征,对比不同催化剂催化臭氧氧化对RO浓液COD去除及可生化性的影响,通过降解产物光谱分析明晰腐殖质的降解机制。结果表明,铈氧化物是以CeO₂萤石晶型的形式负载在AC上,负载后的AC比表面积和孔容积减少,平均孔径增加。催化剂Ce-AC对COD和UV₂₅₄的去除效果最好,为44.7%和67.3%,出水可生化性显著提升,B/C比从0.06提升到0.47。紫外-可见光谱表明,体系代表腐殖质的芳香类化合物降解效率明显;三维荧光光谱表明体系中腐殖质类物质被极大程度地降解,荧光区域积分的结果表明腐殖质类物质的去除效率达到了66.7%;傅里叶红外光谱表明腐殖质类物质被氧化分解成了相对小分子的碳水化合物和有机胺、硫和醇等。     

Use of modified activated carbon for the oxidation of aqueous sulfide

The oxidation of aqueous sulfide promoted by activated carbon (AC) was investigated. Raman, infrared, X-ray diffraction, ultraviolet–visible spectroscopy and electron paramagnetic resonance analyses show that AC oxidizes aqueous sulfide to form a complex mixture of polysulfides and sulfur oxide species. This oxidation is strongly promoted by the presence of oxygen surface groups introduced by oxidation of the AC as shown by kinetic measurements. These results are discussed in terms of the similarities the AC have with enzymatic systems, i.e. redox surface groups (e.g. quinone) combined with an efficient electron conduction system.