Impact of impregnation pressure on desulfurization performance of Zn-based sorbents supported on semi-coke

High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke (SC) and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500°C and a simulated coal gas used in this work was composed of CO (33 vol%), H2 (39 vol%), H2S (300 ppm in volume), and N2 (balance). Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach <1 ppm and >99.7%, respectively, before sorbent breakthrough.     

纳米ZnO室温选择氧化H2S特性的研究

碱式碳酸锌在不同焙烧温度下制得的纳米ZnO具有六方晶系纤锌矿结构，平均粒径为15.4 nm、19.1 nm、22.9 nm和33 nm，以其为脱硫剂，对H2S室温脱硫性能进行了研究。利用XRD和XPS技术对脱硫反应前后的样品进行了表征。实验结果表明，纳米ZnO的脱硫性能随粒径的增大而降低，常温、常压下，260 ℃焙烧的纳米ZnO对H2S有高的去除率，并且H2S可选择性地被氧化为单质硫。     

Comparison of reduction behavior of Fe2O3, ZnO and ZnFe2O4 by TPR technique

Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature,regenerable,desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels.As a sort of effective desufurizer,such as Fe2O3,ZnO and ZnFe2O4,it will endure strong reducing atmosphere in desulfurization process.The reduced degree of desufurizer can have an effect on its desulfurization reactivity.In this paper,Fe2O3,ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH.After aging,washing and drying,the solids were calcined at 800℃.The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR).It is found that there are two reduction peaks for Fe203 in TPR,and whereas no reduction peaks for ZnO are found.The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3.ZnFe2O4 is easier to be reduced than Fe2O3.The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.     

汽油催化裂化脱硫USY/ZnO/Al2O3催化剂

提出了汽油经催化裂化脱硫的技术路线,并对催化剂进行了研究.综合采用浸渍和共 沉淀法制备的USY/ZnO/Al2O3汽油催化裂化脱硫催化剂在固定床反应装置上评价结果表明, 具有优异的脱硫活性和硫化物裂化选择性.脱除的硫绝大多数以H2S的形式进入到裂化气中, 仅有少量沉积在催化剂上,这有利于硫的回收利用和环境保护.硫化物的裂化脱硫是裂化和 氢转移反应协同作用的结果,高温有利于裂化反应,而相对较低的温度对氢转移有利,420 ℃左右为汽油裂化脱硫的最佳温度是这对矛盾作用的结果.     

Comparative study on the reaction of methane over a ZnO bed in the absence and presence of CO2

The reaction of zinc oxide with methane in the absence and presence of CO2 were theoretically and experimentally investigated using HSC Chemistry 5.1 software and a fixed bed reactor, respectively. In the absence of CO2 at 1193 K, the reduction of ZnO was accompanied with methane cracking, and metallic zinc, CO, and H2 were the main reaction products. This system could be utilized for the co-production of metallic zinc and synthesis gas, in which ZnO was a donor of oxygen. In the presence of CO2, ZnO plays as a catalyst in the CO2 reforming of methane and produces syngas with the average H2/CO ratio of 0.88 at 1193 K, which was close to the total reaction theoretic value of 1. It was also found that higher temperature favored high CH4 and CO2 conversions. XRD technique was used to characterize the ZnO species. The result showed that there were no differences in the peak profiles of the XRD patterns of the ZnO powder obtained before and after passing the CH4/CO2 mixed gases for 6 h at 1193 K. It is suggested that ZnO functions as a catalyst according to the redox cycle and metallic zinc plays the role of intermediate product in this process.     

Desulfurization kinetics of ZnO sorbent loaded on semi-coke support for hot coal gas

Zn-based sorbent (Z20SC) prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp(-8.270×103/RgT) and Dep=1.262×10-4exp(1.522×104/RgT).It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.     

氧化锌脱硫中氢和氧的双气氛效应及动力学研究

用热重法研究了氧化锌脱硫中氢氧的气氛效应以及氢氧共同存在下氧化锌脱硫的微观动力学行为。实验温区为200 ℃～320 ℃，氧化锌粒度为100目～120目。研究结果表明，在0%～40%的体积浓度范围内，氢可促进脱硫反应进行；氧则由于会引起氧化锌表面析硫使得脱硫过程随其浓度的变化复杂化。氢氧双气氛下，氧化锌脱硫动力学行为可用改良收缩核模型进行描述，表面反应活化能和固体扩散活化能分别为14.96 kJ/mol和46.77 kJ/mol。     

尿素/H2O2溶液同时脱硫脱硝机理研究

在填料塔上对尿素/H₂O₂溶液同时脱硫脱硝进行了实验研究。结果表明,尿素溶液对SO₂具有很高的去除效率,但对NO_x的去除受到多种因素的影响。实验主要研究了H₂O₂浓度、吸收反应温度、溶液pH值等因素对脱硝效率的影响,并确定了最佳实验条件,在此条件下脱硫脱硝效率分别达到100%和52.6%。同时,采用化学分析法和气相色谱法对尿素溶液同时脱硫脱硝的反应产物进行分析,推导出尿素/H₂O₂溶液同时脱硫脱硝的反应机理和总化学反应方程式。该技术可用于对现有湿法脱硫技术的改造,使其同时具有脱硫脱硝功能。     

The unexpected desulfurization of 4-aminothiophenols

Thermolysis of 4-aminophenyl benzyl sulfide at 523 K in the hydrogen donor solvent (HDS), 9,10-dihydroanthracene (AnH2), gave 4-aminothiophenol and toluene as the predominant products of the homolytic S-C bond cleavage. Under these conditions, a portion of the 4-aminothiophenol was desulfurized to aniline with first-order kinetics and with a rate constant estimated by kinetic modeling to be 7.0x10(-6) s-1. Starting with 4-NH2C6H4SH at 523 K, it was found that sulfur loss was more efficient in the non-HDSs, anthracene and hexadecane, than in AnH2. Under similar (competitive) reaction conditions, YC6H4SHs with Y=H, 4-CN, and 3-CF3 were completely inert; with Y=4-CH3O, there was some very minor desulfurization, whereas with Y=4-N(CH3)2 and 4-N(CH3)(H), the sulfur extrusions were as fast as that for Y=4-NH2. We tentatively suggest that this apparently novel reaction is a chain process initiated by the bimolecular formation of diatomic sulfur, S2, followed by a reversible addition of ground state, triplet 3S2 to the thiol sulfur atom, 4-NH2C6H4S upward arrow(SS upward arrow)H, and insertion into the S-H bond, 4-NH2C6H4SSSH. In a cascade of reactions, aniline and S8 are formed with the chains being terminated by reaction of 4-NH2C6H4S upward arrow(SS upward arrow)H with 4-NH2C6H4SH. Such a reaction mechanism is consistent with the first-order kinetics. That this reaction is primarily observed with 4-YC6H4SH having Y=N(CH3)2, N(CH3)(H), and NH2 is attributed to the fact that these compounds can exist as zwitterions.     

半焦吸附剂烟气脱硫脱硝性能

采用廉价半焦为原料,经硝酸氧化和高温热处理改性后,负载金属氧化物制备半焦吸附剂,考察吸附剂的脱硫脱硝性能和再生性能,并利用BET、TEM和TPD等手段研究影响半焦吸附剂性能的内在因素.结果表明,当烟气组成为NO-O2-N2时,吸附剂具有良好的脱硝性能,失活吸附剂经水洗再生后,脱硝活性恢复较好;当烟气组成为SO2-O2-...     

钛酸锌脱硫剂硫化过程的动力学分析

利用固定床反应器对钛酸锌高温煤气脱硫剂硫化过程的动力学进行了研究，考察了硫化反应温度、H2S体积分数对脱硫反应过程的影响。结果表明，脱硫剂具有良好的脱硫反应活性，在400 ℃～600 ℃，脱硫剂的硫化反应速率随着硫化反应温度的升高、反应器入口H2S 体积分数的增大而增大。在实验数据的基础上，利用等效粒子模型对其反应动力学进行了分析，发现该脱硫剂的硫化反应主要受固体内扩散控制，固体内扩散活化能为 61.4 kJ/mol，相应的频率因子为 4.4×105 m2/min。硫化反应后脱硫剂比表面积、孔体积显著减小，脱硫剂表面有颗粒聚集物存在，进一步验证了该脱硫剂的硫化反应主要是通过产物层的体相扩散控制的。     

纳米氧化锌的固相合成及其气敏特性

以酒石酸和乙二胺四乙酸为原料,分别与醋酸锌进行固相反应制得前驱化合物,进而热分解得到气敏材料氧化锌。用Ｘ射线粉末衍射和透射电镜对材料的陶瓷微结构进行了表征,并用静态配气法测试了材料在不同工作温度下对乙醇、氨气、液化石油气的灵敏度高,实验结果表明：用这种方法合成的氧化锌具有粒径小,工作温度低及对乙醇气体灵敏度高的特点。     

基于金属氧化物脱硫剂的天然气深度脱硫

确立了基于GC-MS和GC-SCD的天然气中超微量硫化物定性定量分析方法与条件,并分析了北京城市天然气中的硫化物。结果表明,天然气中含有三种硫化物,主要成分为四氢噻吩(THT),占总硫的94.2%。采用共沉淀法制备了ZnO/Al₂O₃脱硫剂,采用浸渍法制备了ZnO/γ-Al₂O₃、CuO/γ-Al₂O₃和CuO-ZnO/γ-Al₂O₃脱硫剂,并进行了天然气中THT深度脱除的实验研究。结果表明, 采用浸渍法制备的CuO/γ-Al₂O₃和CuO-ZnO/γ-Al₂O₃脱硫剂同时具有良好的低温活性和高温活性,可在50~500℃的宽温下将THT脱除至物质的量分数10×10^-9以下,从而能够满足以天然气为燃料的分布式质子交换膜燃料电池电站对脱硫深度和脱硫温宽的要求。     

Regenerable Fe-Mn-ZnO/SiO2 sorbents for room temperature removal of H2S from fuel reformates: performance, active sites, Operando studies

Fe- and Mn-promoted H(2)S sorbents Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) (x, y = 0, 0.025) for desulfurization of model fuel reformates at room temperature were prepared, tested and characterized. Sulfur uptake capacity at 25 °C significantly exceeds that of both commercial unsupported ZnO sorbents and un-promoted supported ZnO/SiO(2) sorbents. Sulfur capacity and breakthrough characteristics remain satisfactory after multiple (～10) cycles of adsorption/regeneration, with regeneration performed by a simple and robust heating in air. XRD shows that both "calcined" and "spent" sorbents contain nano-dispersed ZnO, and XPS confirms conversion of ZnO to ZnS. "Calcined" sorbent contains Fe(3+) and Mn(3+) that are reduced to Mn(2+) upon reaction with H(2)S, but not with H(2). Operando ESR is used for the first time to study dynamics of reduction of Mn(3+) promoter sites simultaneously with measuring sulfidation dynamics of the Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) sorbent. Fe cations are believed to occupy the surface of supported ZnO nanocrystallites, while Mn cations are distributed within ZnO.     

Modification of the ZnO(0001)-Zn surface under reducing conditions

The ZnO(0001)-Zn terminated crystal face was studied after reduction at high temperatures by combination of STM, STS, XPS and TDS. The clean ZnO(0001)-Zn surface exhibits triangular reconstruction in UHV, while after exposure to 10(-5) mbar H(2) at RT this reconstruction is lifted and a rough surface has formed. The roughness as well as the metallic character of the surface increased with the applied low-pressure reduction temperature up to 800 K. XPS revealed that exposure to 1 bar H(2) at RT led to the formation of OH groups; at higher temperatures progressive metallization of the ZnO surface was found to occur. Analysis of the thermal desorption results showed that huge amounts of H(2) dissolved into the ZnO crystal. The results obtained under these conditions were in good accordance with thermodynamic calculations. The experimental ratio between the absorbed amount of H(2) at RT and 800 K amounts to 1000. The ratio calculated from increasing diffusion coefficients with temperature only amounts to 6. This emphasizes the importance of ZnO as a H supplier by spillover, and proves that metallic Zn boosts dissociative adsorption of H(2). This surface modification of the ZnO structure during the reduction promotes an enhanced activity of the Cu/ZnO catalyst at elevated temperatures.     

烟气共存成分对微波辐照活性炭同时脱硫脱硝的影响研究

研究了O₂、CO₂以及水蒸气等各种烟气共存成分对微波辐照活性炭脱硫脱硝的影响。实验结果表明,SO₂对烟气脱硝有一定的抑制作用;烟气中水蒸气会抑制脱硫,低浓度水蒸气含量使脱硝效率上升,但高浓度水蒸气使脱硝效率下降;O₂和CO₂的存在可在一定程度上促进脱硫脱硝,但高浓度的O₂和CO₂会造成活性炭的损耗,从而抑制与脱硫和脱硝有关的还原反应。采用此方法可有效脱除烟气中SO₂和NO_{x,其脱除效率均在90%以上。}     

Characterization of active sites, determination of mechanisms of H(2)S, COS and CS(2) sorption and regeneration of ZnO low-temperature sorbents: past, current and perspectives

The intellectually and technically challenging pursuit of the emerging global environmentally "green" and energy-efficient infrastructure of the 21st century requires the development of a worldwide network of low- to medium-power fuel cell (FC) based portable electric power-generating devices and high-power biomass/clean coal "electric+chemical plants" with zero carbon footprint utilizing integrated coal gasification combined cycle with geologic carbon sequestration (IGCC-GCS) under energy-efficient low-temperature conditions. These emerging technologies require the deep and ultradeep desulfurization of gaseous feeds, since sulfur compounds, especially hydrogen sulfide H(2)S are highly corrosive and poisonous to both technological processes and the environment. Therefore, it is of crucial importance for both academic and industrial research communities to have a solid understanding of the atomic-level structures of active sites and molecular-level mechanisms of surface chemical reactions of the novel deep and ultradeep desulfurization materials, especially desulfurization sorbents. This review critically analyzes the recent literature (last ～20 years) on the experimental determination of molecular and atomic-level nature of adsorption sites, effects of desulfurization promoters, mechanisms of chemical reactions of H(2)S, COS and CS(2) and physical processes during and upon regeneration of "spent" low-temperature H(2)S sorbents based on ZnO that were developed for desulfurization of fuel reformates, syngas and similar streams. Recent trends in research on the ultradeep H(2)S sorbents are discussed with an impetus on real-time in situ and Operando techniques of instrumental chemical analysis, and the challenges of direct determination of the structure of active sites and of the experimental mechanistic studies in general are described.     

不同载体的镍基氧化锌对噻吩的吸附脱除性能

采用混捏法制备了以金属氧化物、黏土及分子筛为载体的三类镍基氧化锌吸附剂,采用FT-IR等分析手段进行表征,探讨了其物化性能的差异,并利用微型固定床反应器考察了上述吸附剂对噻吩的吸附脱除性能。结果表明,不同吸附剂对噻吩的吸附效果不同,黏土载体的吸附剂脱硫性能高于金属氧化物载体的脱硫性能,吸附剂的脱硫活性顺序依次为cay-sorb>diatomite-sorb>Al-sorb>Ti-sorb。利用FT-IR对吸附剂的表面酸性进行了表征。结果表明,吸附剂的脱硫性能与其总L酸量有关,总L酸量高的吸附剂脱硫效果较好。分子筛载体吸附剂的脱硫活性顺序依次为MCM-22-sorb>HY-sorb≥Hβ-sorb>H-mordenite-sorb>HZSM-5-sorb。通过比较分子筛载体的孔道结构表明,分子筛载体孔径大小是影响吸附剂脱硫性能的主要因素。     

STUDY ON PREPARATION OF INORGANIC COMPOSITE MEMBRANE AND ITS PROPERTIES FOR HYDROGEN PERMEATION

IntroductionDevclopmcntoftcchniqucsforthcscparationofgascousmixturesisofgrcatimportancetochemicalindustries.Rccentadvanccsinceramicmaterialprocessinghavcstimulatedtheeffortstodcvclopccramicormctallicmcmbrancsforgasseparation.Suchmembraneswouldbesuitableforthescparationsathightemperatureatx`hichthcx`ellcstablishedorganicpol}mermcmbranescannotfunctionButmostcommercialceramicmembranesxvhichcanbcobtainedinmarkctaremicroporous(porediamcterfromO.ItoloPm)whereseparationmcchanismisgovcrncdbyKnudscnd…     

ZnO超微粒子光催化氧化降解n-C7H16的研究

利用ZnO光催化氧化技术对气相n-C7H16进行了降解研究，考察了氧气、水燕气体积分数等因素对n-C7H16光催化氧化的影响，利用气相色谱－质谱联用仪和气相色谱仪对气相光催化反应过程中的气体组成进行了定性分析，并对主要中间产物丙醛进行了定量分析，结果发现，ZnO超微粒子光催化氧化n-C7H16的降解率较高，n-C7H16绝大部分被完全氧化成CO2，探讨了n-C7H16光催化氧化反尖的动力学行为及机理。