热扩散管反应器中甲烷转化反应的研究

为了实现甲烷的有效转化,使用热扩散管反应器进行了甲烷的脱氢偶联反应. 结果表明,C2至油状产物被生成. 实验表明,由于热扩散作用的存在,当甲烷由上向下通入垂直设置的反应管时,C2烃的选择性较高. 在碳棒温度1470K下甲烷转化率约为36%,C2选择性可达40%,其中乙炔和乙烯的摩尔分数在95%以上. 在添加氢气的(摩尔比:n(H2)/n(CH4)=1/2)情况下,C2选择性上升至68.3%,甲烷气体的转化率约为23%. 在碳棒温度1470K、甲烷由上向下通入反应器,反应器出口气体产物中氢气的摩尔分数在40%以上.     

生物质制取氢气和生物油液体燃料

催化水蒸气重整由生物质快速裂解得到的生物油制取氢气,催化剂C12A7-O^-／15％Mg显示了很高的活性,并在我们所研究的几种催化剂中具有最高的氢产率．在最佳重整条件（T=750℃,S／C=6．0,GHSV=26000h^-1）下,得到70％的氢产率和约93％的最大碳转化率．结果显示,氢产率和碳转化率对温度和S／C（水蒸气和碳的摩尔比）具有选择性．目前结果表明,由水蒸气重整生物油制取的生物油舍成气,用费托合成法直接合成洁净液体生物油燃料将是一个很有前景的选择．研究了由生物油合成气制备的费托合成液体燃料的特征,在典型的反应条件（T=300℃,P=1．5MPa,W／F=12．5gcat·h／mol）下,总碳转化率（包括CO和CO2）约36％,C5＋的选择性约44％．     

不同类型分子筛对甲缩醛的催化性能

在间歇反应方式下, 研究了以甲醛和甲醇为原料合成甲缩醛反应所需的催化剂. 在30 ℃, 醛醇摩尔比为1∶2, 加入5%（质量分数）的催化剂条件下, 考察了HY, HM , Hβ, γ-Al₂O₃和 HZSM-5等催化剂对该合成反应的催化效果, 从中优选出HZSM-5. 进一步对不同硅铝比和 不同交换度的HZSM-5进行评价. 实验结果表明, 硅铝比为38, 交换4次的HZSM-5分 子筛对该 合成反应具有良好的催化作用, 甲醛的转化率为45%, 甲缩醛的选择性达99%. 该催化剂经 20次重复使用, 甲醛的转化率、 甲缩醛的选择性无明显变化, 表现出良好的催化稳定性 .     

Role of support in photothermal carbon dioxide hydrogenation catalysed by Ni/CexTiyO2

Nickel was supported on varied ratios of ceria-titania mixed oxides(Ni/Ce_xTi_yO_2) to evaluate the role the support plays in photothermal carbon dioxide hydrogenation to produce methane. In a batch photothermal reactor system, Ni/CeO_2 achieved the highest conversion rate, reaching a conversion of 93% in approximately60–90 min. To decouple the influence of light and heat, the CO_2 hydrogenation was examined in an in-house designed photothermal reactor, whereby heat can be applied externally. Decoupling experiments revealed that heat from the thermalisation by light was the main driving force for the reaction. In addition, the conversion and temperature profile of the different catalysts revealed that the catalyst performance was governed by catalyst reducibility. H_2-TPR analyses showed that the Ni became more readily reducible with increasing Ce O_2 content,suggesting that the oxide plays a role in activating the Ni. The reduction temperature of the nickel catalyst(following a reduction and passivation process) was below 200 °C, which meant that the inherent heating temperature of the photothermal reactor was sufficient to initiate Ni/CexTiyO_2 catalyst activity. The exothermic methanation reaction was then able to heat the system further, ultimately reaching a temperature of 285 °C. The ancillary rise in temperature promotes further nickel reduction and methane formation, leading to a "snow-ball"effect. The findings demonstrate that, to achieve a "snow-ball" effect in a photothermal system, designing a catalyst which is easy to reduce, active for CO_2 hydrogenation, and capable of converting light to heat for its initial activation is critical.     

负载杂多酸催化剂催化合成直链烷基苯的研究

在固定床反应器和一定的反应条件下，考察了改变苯烯摩尔比对负载杂多酸催化剂催化合成直链烷基苯的活性和选择性的影响。实验结果表明，随着苯烯比的增加，十二烯的转化率和2位-十二烷基苯的选择性均有所增加。在苯烯摩尔比4∶1、液体质量总空速10h^-1、温度120℃和液固反应条件下，对催化剂的稳定性进行了实验考察，结果显示，连续反应70h后，负载杂多酸催化剂的活性明显下降。利用SEM、FT-IR和TG等对失活催化剂进行了基本表征，结果表明积炭可能是引起负载杂多酸催化剂失活的主要原因。     

微反应器中甲醇-水蒸气重整制氢三维模拟

为考察进口温度、速度和水醇比对微反应器中甲醇-水蒸气重整制氢过程的影响,利用计算流体力学软件FLUENT中的通用有限速率模型对自行设计的平板微通道反应器中甲醇-水蒸气重整制氢进行了三维数值模拟.反应动力学采用甲醇分解和蒸气重整双速率幂函数模型.计算表明,在反应物进口速度为2.88 m/s、进口温度为493 K和水醇比为1.3的反应条件下,反应器出口转化率达79.8%.通过模拟可以看出微反应器能够在较大的反应物流量下保持较高的出口氢气含量和较高的甲醇转化率.     

苯酚双氧水氧化法制邻、对苯二酚

对苯酚、双氧水合成邻、对苯二酚的反应体系,采用苯酚溶液一次性加入反应器、双氧水连续滴加的半间歇操作方式,研究了苯酚与双氧水的摩尔配比、苯酚初浓度、双氧水滴加速率、反应温度等因素对苯酚转化率和邻、对苯二酚选择性的影响。在适宜的工艺条件下,苯酚的转化率可达到40%左右,苯二酚的总选择性可达到90%左右,邻/对比为1.6～1.8。     

空气等离子体条件下丙烯氧化反应

为研究空气等离子体对丙烯的活化作用,在室温和常压下,采用介质阻挡放电法,考察玻璃反应器材质种类及长度对丙烯转化率、环氧丙烷选择性及其他产物分布的影响.实验结果表明:介质阻挡放电法可转化丙烯和空气直接生成环氧丙烷;玻璃反应器材质种类对丙烯环氧化反应有显著影响;在其他条件不变的情况下,随着反应器长度增加,丙烯转化率迅速增加,环氧丙烷、丙醛和丙烯醛等C3类氧化产物的摩尔分数均降低.     

CO_2吸附强化模拟生物油重整制氢的实验研究

选用Ce-Ni/Co作催化剂、由醋酸钙煅烧制得的Ca O作重整催化剂、CO2吸附剂,进行模拟生物油吸附强化蒸汽重整制氢的研究.实验结果表明:在相同温度、M(S)/M(C)(加入水蒸气的摩尔质量与生物油模化物中碳的摩尔质量之比)条件下,吸附剂的加入有利于提高氢气摩尔分数和氢气产率;添加吸附剂后,随着温度的升高,氢气摩尔分数、氢气产率均呈现先增大后减小的趋势,在700℃时达到最大;随着M(S)/M(C)的增加,氢气摩尔分数先增大后减小,在M(S)/M(C)=9时氢气摩尔分数达到最大,而氢气产率则在M(S)/M(C)超过9后变化不大;随着M(Ca O)/M(C)(加入的氧化钙的摩尔质量与生物油模化物中碳的摩尔质量之比)的增加,氢气摩尔分数逐渐增大,达到M(Ca O)/M(C)=3后几乎不变,氢气产率则先增大后减小,在M(Ca O)/M(C)=3时达到最大;温度=700℃,M(S)/M(C)=9,M(Ca O)/M(C)=3为模拟生物油重整制氢的最佳条件,在此条件下氢气摩尔分数、氢气产率分别达到92.2%,84.1%.     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

基于双效催化剂的生物油吸附强化重整实验

制备了镍基双效催化剂,并将其应用在多组分生物油模化物吸附强化重整制氢的研究中,考察了重整温度、水碳比、液体质量空速对反应过程的影响.结果表明,在双效催化剂作用下,吸附强化重整阶段获得的氢气体积分数和氢气产率较普通重整阶段显著提升;且随着温度升高、S/C比(水蒸气与碳物质的量之比)增大,氢气产率与氢气体积分数呈现先增加后小幅减少的趋势;且相比于普通重整阶段,最高氢气产率所对应温度明显下降,在650℃,S/C比为4.5时氢气产率达到最大值87.60%,此时氢气体积分数为94.75%.     

Ni/α-Al2O3催化剂上甲烷水蒸气重整本征动力学

在消除扩散影响的条件下，在装填工业Ni/α-Al₂O₃催化剂的微分反应器内进行了甲烷水蒸气重整的本征动力学研究。实验证明在低产物浓度时H_2, CO和CO₂为主要产物，且两者的生成速率均与CH₄分压成正比，同时CO的生成速率与CO₂分压成正比关系，而CO₂的生成速率与H₂O分压成正比关系。考虑了5种可能的模型推导了本征动力学方程，通过参数估计和模型比较确定了比较满意的甲烷水蒸气重整本征动力学方程。     

生物质焦油模化物蒸汽重整实验研究

生物质焦油是生物质热解和气化过程中不可避免的副产物,并且在生物质应用过程中存在有害的影响,因此对于生物质焦油转化的研究受到广泛的关注。本文在试制开发低流阻高强度的蒸汽重整整体式催化剂的基础上,以苯和甲苯作为焦油的模型化合物,在管式反应器上研究了该催化剂作用下,温度、蒸汽量对焦油催化转化以及裂解气体成分的影响;并实验研究了催化剂作用下温度和水碳摩尔比S／C对甲烷转化率的影响。实验发现,苯和甲苯的转化率都随温度的提高而升高。甲苯和苯在裂化温度900℃,S／C=2时整体式催化剂催化作用下转化率分别达到94．1％和77．1％;在600℃时实现了甲烷气体的高效转化;蒸汽量的增加有助于裂解气体成分的调整,同时也促进了消碳反应的进行。     

单极性脉冲电源结合介质阻挡放电降解VOCs

将单极性脉冲高压电源引入介质放电阻挡反应器(螺旋棒式不锈钢电极、石英玻璃介质),分别对氯苯和甲苯的分解特性进行实验.结果发现,这种放电形式可以高效注入能量,兼有脉冲电晕放电和介质阻挡放电的特点.高压脉冲电压使电场强度急剧增强,产生瞬间大功率放电和高能粒子,可以实现对VOCs化学键的高效裂解,从而提高对挥发性有机化合物的降解作用.此外,实验还表明,在相同条件下,氯苯比甲苯难以分解.     

非热等离子体对柴油机尾气中NO_x的治理

为去除柴油机尾气中的氮氧化物(NOx),设计了一套基于介质阻挡放电形式的非热等离子体(non-thermal plasma,NTP)反应器。通过改变放电电压及模拟气体组分,考察了NTP对NOx的还原效果以及对BaO/Al2O3催化剂储存NOx的促进作用。结果表明,NTP直接还原NOx效率不高,但可将NO氧化成NO2;从NO向NO2的转化率随放电电压及含氧量的升高而增加;加入丙烯能提高直接净化NOx的效率;由于NTP的协同,催化剂的NOx储存能力在300℃下提高了68%。     

研究非平衡等离子由CH4加CO2 偶联制C2烃类反应机理

O2电晕放电条件下能产生O/O^-活性粒子,选用CO2作氧化剂,代替O2来实现CH4的氧化偶联,提出了反应机理,并通过CH4/CO2比值对反应体系（封闭）的影响,证实反应机理的可靠性.     

Acetone hydrogenation in exothermic reactor of an isopropanol–acetone–hydrogen chemical heat pump: effect of intra-particle mass and heat transfer

Intra-particle mass and heat transfer plays an important role in performance of the exothermic fixed-bed reactor for an isopropanol-acetone-hydrogen chemical heat pump. In this work, an exothermic fixed-bed reactor model, taking into account the actual packing structure, is established in the commercial software Fluent. A 120° segment of a tube with tube-to-particle diameter ratio （n） of 4, where realistic particles are packed and set to porous media, is used to simulate the 3D external flow, concen- tration and temperature fields in the exothermic packed-bed reactor. The influence of catalyst particle diameter （dp） and micropore diameter （do） on the intra-particle temperature, species distribution, reaction rate and selectivity is dis- cussed. The appropriate dp and do are obtained. Simulation results showed that intra-particle temperature gradient is not obvious. Large dp and small do lead to remarkable gradient of reaction rate inside the catalyst particle and the decrease in the catalyst efficiency and reduce the acetone conversion and the selectivity in isopropanol. The optimal results reveal that the spherical catalyst with dp of 1 mm and dpore of 10 nm is appropriate for high-temperature acetone hydrogenation.     

The kinetic studies of direct methane oxidation to methanol in the plasma process

The research outlined here includes a study of methanol production from direct methane conversion by means of thermal and plasma method. The kinetic study, derived from thermal-based approach, was carried out to investigate thoroughly the possible intermediate species likely to be presented in the process. A set of plasma experiments was undertaken by using dielectric barrier discharge （DBD）, classified as non-thermal plasma, done at atmospheric pressure and room temperature. Plasma process yields more methanol than thermal process at the same methane conversion rates and methane to oxygen feed ratios. Oxidation reaction of thermal process resulted CO and CO2 as the most dominant products and the selectivity reached 19% and 68%, respectively. Moreover, more CO and less CO2 were produced in plasma process than in thermal process. The selectivity of CO and CO2 by plasma was 47% and 20%, respectively. Ethane （C2H6）was detected as the only higher hydrocarbon with a significant concentration. The concentration of ethane reached 9% of the total products in plasma process and 17% in thermal process. The maximum selectivity of methanol, the target material of this research, was 12% obtained by plasma method and less than 5% by thermal process. In some certain points, the kinetic model closely matched with the experimental results.     

Ca（OH）2对污泥中制取富氢气体的影响

以城市污泥转化为富氢气体为目的,使用超临界水（SCW）间歇反应器,以Ca（OH）2为催化剂,主要考察了Ca/C摩尔比、反应温度对城市污泥在SCW条件下生成的气体组成、碳转化率以及CO2吸收率等的影响。实验结果表明,随着Ca/C摩尔比的增加,气相产物中的CO2可以得到有效固定,同时促进碳转化率和H2产率升高。在600℃、30MPa的条件下,当Ca/C摩尔比为0.6时,CO2的吸附率达到95％,H2含量比Ca/C比为0时提高14.7。随温度升高,碳转化率和H2的体积分率逐渐增加,Ca的利用率也逐渐增大。温度为680℃时,CO2吸附率达到99％,H2含量达到43.7％。Ca（OH）2的催化作用在高温下更加显著。     

介质阻挡放电-光催化降解甲苯的实验研究

为有效地去除挥发性有机物VOCs,采用低温等离子体-光催化技术进行了处理甲苯气体的研究.实验在不同的能量密度、气体流量、放电时间以及反应器结构(包括内电极直径和电极结构)条件下,考察了介质阻挡放电驱动光催化剂TiO2对甲苯转化率的影响.结果表明: 添加TiO2能极大地提高甲苯转化率,使甲苯降解更为彻底,并提高产物选择性;随着能量密度的增大,甲苯转化率提高,CO2收率增加;而气体流量增大,甲苯转化率降低;放电5min内甲苯转化率迅速提高,15min后基本维持稳定.另外,实验结果还表明对于甲苯的降解反应器内电极直径存在最佳值.