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1.
考虑了烯烃、醇与酸的再吸附及其非本征效应(烯烃、醇与酸在催化剂孔道中的扩散作用、物理吸附及溶解度效应)对产物分布的影响,推导了基于详细反应机理的亚甲基插入的烷基机理F-T合成校正综合动力学模型.利用文献数据对动力学模型进行了回归,获得了与文献报道结果相一致的动力学参数.由校正动力学模型计算的烷烃、烯烃、醇与酸产物分布及烯烃比、醇烃比及酸烃比与实验数据较好地吻合.动力学计算结果表明,在铁锰催化剂上,烷烃、烯烃、醇与酸生成的反应是平行竞争反应,烯烃、醇与酸在催化剂表面的再吸附及二次反应导致产物分布偏离了ASF分布.动力学研究还表明,相同碳数的醇与酸产物在催化剂表面上再吸附及二次反应的机会比相同碳数的烯烃大.通过比较相同碳数的烯烃、醇与酸的分子体积及沸点,指出了在铁锰催化剂上,低碳数的烯烃、醇与酸的再吸附及二次反应对产物分布影响的非本征效应中,烯烃、醇与酸的扩散阻力不是主导效应.  相似文献   

2.
担体对Fe-MnO催化剂CO加氢合成烯烃性能影响的TPSR表征   总被引:1,自引:0,他引:1  
考察了不同担体担载的Fe-MnO催化剂上CO加氢合成烯烃的反应。结果表明担体直接影响低碳烯烃选择性。通过对催化剂的CO,CO/H2,C2H4等吸附的TPSR表征及催化剂表面CO加氢微观反应的研究,证明以碱性担体为基质的PBC催化剂具有强吸附CO能力,且生成的烯烃不易发生二次反应,因而PBC催化剂具有较高的烯烃选择性;以酸性担体为基质的PAC催化剂对CO为弱吸附,对H2为较强吸附,且烯烃会发生强烈的  相似文献   

3.
PdSAPO-5分子筛在甲醇转化反应中的催化性能及机理   总被引:1,自引:0,他引:1  
用连续-脉冲激反应色谱评价了不同SAPO-5分子筛及一步法合成的PdSAPO-5催化剂对甲醇制烯烃(MTO)反应的催化性能,用TPD-MS及13CCPMASNMR研究了其催化反应机理.结果表明,PdSAPO-5比SAPO-5和Pd/SAPO-5有更高的烯烃选择性,这是由于反应物凝胶中加入的钯对分子筛的酸性具有调节作用,加入不同形式的钯源,其调节作用有较大的差别,并使分子筛上甲醇及生成的二甲醇的脱附温度不同.此外,钯还充当了脱氢中心,可从二甲基已基氧离子中脱下一个氢原子,从而有利于乙烯的生成.NMR结果表明,此类催化剂上的结炭存在多种形式.反应生成乙烯的甲氧基离子主要是二甲基乙基氧离子;甲醇在此类催化剂的部分钯粒子上脱氢生成CH2O.  相似文献   

4.
制备了以γ-Al2O3为载体的Ni-Mo催化剂,并用于FCC汽油的加氢硫转移反应。对Ni-Mo/Al2O3催化剂上的硫转移反应机理进行了研究,考察了不同反应条件对硫转移反应的影响。实验结果表明,硫醇与烯烃的反应在催化剂表面的加氢活性位上进行,小分子的硫醇发生加氢脱硫,生成吸附态H2S,吸附态的H2S与烯烃反应,生成大分子硫醇和硫醚;另外小分子硫醇还可直接与烯烃发生反应,生成硫醚。提高反应温度、压力、氢油比或降低空速,均可提高催化剂的硫转移反应活性,轻质硫转化率得到明显提高,且单烯选择性还能维持在98%左右。  相似文献   

5.
实验研究了在氢气存在下,一氧化碳与亚硝酸乙酯偶联合成草酸二乙酸反应体系在典型操作条件下的化学反应和反应性能,结果表明氢气只与反应体系中的亚硝酸乙酯反应生成乙醇。由于氢气与一氧化碳在催化剂表面竞争吸附,并且氢的存在打破了生成草酸二乙酯所必需的正常的氧化还原过程:Pd^0→Pd^2 →Pd^0,因此氢的引入使一氧化碳转化率及草酸二乙酯选择性下降。此外,化学吸附测试结果表明氢气和一氧化碳是在催化剂表面同一活性中心上吸附。  相似文献   

6.
Ni/Al2O3催化剂上甲烷部分氧化制合成气反应CO2主要来源   总被引:1,自引:0,他引:1  
负载型金属催化上甲烷催化部分氧化剂合成反应机理存在着燃烧-重整机理和直接氧化之争,如果反应按燃烧-重整机理进行,则CO2则是反应的一次产物而CO2是二次产物;如果反应按直接氧化机理进行,则CO是一次产物。本文采用同位素瞬变技术,对Ni/Al2O3催化上甲烷部分氧化制合成气反应中CO2的来源进行了研究,结果表明CO2同CO-样,主要来源于催化剂表面NiO与甲烷分解生成的NixC的反应,这就有力地证明  相似文献   

7.
研究了端基烯烃和醛肟在氧化剂过硫酸氢钾和催化量碘代烷烃作用下的[3+2]环合反应,合成了一系列具有良好产率及区域选择性的3,5-二取代异噁唑啉化合物.反应中,碘代烷烃先经过氧化分解产生了活泼的次碘酸,再依次与醛肟和烯烃经亲电加成反应生成五元杂环碘代中间体,该中间体通过消除反应得到3,5-二取代异噁唑啉化合物.考察了反应条件的影响,提出了可能的反应机理,为合成3,5-二取代异噁唑啉化合物提供了新方法.  相似文献   

8.
 采用单位键指标-二次指数势(UBI-QEP)方法对模型催化剂Co(0001)晶面进行了费-托(F-T)合成反应的反应能学分析,发现以不含氧的CxHy,s 作为中间体的表面碳化物机理在能量上较为合理,而CH2,s 作为链增长单体的链增长方式是能量上最有利的F-T合成反应途径. 在Co/ZrO2/SiO2催化剂上的非稳态实验研究中发现,在F-T合成的操作温度范围内,H2O的生成是主要的表面O的移去方式; CO解离和表面碳物种Cs加氢可能是F-T合成中的重要速控步骤; 链增长过程是F-T合成反应中较快的基元反应步骤; 甲烷的生成具有多种不同活性的表面前驱体,导致生成的甲烷严重偏离经典的ASF分布规律. 结合F-T合成表面反应的研究结果,初步确定了F-T合成动力学研究中需要考虑的机理模型的范围是以CO解离和表面碳物种Cs加氢为速控步骤,以CH2,s 插入为链增长途径的表面碳化物机理. 该结果缩小了待选动力学模型的范围.  相似文献   

9.
采用unity bond index-quadratic exponential potential(UBI-QEP)方法, 以Co(0001) 单晶为模型催化剂, 对Fischer-Tropsch(F-T)合成的三种可能反应机理(表面碳化物机理、烯醇机理和CO插入机理)进行了全面的能学分析. 计算结果表明, 通过表面碳化物机理生成烃类产物从能学角度看较为合理, 其中COads表面解离和Cads加氢具有较高的活化能垒, 可能是整个F-T反应序列中的慢步骤; 通过CH2,ads插入金属-烷基键实现链增长的活化能垒最低, 是能量上有利的链增长方式; 在Co(0001)晶面上烷基经β-H消除生成烯烃的活化能垒低于加氢生成烷烃, 而通过CO插入机理生成的有机含氧化合物的二次反应能垒较低, 从而导致其在Co催化剂上的低选择性. 此外, 与Fe/W(110)相比, Co金属上的CHx,ads加氢以及CH2,ads插入的活化能垒较低, 从而解释了Co催化剂上甲烷选择性较高和倾向于生成重质烃类产物的特性.  相似文献   

10.
 在浆态反应釜中研究了铁/活性炭催化剂上费-托合成(Fischer-Tropschsynthesis,FTS)反应产物分布和链增长几率(Anderson-Schulz-Flory(ASF)链增长几率和本征链增长几率).产物分布通常在C1处和C2处偏离ASF分布,呈现C1处偏高而C2处偏低的情况.本征链增长几率的研究结果表明,以活性炭为载体的铁基费-托合成催化剂上存在烯烃的再吸附二次反应,使产物分布偏离ASF分布.铁/活性炭催化剂上同时伴随水煤气变换(watergasshift,WGS)反应.XRD检测到铁/活性炭催化剂上存在FexC和Fe3O4两种物相.  相似文献   

11.
Recent experiments concerning prebiotic materials syntheses suggest that the iron-bearing meteorite impacts on ocean during Late Heavy Bombardment provided abundant organic compounds associated with biomolecules such as amino acids and nucleobases. However, the molecular mechanism of a series of chemical reactions to produce such compounds is not well understood. In this study, we simulate the shock compression state of a meteorite impact for a model system composed of CO2, H2O, and metallic iron slab by ab initio molecular dynamics combined with multiscale shock technique, and clarify possible elementary reaction processes up to production of organic compounds. The reactions included not only pathways similar to the Fischer–Tropsch process known as an important hydrocarbon synthesis in many planetary processes but also those resulting in production of a carboxylic acid. It is also found that bicarbonate ions formed from CO2 and H2O participated in some forms in most of these observed elementary reaction processes. These findings would deepen the understanding of the full range of chemical reactions that could occur in the meteorite impact events. © 2018 Wiley Periodicals, Inc.  相似文献   

12.
The kinetics of the formation of iron carbides during the activation of iron-coated catalyst for Fischer–Tropsch synthesis promoted by copper and potassium, and by carbon monoxide and syngas, is studied. It is established that the presence of copper lowers the initial temperature of hematite reduction to magnetite and leads to the formation of carbide in both CO and СО/Н2. Potassium slows the rate of magnetite formation, but it accelerates the formation of iron oxide. It is shown that the rate of carbide formation during magnetite reduction for catalysts is half that in the reaction of hematite reduction to magnetite in both CO and СО/Н2.  相似文献   

13.
The Fischer–Tropsch synthesis using cobalt catalysts supported on zeolitic imidazolate frameworks (ZIFs), ZIF-7 and ZIF-8, has been investigated. ZIF-7, ZIF-8 and corresponding cobalt-containing catalysts, after preparation, were characterized using various techniques. Thermogravimetric analysis results show that ZIF-7 and ZIF-8 supports have good thermal stability for the Fischer–Tropsch synthesis reaction, and weaker interaction between cobalt and zinc in the ZIF-7 and ZIF-8 supports results in more cobalt reduction. The catalytic performance was evaluated in Fischer–Tropsch synthesis and compared with that of a cobalt catalyst supported on SBA-15 promoted with zinc. The pore structure of the ZIF supports plays an essential role in product selectivity for the prepared catalysts. The carbon number in hydrocarbon products and olefin selectivity depend on cobalt dispersion and support structure owing to the impacts of site density and carrier skeleton on the speed of diffusion-enhanced olefin re-adsorption reactions.  相似文献   

14.
It is well known that if the formation of hydrocarbons during Fischer–Tropsch synthesis occurs via the condensation polymerization mechanism, there is little hope for selectivity enhancement in the desired range of products. Recent data on low surface area model catalysts, where readsorption is unlikely, have shown that at low conversions, the product distribution obeys the condensation polymerization mechanism and the distribution of products is shifted to lower-molecular-weight hydrocarbons. We have used a computer simulation of the growth of hydrocarbon chains to obtain a picture of the catalyst surface under synthesis conditions. Such an approach could prove useful in distinguishing between various theoretical models. We have applied the simulation to compare the changes in selectivity when readsorption occurs and when it does not. The dynamic behavior of the reacting system which is obtained from the computer results has shown that selectivity to lower-molecular-weight hydrocarbons is a stronger function of the extent of reaction than the incorporation of readsorption into the chain growth mechanism.  相似文献   

15.
The effects of Mg, La and Ca promoters on primary and secondary CO_2 and H_2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO_2 catalysts are investigated. The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H_2O and CO_2 , respectively. The secondary pathway was the water-gas shift reaction. The results indicated that the CO_2 production led to an increase in both primary and secondary pathways, and H_2 O production decreased when surface basicity of the catalyst increased in the order Ca >Mg >La.  相似文献   

16.
A detailed kinetic model of Fischer–Tropsch synthesis (FTS) product formation, including secondary methane formation and 1‐olefin hydrogenation, has been developed. Methane formation in FTS over the cobalt‐based catalyst is well known to be higher‐than‐expected compared to other n‐paraffin products under typical reaction conditions. A novel model proposes secondary methane formation on a different type of active site, which is not active in forming C2+ products, to explain this anomalous methane behavior. In addition, a model of secondary 1‐olefin hydrogenation has also been developed. Secondary 1‐olefin hydrogenation is related to secondary methane formation with both reactions happening on the same type of active sites. The model parameters were estimated from experimental data obtained with Co/Re/γ‐Al2O3 catalyst in a slurry‐phase stirred tank reactor over a range of conditions (T = 478, 493, and 503 K, P = 1.5 and 2.5 MPa, H2/CO feed ratio = 1.4 and 2.1, and X CO = 16–62%). The proposed model including secondary methane formation and 1‐olefin hydrogenation is shown to provide an improved quantitative and qualitative prediction of experimentally observed behavior compared to the detailed model with only primary reactions.  相似文献   

17.
sec-Alkyl radicals are key reactive intermediates in the hydrocarbon combustion and atmospheric decomposition mechanisms that are formed by the abstraction of hydrogen from an alkane, or as a second generation product of n-alkyl H-migrations, C-C bond scissions in branched alkyl radicals, or the bimolecular reaction between olefins and n-alkyl radicals. Since alkanes and branched alkanes, which the sec-alkyl radicals are derived from, make up roughly 40-50% of traditional fuels an understanding of their chemistry is essential to improving combustion systems. The present work investigates all H-migration reactions initiated from an sec-alkyl radical that involve the movement of a secondary hydrogen, for the 2-butyl through 4-octyl radicals, using the CBS-Q, G2, and G4 composite methods. The resulting thermodynamic and kinetic parameters are compared to similar reactions in n-alkyl radicals in order to determine underlying trends. Particular attention is paid to the effect of cis/trans and 1,3-diaxial interactions on activation energies and rate coefficients. When combined with our previous work on n-alkyl radical H-migrations, a complete picture of H-migrations in unbranched alkyl radicals is obtained. This full data set suggests that the directionality of the remaining branched chains has a minimal effect on the rate coefficients for all but the largest viable transition states, which is in stark contrast to the differences predicted by the structurally similar dimethylcycloalkanes. In fact the initial location of the secondary radical site has a greater effect on the rate than does the directionality of the remaining alkyl chains. The activation energies for secondary to secondary reactions are much closer to those of the secondary to primary H-migrations. However, the rate coefficients are found to be closer to the corresponding primary to primary reaction values. A significant ramification of these results is that there will be multiple viable reaction pathways for these reactions instead of only one dominant pathway as previously believed.  相似文献   

18.
采用原位时间分辨红外光谱和原位显微Raman光谱技术对Ir/SiO2上甲烷部分氧化(POM)制合成气反应的初级产物和反应条件下催化剂表面物种进行了跟踪考察,实验结果表明,在H2预还原的新鲜Ir/SiO2表面,CO是V(CH4):V(O2):V(Ar)=2:1:45混合气反应的初级产物,因而甲烷的直接氧化过程是CO生成的主要途径;而在稳态反应条件下,CO生成的途径可能主要来自CO2和H2O与催化剂表面积碳物种(CHx)和/或CH4的反应.催化剂上生成的积碳可能是导致稳态条件下Ir/SiO2上POM反应机理不同于H2预还原的新鲜催化剂的主要原因.  相似文献   

19.
考察了反应温度对Co/SiO2催化剂在Fischer-Tropsch(F-T)合成中合成气吸附行为及稳定性的影响. 采用FTIR, TPSR, XRD, BET, HTPD和TPR等手段对催化剂进行了表征. 结果表明, CO在催化剂表面的吸附为活化吸附, 在270 ℃仍稳定存在, 随着反应温度的升高, 催化剂上发生的主反应由CO加氢链增长反应向Boudouard反应转化, 当反应温度≥350 ℃时, 以Boudouard反应为主. 另外, 随反应温度升高, 金属钴的烧结现象变得明显, 并伴随着硅酸钴或水合硅酸钴物种的生成. 在催化剂的失活因素中, 烧结为主要原因.  相似文献   

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