H2对CO气相催化偶联制草酸二乙酯反应的失活机理

重点研究了氢气（H₂）对一氧化碳（CO）催化偶联反应制草酸二乙酯的影响,分别考察了不同H₂浓度、不同温度和不同空时条件下加入H₂对CO偶联反应的影响,结果发现H₂的加入使反应过程中CO转化率、草酸二乙酯选择性和空时收率明显下降,且在实验条件范围内,通入H₂浓度越高、反应温度越高,催化剂活性下降越快.研究得出,H₂气氛下CO偶联反应失活动力学方程为：-da/dt=k_dc^0.65_H2.进一步分析失活动力学方程可知,加氢反应过程中,H₂和CO吸附在同一个活性中心上,H₂在活性中心上的吸附抑制了CO在催化剂上的吸附,从而使得CO催化偶联反应生成草酸二乙酯的速率下降,导致加氢后CO转化率、草酸二乙酯选择性和空时收率降低.     

硅橡胶/陶瓷复合膜反应器中CO2合成甲醇(Ⅲ)过程实验研究

对在由硅橡胶 /陶瓷复合膜所构成的膜反应器中进行的CO₂ 加氢合成甲醇的复杂反应体系CO₂ +3H₂=CH₃ OH +H₂ O与CO₂ +H₂=CO +H₂ O开展实验研究 .考察了硅橡胶 /陶瓷复合膜在合成含氧化合物反应过程中的作用 ,并讨论了CO₂ 与H₂ 合成甲醇反应的膜反应过程参数对反应行为的影响 ,对部分理论分析结果进行验证 .在实验条件下 ,CO₂ 合成甲醇复杂反应体系中的主反应转化率较传统的固定床反应器提高了 2 2 %     

硅橡胶/陶瓷复合膜反应器中CO2合成甲醇(Ⅰ)反应动力学

在反应温度为 2 0 0～ 2 5 0℃ ,反应压力为 0 .6～ 1.6MPa ,原料气组成为H₂ 6 0 %～ 75 %、CO₂ 15 %～30 %、CH₄ 5 %～ 10 %的条件下 ,在固定床微分反应器中研究了C30 1催化剂上CO₂ 与H₂ 合成甲醇的反应本征动力学模型 ,提出了反应的控制步骤、模型鉴别及模型参数估值 ,当表面反应为速率控制步骤时所建立的动力学模型是可行的 ,模型计算值与实测值相当吻合     

生物质超临界气化制氢产物高压吸收法分离的气液相平衡分析

通过高压吸收法可以将生物质超临界水气化制氢的气体产物中的CO₂与H₂分离.基于修正的UNIFAC模型、SRK状态方程以及MHV2混合规则，建立了生物质超临界气化制氢产物高压吸收法分离的气液相平衡的计算模型，讨论了CO₂与H₂分离过程中压力和温度等参数对分离效果的影响.计算结果表明：随着分离器中压力的升高，气相产物中H2的摩尔分数增加，CO₂摩尔分数迅速下降，气相中H₂的收率不断降低；随着温度升高，气相产物中H₂的摩尔分数减小，CO₂摩尔分数上升，气相中H₂的收率增加；然而，高压吸收的方法不能将气体产物中的CO、CH₄、C₂H₄、C₂H₆与H₂分离.     

基于NiO载氧体的煤化学链燃烧实验

采用流化床反应器并以水蒸气作为气化-流化介质,研究了以NiO为载氧体在800～960℃内的煤化学链燃烧反应特性。实验结果表明,载氧体与煤气化产物在反应器温度高于900℃体现了高的反应活性。随着流化床反应器温度的提高,气体产物中CO₂的体积浓度(干基)呈单调递增;CO、H₂、CH₄的体积浓度(干基)呈单调递减;煤中碳转化为CO₂的比率逐渐递增,碳的残余率逐渐递减。反应器出口气体CO₂、CO、H₂、CH₄的生成率随反应时间呈单峰特性,H₂生成率的峰值远小于CO的峰值;且随反应器温度升高,CO₂生成率升高,CO、H₂、CH₄的生成率降低。反应温度高于900℃时,流化床反应器NiO载氧体煤化学链燃烧在9 min之内就基本完成,CO₂含量高于92%。     

苯酚低温催化水蒸气重整制氢

以Raney Ni为催化剂,在温和条件下(523～723 K)实现了苯酚催化水蒸气重整制氢反应。研究表明,反应温度、液体空速和原料浓度等反应条件是影响苯酚转化率和H₂选择性的重要因素,较高的反应温度和较低的液体空速有利于提高苯酚转化率,但不利于提高H₂选择性。对比苯酚水相重整制氢过程发现,尽管水蒸气重整反应温度相对较高,且需要汽化原料使反应在气相中进行,但该过程具有比水相重整更高的H₂选择性(93%～100%)。此外,Raney Ni催化剂上苯酚水蒸气重整反应与现有的文献结果比较还具有反应条件温和、催化剂稳定性好(60h)以及CO含量低(CO/CO₂摩尔比为0.01～0.2)等优点。将该技术应用于工业含酚有机废水的资源化处理制备的H₂可以直接作为氢源使用。     

NiO-MgO固溶体蜂窝催化剂部分氧化重整净化生物质气特性

采用分步浸渍法制备了NiO-MgO固溶体蜂窝催化剂,以60 h连续重整实验,考察了不同临氧条件下MCM催化剂催化生物质气重整净化的性能。利用TG-DSC对催化剂的表面积炭进行了分析,采用GC、GC-MS等手段对生物质气组成及焦油转化产物进行了分析。结果表明：加入O₂后进行临氧重整,可改善出口合成气的品质,H₂/CO摩尔比较干重整时提高了10%左右。但当O₂/fuel摩尔比超过0.127时,H₂/CO摩尔比有所下降。O₂的加入可明显提高催化剂的催化活性和稳定性,随着O₂ 含量的增加出口合成气中的CH₄含量降低,临氧重整条件下焦油的转化率较无氧条件时提高了5%,转化率达到99%以上。热重分析表明,O₂ 含量的增加会减少催化剂表面积炭量。实验中添加从气化现场提取的生物质焦油,经检测焦油大部分转化为H₂、CO及痕量轻质组分,且对干重整中难于转化的含氧有机化合物等转化更为彻底。     

基于Fluent软件的生物质气化模拟研究

基于Fluent软件,建立流化床反应器模型,对生物质-水蒸气气化过程进行模拟,研究温度对生物质气化过程的影响,同时分析碳转化率、气体成分以及气体总产率的变化规律。结果表明:模拟结果与实验数据吻合良好,碳转化率及气体总产率随温度的升高而升高,床层高度对CO、 H₂生成具有较大影响。模拟计算条件下,氢气体积分数高达55%,这说明水蒸气作为气化介质有利于气化过程中产生更多的H₂。Fluent软件能够很好的对生物质气化过程进行模拟,可以作为生物质气化研究的一个重要工具。     

工艺条件对Ni/Al2O3和Ni/CeO2-Al2O3催化剂在甲烷自热重整制氢反应中催化性能的影响

采用共沉淀法制备γ-Al₂O₃载体和不同Ce添加量的CeO₂-Al₂O₃载体,然后用浸渍法制备Ni负载质量分数10%的Ni/γ-Al₂O₃和Ni/CeO₂-Al₂O₃催化剂。在固定床微反装置中考察了反应温度、原料气配比和CH₄空速等工艺条件对Ni/γ-Al₂O₃和Ni/Ce₃₀Al₇₀O_δ催化剂在甲烷自热重整制氢反应中催化性能的影响。结果表明,添加Ce的催化剂催化性能有较大提高,在Ni/Ce₃₀Al₇₀O_δ催化剂上,反应温度750 ℃时, CH₄转化率94.3％,与Ni/Al₂O₃催化剂相比,提高20％。Ni/γ-Al₂O₃和Ni/CeO₂-Al₂O₃催化剂的CH₄转化率均随反应温度的升高而增大。原料气中n(O₂)∶n(CH₄)和n(H₂O)∶n(CH₄)的增加均能提高各催化剂的CH₄转化率。但n(O₂)∶n(CH₄)和n(H₂O)∶n(CH₄)的变化对各催化剂的催化性能的影响不同。随着n(O₂)∶n(CH₄)的增大,产物中n（H₂）∶n（CO）降低,n（CO₂）∶n(CO＋CO₂)升高;而n(H₂O)∶n(CH₄)增大时,产物中n（H₂）∶n（CO）和n（CO₂）∶n(CO＋CO₂)均升高。随着CH₄空速的增加,Ni/Al₂O₃催化剂上CH₄转化率、n（H₂）∶n（CO）和n（CO₂）∶n(CO＋CO₂)均较大程度下降;而在Ni/Ce₃₀Al₇₀O_δ催化剂上,随着CH₄空速的增加,CH₄转化率、n（H₂）∶n（CO）和n(CO₂）∶n(CO＋CO₂)变化不大。     

Cu1Zr1Ce9Oδ催化剂选择性氧化CO性能的研究

用共沉淀法制备了Cu₁Zr₁Ce₉O_δ催化剂,考察了反应温度和反应气体中各组分对Cu₁Zr₁Ce₉O_δ催化剂上选择性氧化CO反应的影响。结果表明,降温的过程中Cu₁Zr₁Ce₉O_δ催化剂的活性滞后。H₂的存在有利于CO的脱附,促进了低温下选择性氧化CO的反应;而温度较高时,H₂氧化副反应的发生降低了CO的转化率,反应气中H₂O和CO₂降低了催化剂的活性和选择性,最佳反应温度为（160~200） ℃,O₂的进入量取3为宜。     

三相搅拌反应釜中合成气直接合成二甲醚

引　言二甲醚可替代氟里昂作制冷剂和喷射剂 ,减少对大气的污染 ;可作民用燃料 ,提高热值 ;可代替柴油 ,作柴油发动机燃料 ;可作汽车燃料 ,提高发动机的动力性能 ;可作为优良的溶剂和泡沫塑料的发泡剂 ;可生产Ｎ ,Ｎ -二甲基苯胺、乙酸甲酯等化工产品[1～ 4 ] .最早的二甲醚产品是从高压合成甲醇的副产品中分离回收得到 ,随着新型低压甲醇合成催化剂的开发 ,甲醇的选择性提高 ,这种方法已被淘汰 .目前二甲醚的工业生产主要是二步法 ,即合成气在铜基催化剂上生成甲醇 ,甲醇在分子筛催化剂上脱水生成二甲醚[5] .由于路线长 ,设备投资高 ,开发…     

A novel low-temperature methanol synthesis method from CO/H2/CO2 based on the synergistic effect between solid catalyst and homogeneous catalyst

The activity of a binary catalyst in alcoholic solvents for methanol synthesis from CO/H₂/CO₂ at low temperature was investigated in a concurrent synthesis course. Experiment results showed that the combination of homogeneous potassium formate catalyst and solid copper–magnesia catalyst enhanced the conversion of CO₂-containing syngas to methanol at temperature of 423–443 K and pressure of 3–5 MPa. Under a contact time of 100 g h/mol, the maximum conversion of total carbon approached the reaction equilibrium and the selectivity of methanol was 99%. A reaction pathway involving esterification and hydrogenolysis of esters was postulated based on the integrative and separate activity tests, along with the structural characterization of the catalysts. Both potassium formate for the esterification as well as Cu/MgO for the hydrogenolysis were found to be crucial to this homogeneous and heterogeneous synergistically catalytic system. CO and H₂ were involved in the recycling of potassium formate.     

沉淀型Fe-Mn工业催化剂的F-T反应性能

在积分固定床反应器中系统考察了用于Fischer-Tropsch(F-T)合成的沉淀型Fe-Mn工业催化剂的性能.首先对催化剂进行了2000h的稳定性测试,然后在不同反应温度、原料气H₂/CO比、空速和总压下考察其反应性能.结果表明,在2000h的运行过程中,该催化剂活性和选择性较平稳,失活速率较小,且在较高的反应温度下失活速率更小,显示出该催化剂具有良好的长期稳定性;经2000h的运行后,该催化剂仍表现出较高的反应活性和稳定性,同时,还保持着较高的低碳烯烃和C₅₊选择性.此外,当反应条件在一定范围内发生变化时,低碳烯烃和C₅₊选择性变化不大,说明该催化剂具有良好的可操作性.     

Pd/ZnO催化剂上甲醇水蒸气重整制氢

研究了并流共沉淀法制备的Pd/ZnO催化剂上的甲醇水蒸气重整制氢反应.考察了钯含量、还原温度、反应温度、重时空速（WHSV）和水-甲醇摩尔比（水醇比）对反应的影响.研究结果表明,当钯质量分数为15.9%,反应温度为523～573 K,还原温度为523～573 K,水醇比为1.0～1.2,WHSV=17.2 h^-1时,反应具有较好的CH3OH转化率、CO₂选择性、H₂产率及较低的出口CO摩尔分数.与铜基催化剂相比,Pd/ZnO催化剂表现出较好的稳定性.     

Equilibrium calculations for direct synthesis of dimethyl ether from syngas

Thermodynamic analysis of single‐step synthesis of dimethyl ether (DME) from syngas over a bi‐functional catalyst (BFC) in a slurry bed reactor has been investigated as a function of temperature (200–240°C), pressure (20–50 bar), and composition feed ratio (H₂/CO: 1–2). The BFC was prepared by physical mixing of CuO/ZnO/Al₂O₃ as a methanol synthesis catalyst and H‐ZSM‐5 as a methanol dehydration catalyst. The three reactions including methanol synthesis from CO and H₂, methanol dehydration to DME and water–gas shift reaction were chosen as the independent reactions. The equilibrium thermodynamic analysis includes a theoretical model predicting the behaviour and a comparison to experimental results. Theoretical model calculations of thermodynamic equilibrium constants of the reactions and equilibrium composition of all components at different reaction temperature, pressure, and H₂/CO ratio in feed are in good accordance with experimental values.     

Low-pressure DME synthesis with Cu-based hybrid catalysts using temperature-gradient reactor

Dimethyl ether (DME), the target product of this study, has many advantages as diesel fuel. The aim of this study is to develop a catalytic process in which 90% CO conversion to DME and CO₂ from syngas (3CO+3H₂→DME+CO₂) is attained at 1–3 MPa. In such a process, both recycling loop and compression of syngas can be omitted resulting in an economic process based on unused, dispersed and small-scale carbon resources. To overcome the equilibrium conversion limit we designed temperature-gradient reactor (TGR). In TGR, the temperature of the catalyst bed decreases along with the down flow of reaction gas. The performance of the catalyst in TGR was much higher than that in a conventional isothermal fixed bed reactor. For example, 90% CO conversion and high STY (1.1 kg MeOH eqiv./kg cat./h) was attained at the same time in TGR at 550–510 K, 3 MPa.     

还原空速对Fe/Cu/K/SiO2催化剂浆态床F-T合成性能的影响

在浆态床反应器中详细考察了合成气还原空速对微球状工业铁基催化剂还原和反应后的物相以及F-T合成反应性能的影响. 研究结果表明：空速能够影响铁基催化剂还原反应进程，催化剂在较高的空速下易被还原，还原后催化剂的比表面积降低，平均孔径增大. 在较低空速下还原时，还原形成的高的CO₂分压对铁物相有一定的氧化作用，使得还原态催化剂中的Fe³⁺(spm)含量增大. 还原空速对F-T合成烃产物分布影响不明显，但对催化剂的反应活性和运行稳定性影响较大，较低和较高空速还原后的催化剂失活速率均较高，适宜的还原空速为1.0～2.0 L•（g cat）^-1•h^-1.     

Synthesizing methanol from nitrogen-ballasted syngas

The possibility of the effective catalytic synthesis of methanol from nitrogen-ballasted syngas was studied. Syngas was obtained during the operation of power machines such as diesel engines or gas turbines. The dependences of CO and CO₂ conversion per cycle, the quality of methanol, et cetera on the composition of syngas are characterized. The kinetic dependences of methanol synthesis on G-79-7GL catalyst (Zud Chemie) are described. For nitrogen-ballasted syngas, the dependences of the CO and CO₂ conversion and the output and quality of methanol on the reaction conditions (pressure, temperature, and gas mixture feed rate) are the same as for nitrogen-free syngas, though the CO conversion declined considerably when the concentration of ballast nitrogen was increased. These studies served as the basis for the creation of energy-independent units for processing hydrocarbon gases into methanol and motor fuels.     

Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.