甲烷催化部分氧化制合成气反应机理

甲烷催化部分氧化制合成气在负载型金属催化上的反应机理目前仍然存在争议。一种观点认为,甲烷先与氧气燃烧生成水和二氧化碳,在燃烧过程中氧气完全消耗,剩余的甲 烷再与水和二氧化碳进行重整反应生成氢气和一氧化碳,即燃烧－重整机理;另一种观点认为,甲烷直接在催化剂上分解生成氢气和表面碳物种、表面碳再与表面氧反应生成一氧化碳,即直接氧化机理。对复合氧化物催化剂上的反应机理,一致认为甲烷与氧气在催化剂表面上先形成氧化物,氧化物再分解生成氢气和一氧化碳。对有关甲烷催化部分氧化制合成气反应机理的不同观点进行了介绍,并结合作者在Ni/Al2O3催化剂方面的研究结果,对负载型镍催化剂上的反应机理进行了讨论。     

甲烷部分氧化与甲烷二氧化碳重整耦合制合成气Co系催化剂研究

研究了Co／γ-Al2O3，Co／α-Al2O3和Co／SiO2催化剂上的甲烷部分氧化与甲烷二氧化碳重整制合成气反应，只有Co／α-Al2O3是有效的．证明Co和载体的相互作用过强或过弱都不利与此耦合反应．Co和α-Al2O3的作用正好合适．此外，Co的担载量和催化剂稳定性关系很大，Co量过低则在反应过程中会因Co^D→CoAl2O4而失活，Co担载量过高则会导致严重结碳．     

甲烷催化部分氧化制合成气反应机理

甲烷催化部分氧化制合成气在负载型金属催化剂上的反应机理目前仍然存在争议。一种观点认为 ,甲烷先与氧气燃烧生成水和二氧化碳 ,在燃烧过程中氧气完全消耗 ,剩余的甲烷再与水和二氧化碳进行重整反应生成氢气和一氧化碳 ,即燃烧重整机理 ;另一种观点认为 ,甲烷直接在催化剂上分解生成氢气和表面碳物种 ,表面碳再与表面氧反应生成一氧化碳 ,即直接氧化机理。对复合氧化物催化剂上的反应机理 ,一致认为甲烷与氧气在催化剂表面上先形成氧化物 ,氧化物再分解生成氢气和一氧化碳。对有关甲烷催化部分氧化制合成气反应机理的不同观点进行了介绍 ,并结合作者在Ni/Al2 O3 催化剂方面的研究结果 ,对负载型镍催化剂上的反应机理进行了讨论     

甲烷部分氧化制合成气反应中热点位置的研究

将热电偶插入Ｌａ２Ｏ３－Ｎｉ／ＭｇＡｌ２Ｏ４催化剂反应床层,通过移动热电偶详细考察了反应炉温、空速、原料气组成和加入水蒸气对甲烷部分氧化制合成氯反应床层温升的影响。结果表明,反应热点位于催化剂床层入口片,而且热点位置不受上述反应因素的影响。但是,其温升值随空速的增大而升高,随反应炉温的升高而降低。反应中引入水蒸气可以降低反应热点的温度,但同时使产物中ＣＯ２含量增大。根据反应热计算了燃烧－重整机理和     

微波场中甲烷部分氧化制合成气：Ni／ZrO2催化剂在微波？…

考察了不同Ｎｉ含量的Ｎｉ／ＺｒＯ２催化剂在微波场中的升温行为及１０％Ｎｉ／ＺｒＯ２催化氧化甲烷制合成气的反应活性，并与常规加热条件下的反应活性进行了对比。结果表明，四种Ｎｉ含量的Ｎｉ／ＺｒＯ２催化剂在微波场中均能够升温；在达到桢的Ｃ论率时，微波活化方式下催化剂床层温度比常规加热低得多，且产物中Ｈ２和ＣＯ明显主于后者。     

微波场中甲烷部分氧化制合成气的反应机理

用ＸＰＳ技术对催化剂进行了测试，结果表明，催化剂表面上均存在着两类不同的表面氧种：晶格氧和吸附氧，且这两类表面氧种的相对含量与催化剂的活化方式有关。微波活化方式下的表面晶格氧含量普遍比常规活化方式下的高，这可归之于微波场加速了可动晶格氧的迁移所致。微波辐照下的ＰＯＭ反应可能是按甲烷解离机理来进行的，甲烷的解离是反应的决速步骤。     

CaO-La_2O_3-NiO/γ-Al_2O_3催化剂上甲烷部分氧化制合成气研究

采用微型固定床流动反应装置研究了在La2 O3 NiO/γ Al2 O3 催化剂上添加CaO对甲烷部分氧化制合成气的影响 .结果表明 ,添加CaO后 ,催化剂活性明显提高 ,引发温度降低 ,CH4的转化率和CO的选择性升高 ,1 ?O 2 %La 1 2 %Ni/γ Al2 O3 是较适宜的催化剂在中低温区 ,随反应温度升高 ,CH4的转化率和CO的选择性升高 ,催化反应的适宜温度为 6 0 0℃～70 0℃ .     

甲烷部分氧化制合成气反应中热点位置的研究

将热电偶插入La2 O3 Ni/MgAl2 O4 催化剂反应床层 ,通过移动热电偶详细考察了反应炉温、空速、原料气组成和加入水蒸气对甲烷部分氧化制合成气反应床层温升的影响。结果表明 ,反应热点位于催化剂床层入口处 ,而且热点位置不受上述反应因素的影响。但是 ,其温升值随空速的增大而升高 ,随反应炉温的升高而降低。反应中引入水蒸气可以降低反应热点的温度 ,但同时使产物中CO2 含量增大。根据反应热计算了燃烧重整机理和直接转化机理的绝热温升 ,与实验结果的对比表明 ,反应床层的温升主要来自于部分氧化反应的放热 ,即甲烷部分氧化制合成气可能是按直接转化机理进行的。极高空速时低甲烷转化率下合成气的选择性并未发生明显的变化 ,这也进一步证明了上述结论     

载体盐助分散Ni/Al2O3催化剂上甲烷部分氧化制合成气

用ＴＰＲ,ＴＰＤ,ＴＰＭＣ（程序升温甲烷解离积炭）和活性评价等方法研究载体盐助分散浸渍法与普通浸渍法制备的Ｎｉ基催化剂对ＣＨ４部分氧化制合成气性能的影响,结果表明载体盐助分散浸渍法制备的催化剂其Ｎｉ－Ｏ－Ａｌ间作用较强,分散度增加２６％,抗积炭能力增加４．４倍。     

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.     

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.     

Partial oxidation of methane to syngas in a mixed-conducting oxygen permeable membrane reactor

Mixed-conducting oxygen permeable membranes represent a class of novel ceramic membranes, which exhibit mixed oxygen ionic and electronic conductivities. At high temperatures, oxygen can permeate through the membrane from the high to low oxygen pressure side under an oxygen concentration gradient. Theoretically, the permselectivity of oxygen is 100%. Recently, a novel mixed-conducting membrane—Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ has been developed, which shows extremely high oxygen permeability and promising stability. Furthermore, the reactor made with such membranes was successfully applied to the partial oxidation of methane to syngas reaction using air as the oxygen source, which realized the coupling of the separation of oxygen from air and the partial oxidation of membrane reaction in one process. At 850°C, methane conversion > 88%, CO selectivity > 97% and oxygen permeation rate of about 7.8 mL/(cm² · min) were obtained.     

负载型金属催化剂的研究进展

综述了负载型过渡金属催化剂的一些最新研究进展,如负载型Ni、Pd配合物均相催化剂,负载型Fe、Co配合物均相催化剂,负载型钼基催化剂等,并指名了其目前存在的问题和研究方向。     

透氧膜反应器中合成气制备过程研究

以内表面积为4.1 cm2的La2NiO4致密管状透氧陶瓷膜构建膜反应器,以CH4与CO2混合进气,在880°C的条件下,通过CH4的催化部分氧化反应及CO2重整反应制备了合成气;当CH4的进气流量控制在14.1 cm3/min,CO2流量为5.6 cm3/min时合成气生成速率为36 cm3/min,CH4与CO2的转化率分别为87%和83%;与CH4单独进料相比,合成气的产率增加了约60%,H2与CO体积比从1.7下降到1.3。实验结果,在透氧膜反应器中可实现CH4、CO2共进料制备合成气。     

Partial oxidation of methane to syngas in tubular oxygen-permeable reactor

A dense Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ membrane tube was prepared by the extruding method. Furthermore, a membrane reactor with this tubular membrane was successfully applied to partial oxidation of methane (POM) reaction, in which the separation of oxygen from air and the partial oxidation of methane are integrated in one process. At 875℃, 94% of methane conversion, 98% of CO selectivity, 95% of H₂ selectivity, and as high as 8.8 mL/(min · cm²) of oxygen flux were obtained. In POM reaction condition, the membrane tube shows a very good stability.     

流化床上甲烷催化转化制合成气Ni/SiO2催化剂性能研究

考察了流化床上Ni／SiO2催化剂对甲烷部分氧化和甲烷二氧化碳重整耦合反应的催化性能．研究了Ni负载量，反应温度、预还原温度对催化性能的影响．结果表明，镍基催化剂具有很高的初活性，但是在线反应6h后催化剂很快失活．TG、XRD和TEM分析结果显示高温下镍晶粒的聚集长大是催化剂活性显著下降的主要原因．     

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.