甲烷部分氧化制含氧化合物的研究
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摘要
甲烷为天然气的主要成分,目前天然气作为化工原料的应用主要通过间接的方式实现,即将其制成合成气后再转化为合成氨和甲醇等。本文探索的是一种直接利用天然气的方法,主要目的是研制出一种高效催化剂体系,将甲烷在相对温和的条件下直接氧化成便于安全运输的含氧化合物。该体系以活性炭负载杂多酸为催化剂,空气中的氧为氧化剂,醋酸为反应溶剂,构建一个气液固三相催化剂体系,该反应体系能有效解决气固反应体系中含氧化合物的选择性低和气液反应体系中液相介质对设备的腐蚀性强等问题。实验研究了活性炭负载不同种类和不同含量的杂多酸或其它物质制得的催化剂的催化性能,建立一个相对理想的催化体系——活性炭同时负载磷钼酸和钒酸钠,且在液相中添加一定量的醋酸钴。在该催化体系的作用下,甲烷的转化率较高。随后的实验对该催化体系进行了优化,优化后的催化体系能较为明显的提高反应中甲烷的转化率,最优催化体系为：活性炭同时负载磷钼酸和钒酸钠,其中磷钼酸负载量为30%,磷钼酸与钒酸钠的摩尔比为1：3,同时液相中添加一定量的醋酸钴,其浓度为1.68×10"2mol/L。最后实验还分别研究了温度、压力、溶液配比和气体流量等工艺条件的变化对甲烷转化率的影响,结果表明：溶液的配比对甲烷的转化率有显著的影响,温度、压力以及气体流量的变化对实验结果也有一定影响。当反应工艺条件得到优化后,甲烷的转化率能达到6.67%,说明该催化体系具有深入研究的价值。
Natural gas, which main component is methane, is one of the most important raw materials. It is used to synthesize methanol or ammonia through an indirect way of which the syngas is produced firstly. This paper explores a direct way of using natural gas and develops a high-effective catalyst system that can directly change methane into oxygenated hydrocarbons under mild reaction conditions. The oxygenated hydrocarbons are liquid under normal pressure and temperature and their chemical properties are stable, so they can be transported conveniently. The experiment has utilized three-phase system and semi-continuous operation into the reaction for the first time. The gas phase is continuous and the liquid and solid phases are both intermittent. The active carbon is used to load heteropoly acids as the carrier and air is used as the oxidant. This reaction system solves the problem existed in gas-solid or gas-liquid reaction system such as the high cost of the equipments in those systems and the low selection of oxygenated hydrocarbons. The catalytic properties of active carbon loading different heteropoly acid and other substances have been studied in this paper and a more appropriate catalytic systems is established based on the experiment results.
The solid phase is the active carbon loading H3O40PMo12 and Na3VO4 and liquid phase contains some amount of the Co(Ac)2 in the new system. In those catalytic systems, the conversion of methane reaches higher level. Meanwhile the catalytic systems have been optimized, and a higher conversion is achieved. In the catalytic systems, the charge number of H3O40PMo12 reach 30%, and the mole ratio of H304oPMo12 and Na3VO4 is 1:3, the suitable molarity of Co(Ac)2 is 1.68xlO-2mol/L. Finally, the experiment studies the impact of the changes of pressure, temperature and other impact factors to the methane oxidation reaction. The results show that the ratio of the solution has significant influence on the conversion of methane.The pressure, the temperature and the gas flow also have some effect on the conversion. When the reaction process conditions are optimized, methane conversion can achieve 6.67%, so the catalytic systems have further research value.
Natural gas, which main component is methane, is one of the most important raw materials. It is used to synthesize methanol or ammonia through an indirect way of which the syngas is produced firstly. This paper explores a direct way of using natural gas and develops a high-effective catalyst system that can directly change methane into oxygenated hydrocarbons under mild reaction conditions. The oxygenated hydrocarbons are liquid under normal pressure and temperature and their chemical properties are stable, so they can be transported conveniently. The experiment has utilized three-phase system and semi-continuous operation into the reaction for the first time. The gas phase is continuous and the liquid and solid phases are both intermittent. The active carbon is used to load heteropoly acids as the carrier and air is used as the oxidant. This reaction system solves the problem existed in gas-solid or gas-liquid reaction system such as the high cost of the equipments in those systems and the low selection of oxygenated hydrocarbons. The catalytic properties of active carbon loading different heteropoly acid and other substances have been studied in this paper and a more appropriate catalytic systems is established based on the experiment results.
The solid phase is the active carbon loading H3O40PMo12 and Na3VO4 and liquid phase contains some amount of the Co(Ac)2 in the new system. In those catalytic systems, the conversion of methane reaches higher level. Meanwhile the catalytic systems have been optimized, and a higher conversion is achieved. In the catalytic systems, the charge number of H3O40PMo12 reach 30%, and the mole ratio of H304oPMo12 and Na3VO4 is 1:3, the suitable molarity of Co(Ac)2 is 1.68xlO-2mol/L. Finally, the experiment studies the impact of the changes of pressure, temperature and other impact factors to the methane oxidation reaction. The results show that the ratio of the solution has significant influence on the conversion of methane.The pressure, the temperature and the gas flow also have some effect on the conversion. When the reaction process conditions are optimized, methane conversion can achieve 6.67%, so the catalytic systems have further research value.
引文
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[10]Xiaoxing Wang, Ye Wang, Qinghu Tang, et al. MCM-41-supported iron phosphate catalyst for partial oxidationof methane to oxygenates with oxygen and nitrous oxide [J]. Journal of Catalysis.,2003,217:457-467.
[11]Lin Chena, Xing Wang Zhang, Liang Huang, et al. Partial oxidation of methane with air for methanol production in a post-plasma catalytic system [J]. Chemical Engineering and Processing.,2009,48:1333-1340.
[12]Qijian Zhang, Dehua He, Zhangsheng Han, et al. Controlled partial oxidation of methane to methanol/formaldehyde over Mo-V-Cr-Bi-Si oxide catalysts [J]. Fuel., 2002,81:1599-1603.
[13]张昕,贺德华,张启俭,等.Mo/La-Co-O催化剂上甲烷选择氧化制甲醇反应[J].催化 学报,2003,24(4)：305-311
[14]杨晓强,董国利,贺德华.负载WOx的Co-Fe-Mo-O催化剂催化甲烷氧化反应[J].石油化工,2005,34(12)：1134-1139.
[15]杨晓强,董国利,贺德华.填充惰性材料对甲烷部分氧化反应的影响[J].天然气化工,2006,31：1-6.
[16]Qijian Zhang, Dehua He, QimingZhu. Direct partial oxidation of methane to methanol: Reaction zones and role of catalyst location [J]. Journal of Natural Gas Chemistry., 2008,17:24-28.
[17]J.A. Barbero, M.A. Banares, M.A. Pena, et al. Partial oxidation of methane into C1-oxygenates:role of homogeneous reactions and catalyst surface area [J]. Catalysis Today.,2001,71:11-19.
[18]Antonius Indarto, Jae-Wook Choi, Hwaung Lee, et al. Partial Oxidation of Methane with Sol-Gel Fe/Hf/YSZ Catalyst in Dielectric Barrier Discharge:Catalyst Activation by Plasma [J]. JOURNAL OF RARE EARTHS.,2006,24:513-518.
[19]Antonius Indarto, Dae Ryook Yang, Jelliarko Palgunadi, et al. Partial oxidation of methane with Cu-Zn-Al catalyst in a dielectric barrier discharge [J]. Chemical Engineering and Processing.,2008,47:780-786.
[20]Ouarda Benlounes, Sadia Mansouri, Ch'erifa Rabia, et al. Direct oxidation of methane to oxygenates over heteropolyanions [J]. Journal of Natural Gas Chemistry., 2008,17:309-312.
[21]Yonghong Teng, Hiroaki Sakurai, Kenji Tabata, et al. Methanol formation from methane partial oxidation in CH4-O2-NO gaseous phase at atmospheric pressure [J]. Applied Catalysis A:General.,2000,190:283-289.
[22]Tetsuya Takemoto, Kenji Tabata, Yonghong Teng, et al. The effects of reaction pressures on the production of methanol through the selective oxidation of methane in CH4-O2-NOx (x=1 or 2) [J]. Applied Catalysis A:General.,2001,205:51-59.
[23]David W. Larkin, Lance L. Lobban, Richard G. Mallinson. The direct partial oxidation of methane to organic oxygenates using a dielectric barrier discharge reactor as a catalytic reactor analog [J]. Catalysis Today.,2001,71:199-210.
[24]Qijian Zhang, Dehua He, Jinlu Li, Boqing Xu, et al. Comparatively high yield methanol production from gas phase partial oxidation of methane [J]. Applied Catalysis A: General.,2002,224:201-207.
[25]张听,贺德华,张启俭,等.甲烷气相均相选择氧化合成甲醇[J].石油化工,2003,32(3)：195-199.
[26]Takafumi Sato, Masaru Watanabe, Richard L. Smith Jr, et al. Analysis of the density effect on partial oxidation of methane in supercritical water [J]. J. of Supercritical Fluids.,2004,28:69-77.
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