几种随车甲醇裂解制氢铜催化剂的评价
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摘要
考察了几种铜催化剂的甲醇裂解催化性能,并模拟汽车行驶温度的波动,测试其空气再生性能。结果表明,Cu/活性炭(AC)、工业铜锌铝和Cu/SiO_2催化剂在420℃高温下活性较低,比活性(甲醇转化率/铜含量)分别为2.08、1.4和0.48;Cu/Al_2O_3和Cu/ZSM-5催化剂对产物的H_2+CO选择性较低,其摩尔分数不超过50%;铜水泥催化剂在高温下能维持高比活性,在420℃下比活性为2.9。另外,铜水泥催化剂对H_2+CO的选择性在90%,且该催化剂的稳定性和再生性能好,能基本满足随车制氢催化剂的要求。TPR表征发现铜分布状态差别较大,而水泥催化剂存在高温还原峰,推测高温还原峰有利于提高水泥催化剂的热稳定性。
The catalytic performance of several copper catalysts for methanol cracking was investigated,and its air regeneration performance was tested with temperature fluctuation in the car.The results show that Cu/AC(activated carbon),industrial copper-zinc-aluminum and Cu/SiO_2 catalyst have low activity at 420℃,and the specific activity(methanol conversion/copper content)is 2.08,1.4 and 0.48 respectively.Cu/Al_2O_3 and Cu/ZSM-5 catalyst has low selectivity to H_2+CO and the molar fraction is less than 50%.The copper cement catalyst can maintain high specific activity at high temperature and 2.9 at 420℃.In addition,the selectivity of the copper cement catalyst to H_2+CO is 90%,and the stability and regeneration performance of the catalyst were good,which could meet the requirement of onboard hydrogen generation catalyst.TPR characterization shows that the copper distribution is quite different,while the cement catalyst has high temperature reduction peak,and it is inferred that the high temperature reduction peak is beneficial to improve the thermal stability of the cement catalyst.
The catalytic performance of several copper catalysts for methanol cracking was investigated,and its air regeneration performance was tested with temperature fluctuation in the car.The results show that Cu/AC(activated carbon),industrial copper-zinc-aluminum and Cu/SiO_2 catalyst have low activity at 420℃,and the specific activity(methanol conversion/copper content)is 2.08,1.4 and 0.48 respectively.Cu/Al_2O_3 and Cu/ZSM-5 catalyst has low selectivity to H_2+CO and the molar fraction is less than 50%.The copper cement catalyst can maintain high specific activity at high temperature and 2.9 at 420℃.In addition,the selectivity of the copper cement catalyst to H_2+CO is 90%,and the stability and regeneration performance of the catalyst were good,which could meet the requirement of onboard hydrogen generation catalyst.TPR characterization shows that the copper distribution is quite different,while the cement catalyst has high temperature reduction peak,and it is inferred that the high temperature reduction peak is beneficial to improve the thermal stability of the cement catalyst.
引文
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[2]杨成,郑道昌,王炳辉.一种甲醇低温裂解反应器设计及反应特性研究[J].现代化工,2009,29(4):72-74.
[3]Frolich P K,Fenske M R,Quiggle,D.Catalysts for the formation of alcohols from carbon monoxide and hydrogenⅠ-decomposition of methanol by catalysts composed of copper and zinc[J].Industrial and Engineering Chemistry,1928,20(1):694-698.
[4]Seelig H S,Marschner R F.Production of synthesis gas by catalytic decomposition of Methanol[J].Industrial and Engineering Chemistry,1948,40(4):583-586.
[5]Zhao M,Wang H R,Cai L,et al.Effect of different supports on performance of palladium Methanol decomposition catalyst[J].Rare Metal Materials and Engineering,2010,39(3):519-522.
[6]邱诗铭,庆绍军,侯晓宁,等.随车制氢甲醇裂解铜水泥催化剂的研究[J].石油化工,2011,40(8):813-819.
[7]Tsoncheva T,Genova I,Dimitrov M,et al.Nanostructured copper-zirconia composites as catalysts for methanol decomposition[J].Applied Catalysis B Environmental,2015,165:599-610.
[8]Lars Pettersson,Krister Sjostrom.Decomposed methanol as a fuel-a review[J].Combust Sci Tech,1991,80:265-303.
[9]Yakerson V I,Golosman E Z.Scientific bases for the preparation of new cement containing catalysts[J].Studies in Surface Science&Catalysis,1995,91(6):879-884.
[10]Kim S D,Baek S C,Lee Y.Effect ofγ-Alumina content on catalytic performance of modified ZSM-5for dehydration of crude Methanol to dimethyl ether[J].Applied Catalysis A:General,2006(309):139-143.