低碳烷烃循环流化床脱氢工艺条件优化
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摘要
针对PBD型脱氢催化剂,采用循环流化床中试装置对低碳烷烃(丙烷、异丁烷、正丁烷)单独脱氢以及不同配比混合低碳烷烃进行了较为系统的工艺条件优化研究。结果表明,反应温度和空速对低碳烷烃脱氢过程的影响至关重要,不同脱氢原料具有不同的适宜操作工况,其中丙烷脱氢在600℃和1 700 h~(-1)条件下,转化率为39%,丙烯收率达33%;异丁烷脱氢在580℃和1 700 h~(-1)条件下,转化率为48%,异丁烯收率为45%;正丁烷脱氢在580℃和1 700 h~(-1)条件下,转化率为40%,丁烯收率高达32%。PBD型催化剂对于不同配比混合低碳烷烃具有较高的催化活性。最终获得的不同脱氢原料适宜的操作工况下,可以为循环流化床低碳烷烃脱氢装置的工程设计与放大和工业装置的生产调优提供基础数据与理论支持。
Optimization studies on operation conditions for the dehydrogenation process of low-carbon alkanes( propane,iso-butane,n-butane and their mixtures) are carried out by employing a pilot-scale circulating fluidized bed( CFB) unit.PBD,a catalyst developed by Yantai University,is used in this study.Experimental findings indicate that the reaction temperature( T) and the gas hourly space velocity( GHSV) have great influences on the dehydrogenation process of low-carbon alkanes.Proper operation conditions are different according to different feedstocks.Under conditions of T =600℃ and GHSV = 1 700 h~(-1),the conversion rate of propane can reach 39% and the yield of propylene can achieve 33%.Under the conditions of T = 580℃ and GHSV = 1 700 h~(-1),the conversion rate of iso-butane can reach 48% and the yield of iso-butylene can achieve 45%. Under the conditions of T = 580℃ and GHSV = 1 700 h~(-1),the conversion rate of nbutane can reach 40% and the yield of n-butylene can achieve 32%.Additionally,the catalyst PBD shows high catalytic performances in dehydrogenation of low-carbon alkane mixtures with different ratios.Finally,the obtained proper operation conditions for different feedstocks can provide with fundamental data and theoretical support for engineering design and scale up of circulating fluidized bed( CFB) dehydrogenation units,as well as the control and optimization of industrial CFB dehydrogenation plant.
Optimization studies on operation conditions for the dehydrogenation process of low-carbon alkanes( propane,iso-butane,n-butane and their mixtures) are carried out by employing a pilot-scale circulating fluidized bed( CFB) unit.PBD,a catalyst developed by Yantai University,is used in this study.Experimental findings indicate that the reaction temperature( T) and the gas hourly space velocity( GHSV) have great influences on the dehydrogenation process of low-carbon alkanes.Proper operation conditions are different according to different feedstocks.Under conditions of T =600℃ and GHSV = 1 700 h~(-1),the conversion rate of propane can reach 39% and the yield of propylene can achieve 33%.Under the conditions of T = 580℃ and GHSV = 1 700 h~(-1),the conversion rate of iso-butane can reach 48% and the yield of iso-butylene can achieve 45%. Under the conditions of T = 580℃ and GHSV = 1 700 h~(-1),the conversion rate of nbutane can reach 40% and the yield of n-butylene can achieve 32%.Additionally,the catalyst PBD shows high catalytic performances in dehydrogenation of low-carbon alkane mixtures with different ratios.Finally,the obtained proper operation conditions for different feedstocks can provide with fundamental data and theoretical support for engineering design and scale up of circulating fluidized bed( CFB) dehydrogenation units,as well as the control and optimization of industrial CFB dehydrogenation plant.
引文
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[2]Gascón J,Téllez C,Herguido J,et al.Propane dehydrogenation over a Cr2O3/Al2O3,catalyst:Transient kinetic modeling of propene and coke formation[J].Applied Catalysis A General,2003,248(1):105-116.
[3]张海娟,高杰,张浩楠,等.低碳烷烃深加工制烯烃技术的研究进展[J].石油化工,2016,45(12):1411-1419.
[4]烟台大学.介孔材料及其制备方法与催化剂及其制备方法:CN,102688769A[P].2012-06-14.
[5]烟台大学.一种介孔材料及其制备方法与催化剂及其制备方法:CN,102698814A[P].2012-03-09.
[6]烟台大学.一种高强度低碳烷烃脱氢催化剂及其制备方法:CN,104043443[P].2014-06-13.
[7]烟台大学.一种水热稳定性好的低碳烷烃脱氢催化剂及其制备方法:CN,104128175A[P]:2014-07-24.
[8]Fang Deren,Zhao Jinbo,Li Wanjun,et al.Investigation of the characteristics and deactivation of catalytic active center of Cr-Al2O3catalysts for isobutane dehydrogenation[J].Journal of Energy Chemistry,2015,24(1):101-107.
[9]刘尚,房德仁,任万忠,等.流化床用异丁烷脱氢催化剂性能比较[J].石油化工,2015,44(6):695-700.
[10]杜玉朋,孙乐晶,徐腾,等.低碳烷烃脱氢催化剂流化特性与耐磨性能[J].化工进展,2018,37(2):587-591.
[11]谭晓林,马波,张喜文,等.Cr系丙烷脱氢催化剂研究进展[J].化工进展,2010,29(1):51-57.
[12]杜玉朋,孙乐晶,房德仁,等.CFD在丙烷脱氢流化床反应器中的应用[J].石油炼制与化工,2018,49(4):58-63.
[13]Vernikovskaya N V,Savin I G,Kashkin V N,et al.Dehydrogenation of propane-isobutane mixture in a fluidized bed reactor over Cr2O3/Al2O3,catalyst:Experimental studies and mathematical modelling[J].Chemical Engineering Journal,2011,176/177:158-164.
[14]钱伯章.UOP公司技术被山东京博石化选用于生产丙烯和异丁烯[J].化学反应工程与工艺,2012,(3):285-285.
[15]李春义,王国玮.丙烷/异丁烷脱氢铂系催化剂研究进展Ⅰ.烷烃脱氢反应的热力学、动力学及反应机理[J].石化技术与应用,2017,35(1):1-5.
[16]徐春明,杨朝合.石油炼制工程[M].北京:石油工业出版社,2009.
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