【作者】 徐向阳；

【导师】 陈新志；

【作者基本信息】 浙江大学 ， 化学工程， 2013， 硕士

【摘要】 裂解C9馏分作为乙烯装置的副产物,近几年来,随着乙烯行业的迅猛发展,其产量也在不断增加。该馏分组分复杂,含有大量的C9芳烃、苯乙烯类、茚类、萘类、双环戊二烯(DCPD)、甲基环戊二烯二聚体(DMCPD)及环戊二烯与甲基环戊二烯(CPD+MCPD)的二聚体等。其中,DCPD(CPD)与DMCPD (MCPD)均为重要的精细化工原料,附加值高,具有广阔的市场发展前景。本文在阅读大量文献,及对某炼化裂解C9原料分析的基础上,采用液相解聚工艺,对裂解C9中的DCPD与DMCPD进行分离。通过大量的小试实验,确定了从裂解C9中分离DMCPD及DCPD的基本工艺路线为采用液相解聚的方法,一次解聚单体分离,得到高纯度CPD和粗MCPD,由CPD直接二聚得到高纯度的DCPD (>97%),对MCPD二聚后得到的粗DMCPD进行切轻、切重,得到高纯度的DMCPD (>95%)。具体工艺条件如下：1.采用解聚塔与单体分离塔串联,连续解聚单体分离工艺路线进行DCPD及DMCPD的解聚,解聚塔的最佳理论板为15块,单体分离塔为20块,解聚塔塔顶采出CPD与MCPD的混合物,单体分离塔在离塔釜5块理论板处采出MCPD,塔顶采出CPD。解聚最佳采出温度为80～90℃,单体分离塔塔顶最佳采出温度为40℃,侧线采出温度为70～80℃。解聚塔塔顶最佳回流比为1：1,单体分离塔塔顶最佳回流比为1：1,侧线为2：1。解聚塔解聚温度为180～200℃,单体分离塔塔釜温度为180～200℃。采用500ppm的对苯醌作为裂解C9原料解聚时的阻聚剂。2.将上述解聚分离过程中得到的单体MCPD、CPD进行二聚反应,聚合温度在80～90℃,停留时间在540min时,可以满足二聚时的转换需求。单体CPD馏分通过二聚后,即可得到高纯度的DCPD产品；而单体MCPD二聚后,得到的为粗DMCPD产品,后续还需要进行精制分离,才能得到高纯度的DMCPD产品。3.在对DMCPD进行精制的过程中,保持精馏温度为115～125℃(0.095MPa真空度),塔顶采用内回流,不考虑外回流。采用切轻、切重分离方法,切轻温度小于90℃,切重温度小于105℃,DMCPD采出温度在90～105℃为最优。通过放大试验进行验证,并在此基础上应用化工模拟软件对整个工艺进行模拟计算,确定了整个流程的工艺条件及设备参数,开发了一套从裂解C9馏分中分离DCPD与DMCPD的生产装置。将其投产后,生产运行稳定,所得DMCPD产品纯度在95%以上,DCPD产品纯度在97%以上。更多还原

【Abstract】 With the development of ethylene industry, the yield of cracking C9fraction has continuously increased.The components of cracking C9are complex, which contain a large number of C9aromatics, styrene, indene, naphthalene, dicyclopentadiene (DCPD), methyl cyclopentadiene dimer (DMCPD), cyclopentadiene with methyl cyclopentadiene (CPD+MCPD) dimer, etc. DCPD (CPD) and DMCPD (MCPD) are important chemical raw materials and valuable products, which have broad market prospects.After reading aomunts of literatures and analyzing the cracking C9raw materials, liquid phase depolymerization process for separating DCPD and DMCPD was used. The high purity CPD and the crude MCPD was obtained by separation of the depolymerized monomer. DCPD (>97%) was obtained by dimerization of the CPD while DMCPD (>95%) was obtained after cutting the light constituent and heavy constituent. The separation condition and equipment parameters were optimized as follow:1. Cleavage column and monomer separating column were used in series to depolymerize. The optimal theoretical plate for cleavage column was15and the optimal theoretical plate for monomer separating column was20. The mixture of CPD and MCPD was obtained from the top of the cleavage column. MCPD was obtained form the fifth plate. CPD was obtained form the bottom of the column. The best depolymerization extraction temperature was80～90℃, the best extraction temperature at the top of the monomer separating column was40℃and the best siding extraction temperature was70～80℃. The best reflux ratio for the top of the cleavage column was1:1, the best reflux ratio for the top of the monomer separating column was1:1and the best reflux ration for siding was2:1. The depolymerization temperature for the cleavage column was180～200℃. The bottom temperature for the monomer separating column was180～200℃.500ppm para-quinone was used as the polymerization inhibitor.2. With the dimerization reaction of MCPD and CPD, the highly purified DCPD and the crude DMCPD was obtained. The polymerization temperature was80～90℃and the residence time was540min. 3. During the purification of DMCPD, the fractionating temperature was115～125℃(0.095MPa). The top of column was under internal reflux. By the separation of cutting the light constituent and heavy constituent, the highly purified DMCPD was obtained. The cut light temperature was lower than90℃and the cut heavy temperature was lower than105℃. The optimal extraction temperature for DMCPD was90～105℃.The whole process was simulated by Aspen Plus. A set of production device was developed to separate methyl cyclopentadiene dimer and dicyclopentadiene from the cracking C9fraction. After the device put into operation, the production line is operating stably. The purity of DMCPD is more than95%and DCPD is more than97%.更多还原