Chen Zhiwei, Gao Feng, Ren Kun, Wu Quangui, Luo Yan, Zhou Hongjun, Zhang Meng, Xu Quan
State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing Beijing China 102249
Dongying Keerte New Material Co., Ltd Dongying Shandong 257081 China.
RSC Adv. 2018 Jan 17;8(7):3392-3398. doi: 10.1039/c7ra12629h. eCollection 2018 Jan 16.
Submicron-size HY zeolites with a particles size of 200-700 nm were synthesized employing a crystal precipitation method in this study. The catalytic activity for the isobutane/butene alkylation was evaluated. The results indicated that butene conversion was above 90% and the selectivity of expected products (C8) was nearly at 90% within 72 h. The micropores-blocking and coverage of acid sites resulting from high hydrocarbons increased the difficulty for the diffusion of products to the bulk and inhibited the adsorption of reactant on activity sites, which caused deactivation of catalyst. The ultimate C12 content in alkylate oil, stemmed from trimerization of butene, was reduced the addition reaction with butene to C16 and the cracking to C5-C7. The formation mechanisms and transformation processes of byproducts in alkylate oil revealed that the source of C9-C11 switched from cracking of C16+ to the addition of C5-C7 carbocations with butene when acid sites concentration was reduced by accumulating oligomers.
本研究采用晶体沉淀法合成了粒径为200-700nm的亚微米级HY沸石。对异丁烷/丁烯烷基化的催化活性进行了评价。结果表明,在72h内丁烯转化率高于90%,预期产物(C8)的选择性接近90%。高碳氢化合物导致的微孔堵塞和酸性位点覆盖增加了产物向主体扩散的难度,并抑制了反应物在活性位点上的吸附,从而导致催化剂失活。烷基化油中最终的C12含量源于丁烯的三聚反应,通过与丁烯加成生成C16以及裂化生成C5-C7而降低。烷基化油中副产物的形成机理和转化过程表明,当通过积累低聚物降低酸性位点浓度时,C9-C11的来源从C16+的裂化转变为C5-C7碳正离子与丁烯的加成。