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汽油烷基化脱硫中己烯的聚合及对噻吩烷基化的影响
张泽凯1,2,牛雄雷1,2,朱向学1,刘盛林1,王清遐1,徐龙伢1
(1.中国科学院大连化学物理研究所,辽宁大连116023 ;2.中国科学院研究生院,北京100048)
摘要:
以Hp分子筛作为催化剂,考察了在汽油噻吩烷基化反应脱硫过程中,己烯的聚合对噻吩烷基化反应和Hp的 催化性能的影响。结果表明,在Hp分子筛上,己烯先与噻吩进行反应,n(己烯)/n(噻吩)=1时,90%以上的己烯与 噻吩进行烷基化反应而不发生聚合;当n(己烯)At(噻吩)^2时,己烯出现聚合,且反应程度随其含量的增加而近似 线性增加,与此同时,该反应维持平衡的时间则逐渐缩短;当n(己烯)/?(噻吩)=9时,己烯聚合量一度达到11%,
关键词:  己烯聚合  噻吩烷基化  脱硫  汽油 中图分类号:TE 624.48 文献标识码:A
DOI:
分类号:
基金项目:国家9?3计划项0 (2005CB2214)
Oligomerization performance of hexene and its influence on olefinic alkylation of thiophenic sulfur in gasoline
ZHANG Ze-Kai1,2,NIU Xiong-lei1,2,ZHU Xiang-xue1,LIU Sheng-lin1,WANG Qing-xia1,XU Long-ya1
(1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China ;2. Graduate School of Chinese Academy of Sciences, Beijing 10004S f China)
Abstract:
The influence of hexene concentration on the behavior of thiophene alkylation over Hp zeolite was investigated.The results show that thiophene had superior reactivity to the hexene oligomerization. When the n( hexene)/n( thiophene) equals 1,over 90% hexene reacts with thiophene while hexene oligomerization doesn't happen. When the rt(hexene)/^(thiophene) is greater than or equals 2, the hexene oligomerization happens, and the dimeric content increased with the hexene concentration increasing linearly, however, the stable period became short. When the n( hexene)/n( thiophene) equals 9, the dimeric content of hexene got to 11%,but after 3 h, it decreased below 5%. When the n( hexene)/n( thiophene) is smaller than 9, the increment of hexene did not influence the thiophene alkylation obviously, the conversion rate of thiophene was kept at above 99% in react time. When the n( hexene)/n( thiophene) is smaller than or equals 3,the increment of hexene was favorable for the thiophene dialkylation and the relative contwits of dihexylthiophene increased with the hexene concentration ,while the effect was just the reverse when the n ( hexene )/ra (thiophene ) is greater than or equals 4, When n (hexene)/n{ thiophene) is from 2 to 9, the hexene oligomerization only increased the carbon deposition from 5. 4% to 5. 9% , and did not decrease the acidity of the catalyst. As a result, the influence of hexene oligomerization on the thiophene alkylation comes from the competition of hexene with thiophene to get C6+ carbonium, Iwhich decreased the probability of thiophene alkylation.
Key words:  hexene oligomerization thiophene alkylation  desulfurization  gasoline
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