丙烯齐聚制备柴油组分催化剂及其性能研究
文献类型：学位论文
| 作者 | 李学民 |
| 学位类别 | 硕士 |
| 答辩日期 | 2015-05 |
| 授予单位 | 中国科学院大学 |
| 授予地点 | 北京 |
| 导师 | 王辉,王志奇 |
| 关键词 | 丙烯,烯烃齐聚,Ni/HZSM-5,柴油组分 |
| 其他题名 | 无 |
| 学位专业 | 化学工程 |
| 中文摘要 | 随着国民经济的平稳发展，能源需求不断增长，以化石燃料为主的传统能源的短缺以及环境污染等问题日益突出，寻找化石燃料的替代品受到了广泛的关注。低碳烯烃齐聚合成液体燃料的工艺路线有可能成为未来提供液体燃料的一种重要的选择途径，而其最大的挑战在于高效催化剂的开发。 本文基于分子筛催化剂，结合烯烃齐聚反应的特点，选择了HZSM-5催化剂和金属改性催化剂催化丙烃齐聚反应，并对工艺条件进行了优化，通过对催化剂进行综合表征，探讨了催化剂结构、性质与催化性能之间的关系。 首先对丙烯齐聚反应的催化剂体系进行了筛选，分别选择了HZSM-5催化剂和金属改性的分子筛催化体系，考察了Ni金属不同盐(NiSO4, Ni(NO3)2)负载的分子筛催化剂以及不同金属(NiSO4, FeSO4)改性的分子筛催化剂对其催化丙烯齐聚反应性能的影响，初步筛选出NiSO4/HZSM-5催化剂作为丙烯齐聚反应制备柴油组分的催化剂。 然后对Ni/HZSM-5催化体系内丙烯齐聚制备柴油反应进行了系统研究，考察了Ni负载量、反应温度等因素对丙烯齐聚反应性能的影响，确定了催化剂组分及最优工艺条件。当NiSO4负载量为2.21 wt.%，反应温度为270 oC，压力4.0 MPa时丙烯的转化率达到75.4%，柴油组分的选择性达到78.88%。 最后进一步对NiSO4/HZSM-5催化剂上丙烯齐聚反应的活性中心进行了初步探究，分别对HZSM-5催化剂、NiSO4/HZSM-5催化剂、Ni(NO3)2/HZSM-5及(NH4)2SO4/HZSM-5催化剂进行了晶体结构、配位形式、化合价、酸性等的表征，结合催化剂评价结果，初步研究了催化剂表面酸性位点和金属活性中心与催化性能之间的关系。研究发现金属活性位点和酸性活性中心协同作用是催化剂具有较好丙烯齐聚制柴油催化性能的关键因素，NiSO4的引入有利于调变分子筛上不同酸性位点的分布。 |
| 英文摘要 | With the development of the national economy, the demand for fossil fuel-based traditional energy is growing up, and environmental pollution problems have been becoming increasingly prominent. Looking for alternatives to fossil fuels has been widespread concerned. The olefins oligomerization route for liquid fuels is likely to become an important way to provide liquid fuels. Based on the molecular sieve catalysts, and metal modified catalysts combining the characteristics of the oligomerization of olefins, we chose the HZSM-5 zeolites as well as metal-modified zeolites to catalyze propene oligomerization for diesel fractions and the reaction conditions were optimized. With a comprehensive characterization of catalysts, the relationship between catalyst structure, properties and the performance was also discussed. Firstly, the HZSM-5 catalyst and metal-modified catalysts were investigated. By comparing the different metals such as Fe and Ni, as well as different salt precursorces including NiSO4 and Ni(NO3)2, the catalyst for the propene oligomerization was selected and the NiSO4/HZSM-5 catalyst was proved to be a good catalyst for the propene oligomerization reaction to diesel fractions. Then the HZSM-5 catalyst and HZSM-5 loaded with different Ni loadings, including 1%, 3%, 5%, and 7% wt.%, were investigated. The reaction conditions were studied systematically, and the optimized catalyst composition and reaction conditions were obtained. As for the NiSO4/HZSM-5 with Ni loading of 2.21wt.%, under the reaction conditions of 270 oC and 4.0 MPa, it shows best catalytic performance, with propene conversion of 75.4%, and the diesel fractions selectivity of 78.88%. And the relationship between catalytic performance and catalyst structure on NiSO4/HZSM-5 catalyst were also carried out. It was found that the catalyst structure has an influence on the oligomerization product distribution. The coordinating action between nickle and acidity sites were the main factor for the high catalytic performance of the the propene oligomerization. The study found that Niδ+(δ≤2) might act as active center for the oligomerization reaction. And the existance of SO42- can tune the distibution density of Brönsted and Lewis acid sites effectively and favore for the diesel fractions produced. |
| 学科主题 | 工学 |
| 语种 | 中文 |
| 公开日期 | 2020-09-30 |
| 源URL | [http://ir.qibebt.ac.cn/handle/337004/8100]  |
| 专题 | 青岛生物能源与过程研究所_热化学转化事业部 |
| 作者单位 | 中国科学院大学，中科院青岛生物能源与过程研究所 |
| 推荐引用方式 GB/T 7714 | 李学民. 丙烯齐聚制备柴油组分催化剂及其性能研究[D]. 北京. 中国科学院大学. 2015. |
入库方式： OAI收割
来源：青岛生物能源与过程研究所
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