钛硅分子筛催化1-戊烯环氧化固定床工艺研究
收稿日期: 2022-06-13
网络出版日期: 2023-03-17
Study on epoxidation of 1-pentene catalyzed by TS-1 in fixed-bed reactor
Received date: 2022-06-13
Online published: 2023-03-17
以成型钛硅分子筛（TS-1）为催化剂、过氧化氢（H2O2）为氧化剂，研究TS-1催化剂催化1-戊烯环氧化制环氧戊烷的固定床工艺。考察了反应温度、反应压力、过氧化氢空速、溶剂种类、甲醇与过氧化氢物质的量比、1-戊烯与过氧化氢物质的量比及过氧化氢空速对TS-1催化剂催化活性和选择性的影响。实验结果表明，采用固定床工艺TS-1催化1-戊烯环氧化具有良好的催化活性和产物选择性。反应温度对催化剂稳定性的影响较大，高温反应时催化剂的活性下降快；反应压力对催化剂反应性能的影响较小；甲醇是适宜的TS-1催化1-戊烯环氧化反应的溶剂。在优化工艺条件（35 ℃、1.5 MPa、过氧化氢空速为0.08 h-1、甲醇与过氧化氢物质的量比为19.9、1-戊烯与过氧化氢物质的量比为1.5~2.0）下，催化连续运行132 h，过氧化氢转化率和环氧戊烷选择性保持在95%以上。通过对使用后的催化剂进行分析，发现1-戊烯环氧化过程中催化剂微孔孔道堵塞是其活性降低的主要原因，非永久性失活，可以通过原位再生处理恢复催化剂的活性。
宋万仓 , 臧甲忠 , 乔宾 , 岳思宇 , 洪鲁伟 , 李晨 . 钛硅分子筛催化1-戊烯环氧化固定床工艺研究[J]. 无机盐工业, 2023 , 55(3) : 126 -133 . DOI: 10.19964/j.issn.1006-4990.2022-0357
The fixed bed process of epoxidation of 1-pentene to epoxypentane catalyzed by formed titanium silicalite（TS-1） was studied by using TS-1 as catalyst and hydrogen peroxide（H2O2） as oxidant.The effects of reaction temperature，reaction pressure，hydrogen peroxide space velocity，solvent type，the molar ratio of methanol to hydrogen peroxide，the molar ratio of 1-pentene to hydrogen peroxide，and hydrogen peroxide space velocity on the catalytic activity and selectivity of TS-1 catalyst were investigated.The experimental results showed that the fixed bed process of TS-1 had good catalytic activity and product selectivity for the epoxidation of 1-pentene.The reaction temperature had great influence on the stability of the catalyst，and the activity of the catalyst was decreased rapidly at high temperature.The reaction pressure had little effect on the reaction performance of the catalyst，and methanol was the suitable solvent for the epoxidation of 1-pentene catalyzed by TS-1.Under the optimized process conditions（35 ℃，1.5 MPa，hydrogen peroxide space velocity 0.08 h-1，methanol to hydrogen peroxide mass ratio of 19.9，1-pentene to hydrogen peroxide mass ratio of 1.5~2.0），the catalyst was continuously operated for 132 h，and the hydrogen peroxide conversion rate and epoxypentane selectivity remained above 95%.Through the analysis of the catalyst after use，it was found that the main reason for the reduction of its activity was the blockage of the catalyst micropores in the process of 1-pentene epoxidation.The catalyst activity could be restored by in-situ regeneration due to non-permanent deactivation.
Key words： TS-1; 1-pentene; epoxidation; fixed-bed reactor; 1,2-epoxypentane
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