碱性添加剂在钛硅分子筛/H2O2催化丙烯环氧化反应中的作用

doi:10.16085/j.issn.1000-6613.2019-0767

化工进展 ›› 2020, Vol. 39 ›› Issue (3): 1021-1028.DOI: 10.16085/j.issn.1000-6613.2019-0767

碱性添加剂在钛硅分子筛/H₂O₂催化丙烯环氧化反应中的作用

宋万仓¹(),熊光²,臧甲忠¹,于海斌¹,王祥生²

^1.中海油天津化工研究设计院有限公司催化技术重点实验室，天津 300131
^2.大连理工大学化工与环境生命学部化工学院，精细化工国家重点实验室，辽宁大连 116024

收稿日期:2019-05-13 出版日期:2020-03-05 发布日期:2020-04-03
通讯作者: 宋万仓
作者简介:宋万仓（1985—），男，博士，研究方向为分子筛合成、改性及催化选择性氧化。E-mail：songcwjin@163.com。
基金资助:
国家自然科学基金(21473016);中海油集团公司科技项目

Effect of basic additive in feedstock on propylene epoxidation catalyzed by TS-1/H₂O₂

Wancang SONG¹(),Guang XIONG²,Jiazhong ZANG¹,Haibin YU¹,Xiangsheng WANG²

^1.Key Laboratory of Catalysis Technology, CNOOC Tianjin Chemical Research and Design Institute Co. , Ltd. , Tianjin 300131, China
^2.State Key Laboratory of Fine Chemicals, Faculty of Chemical, Environmental and Biological Science and Technology, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2019-05-13 Online:2020-03-05 Published:2020-04-03
Contact: Wancang SONG

摘要/Abstract

摘要：

考察了反应溶液中碱性添加剂{氨水（NH₄OH）、氢氧化钠（NaOH）、碳酸钠（Na₂CO₃）、碳酸铵[(NH₄)₂CO₃]和四甲基氢氧化铵（TMAOH）}及其浓度对钛硅分子筛（TS-1）催化丙烯环氧化反应性能的影响，并采用紫外拉曼光谱（UV-Raman）与气相色谱（GC）联用原位分析（Raman-GC）碱性添加剂的作用机理。结果表明：反应体系中添加碱性添加剂可有效改善TS-1催化丙烯环氧化反应的选择性。不同碱性添加剂对TS-1催化丙烯环氧化活性和稳定性影响不同，NaOH、Na₂CO₃和TMAOH的添加造成催化活性和稳定性降低。NH₄OH或(NH₄)₂CO₃作为添加剂改善环氧化反应选择性的同时提高了反应稳定性，其中以(NH₄)₂CO₃效果最佳。添加(NH₄)₂CO₃浓度为8.0×10^-4mol/L时，TS-1催化丙烯环氧化在固定床反应器上连续运行336h时，X(H₂O₂)仍保持在90%以上。原位Raman-GC分析发现，反应体系中NH₄OH和(NH₄)₂CO₃添加可加快反应活性中间体Ti-OOH(η²)基团的生成，促进反应产物从活性中心快速扩散，从而提高丙烯环氧化反应选择性和稳定性。

关键词: 催化, 丙烯环氧化, 钛硅分子筛, 碱性添加剂, 原位拉曼光谱气相色谱分析, 稳定性

Abstract:

NH₄OH, NaOH, Na₂CO₃, (NH₄)₂CO₃ and TMAOH were selected as the basic additive in the feedstock of propylene epoxidation reaction and their effects on the performance of TS-1 catalysis were evaluated by in-situ Raman spectrometry-gas chromatography. The experimental results suggested that the performance of the TS-1 catalyst was influenced significantly by the composition of feedstock. However, the presence of NH₄OH or (NH₄)₂CO₃ at a suitable concentration could improve the catalytic activity, selectivity and the stability of the TS-1 catalyst. When (NH₄)₂CO₃ concentration in feedstock was 8.0×10^-4mol/L, the best catalytic performance was obtained. The X(H₂O₂) still remained above 90% after a long-term run of 336h in a fixed-bed reactor. In-situ Raman-GC showed that the basic additive promoted the formation of the reactive intermediates Ti-OOH(η²) and accelerated the diffusion of reaction products from active centers.

Key words: catalysis, propylene epoxidation, TS-1 molecular sieves, basic additive, in-situ UV-Raman, stability

中图分类号:

宋万仓,熊光,臧甲忠,于海斌,王祥生. 碱性添加剂在钛硅分子筛/H₂O₂催化丙烯环氧化反应中的作用[J]. 化工进展, 2020, 39(3): 1021-1028.

Wancang SONG,Guang XIONG,Jiazhong ZANG,Haibin YU,Xiangsheng WANG. Effect of basic additive in feedstock on propylene epoxidation catalyzed by TS-1/H₂O₂[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1021-1028.

图/表 1

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碱性添加剂在钛硅分子筛/H₂O₂催化丙烯环氧化反应中的作用

Effect of basic additive in feedstock on propylene epoxidation catalyzed by TS-1/H₂O₂

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