富含氢键硅羟基的silicalite-1沸石纳米片应用于气相贝克曼重排:一步法合成与理论研究

doi:10.1016/S1872-2067(24)60160-9

催化学报 ›› 2024, Vol. 67: 82-90.DOI: 10.1016/S1872-2067(24)60160-9

富含氢键硅羟基的silicalite-1沸石纳米片应用于气相贝克曼重排:一步法合成与理论研究

宰天明^a^,¹, 陈伟^b^,¹, 袁家敏^b, 马野^c, 吴勤明^a(), 易先锋^b, 刘志强^b, 孟祥举^a, 刘未了^d, 盛娜^d, 王韩^d, 郑安民^b, 肖丰收^a()

^a浙江大学化学与生物工程学院, 浙江杭州 310007
^b中国科学院精密测量科学与技术创新研究院, 波谱与原子分子物理国家重点实验室,武汉国家磁共振中心, 湖北武汉 430071
^c上海科技大学物理科学与技术学院, 上海 201210
^d浙江恒逸石化研究院有限公司, 浙江杭州 310027

收稿日期:2024-08-15 接受日期:2024-09-19 出版日期:2024-12-18 发布日期:2024-11-30
通讯作者: 吴勤明,郑安民,肖丰收
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(22288101);国家自然科学基金(22172141);浙江省自然科学基金(LR24B030001);武汉市自然科学基金(2024040701010058)

Silicalite-1 zeolite nanosheets with rich H-bonded silanols for boosting vapor-phase Beckmann rearrangement: One-pot synthesis and theoretical investigation

Tianming Zai^a^,¹, Wei Chen^b^,¹, Jiamin Yuan^b, Ye Ma^c, Qinming Wu^a(), Xianfeng Yi^b, Zhiqiang Liu^b, Xiangju Meng^a, Weiliao Liu^d, Na Sheng^d, Han Wang^d, Anmin Zheng^b, Feng-Shou Xiao^a()

^aCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310007, Zhejiang, China
^bState Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, Hubei, China
^cSchool of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
^dZhejiang Hengyi Petrochemical Research Institute Co., Ltd., Hangzhou 310027, Zhejiang, China

Received:2024-08-15 Accepted:2024-09-19 Online:2024-12-18 Published:2024-11-30
Contact: Qinming Wu, Anmin Zheng, Feng-Shou Xiao
About author:
¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22288101);National Natural Science Foundation of China(22172141);Zhejiang Provincial Natural Science Foundation of China(LR24B030001);Natural Science Foundation of Wuhan(2024040701010058)

摘要/Abstract

摘要：

己内酰胺作为生产尼龙6纤维和聚酰胺工程塑料的重要中间体, 其主要生产工艺是以发烟浓硫酸为催化剂的环己酮肟液相贝克曼重排. 但是, 发烟浓硫酸不仅会腐蚀设备, 而且产生大量低价值的硫酸铵, 因此特别期望气相贝克曼重排工艺取代液相工艺. 沸石分子筛催化剂由于其理论上100%的原子利用率, 反应不生成硫酸铵以及具有较好的环己酮肟转化率和己内酰胺的高选择性而受到广泛关注. 其中, silicalite-1沸石通过骨架上的硅羟基有效活化环己酮肟, 在气相重排中具有很好的活性. 然而, silicalite-1沸石催化剂的反应选择性仍然比发烟浓硫酸低了几个百分点, 这制约了其工业应用. 因此, 提高silicalite-1沸石的反应选择性与发烟浓硫酸相当仍然具有挑战性, 提高沸石催化剂的传质和对催化活性位点硅羟基进行有效调控是有效解决方案.

本文提出了一步法合成富含氢键作用的硅羟基silicalite-1沸石纳米片, 其中纳米片可以有效提高反应传质而含氢键作用的硅羟基可以增加催化活性中心位点. 合成体系中使用尿素是成功合成材料的关键. 通过调节四丙基氢氧化铵或尿素的量, 得到不同厚度和长度的silicalite-1沸石纳米片. 扫描电子显微镜结果表明, 纳米片厚度可以达到80 nm, 高分辨率透射电子显微镜中沿a轴方向的正弦微孔给出了清晰的直通孔道. 环己酮肟的气相贝克曼重排的催化试验表明, 与传统的silicalite-1沸石相比, silicalite-1沸石纳米片对己内酰胺的选择性更高, 反应寿命更长. X射线光电子能谱结果表明, 环己酮肟的贝克曼重排也可能发生在silicalite-1沸石晶体内部. 在该情况下, 具有良好传质性能的silicalite-1纳米片有利于提高催化活性和抗积碳能力. ²⁹Si固体核磁和¹H固体核磁结果表明, silicalite-1沸石纳米片比传统silicalite-1沸石具有较少的末端硅羟基和更多的具有中等和强氢键作用的硅羟基, 这也是其具有更好贝克曼重排反应性能的原因. 理论计算结果表明, 具有氢键作用的硅羟基对尿素分解产生的多个氨分子有更强的吸附能力, 从而阻碍了氢键作用的硅羟基和硅源形成Si‒O‒Si键, 但是末端硅羟基却不受其影响.

综上, 本文提出了一步法合成silicalite-1分子筛纳米片, 该方法对环己酮肟气相贝克曼重排制己内酰胺非常有效. 该方法的关键是添加尿素以形成具有氢键作用的硅羟基和纳米形貌, 具有氢键作用的硅羟基有利于贝克曼重排, 纳米片形貌有利于反应传质. 因此, 环己酮肟在该分子筛上的气相贝克曼重排显示出对己内酰胺的高选择性和长反应寿命, 甚至与发烟硫酸催化剂相当. 本文工作为未来设计和制备新一代气相贝克曼重排催化剂提供参考.

关键词: silicalite-1沸石纳米片, 富含氢键作用的硅羟基, 一步法合成, 气相贝克曼重排, 理论研究

Abstract:

Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging. Herein, we show a one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols. The key to this success is the use of urea in the synthetic system. Catalytic tests of cyclohexanone oxime gas-phase Beckmann rearrangement show that the silicalite-1 zeolite nanosheets with H-bonded silanols exhibit higher selectivity for caprolactam and longer reaction lifetime than those of the conventional silicalite-1 zeolite. Theoretical simulations reveal that the ammonium decomposed by urea is a critical additive for the formation of H-bond silanols. Obviously, one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols plus excellent catalytic performance in the Beckmann rearrangement offer a new opportunity for development of highly efficient zeolites for catalytic applications in the future.

Key words: Silicalite-1 zeolite nanosheets, Rich H-bonded silanols, One-pot synthesis, Vapor-phase Beckmann rearrangement, Theoretical investigation

宰天明, 陈伟, 袁家敏, 马野, 吴勤明, 易先锋, 刘志强, 孟祥举, 刘未了, 盛娜, 王韩, 郑安民, 肖丰收. 富含氢键硅羟基的silicalite-1沸石纳米片应用于气相贝克曼重排:一步法合成与理论研究[J]. 催化学报, 2024, 67: 82-90.

Tianming Zai, Wei Chen, Jiamin Yuan, Ye Ma, Qinming Wu, Xianfeng Yi, Zhiqiang Liu, Xiangju Meng, Weiliao Liu, Na Sheng, Han Wang, Anmin Zheng, Feng-Shou Xiao. Silicalite-1 zeolite nanosheets with rich H-bonded silanols for boosting vapor-phase Beckmann rearrangement: One-pot synthesis and theoretical investigation[J]. Chinese Journal of Catalysis, 2024, 67: 82-90.

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图/表 4

Fig. 1. Structure investigation. (a?c) SEM images of S-1-U1, S-1-U2 and S-1-U3 zeolites and (d?f) iDPC-STEM images of S-1-U1 sample viewed along with different axis.

Fig. 2. Catalytic performance of vapor-phase Beckmann rearrangement. (a) Dependences of CHO conversion on reaction time over various S-1 zeolite catalysts. Reaction condition: 35 wt% CHO and 0.7 wt% H2O in ethanol, 0.3 g of catalyst, WHSV of 6 h?1, and temperature at 380 °C. (b) Dependences of CHO conversion on reaction time over S-1-C and S-1-U1 under conditions of high WHSV. Reaction condition: 35 wt% CHO and 0.7 wt% H2O in ethanol, 0.05 g of catalyst, WHSV of 100 h?1, and temperature at 350 °C. (c) Product selectivity over various S-1 zeolite catalysts at reaction time of 6 h.

Fig. 3. Silanol investigation. (a) 29Si MAS NMR spectra, (b) 1H MAS NMR spectra and (c) FT-IR spectra of the dehydrated S-1 zeolites in OH-stretch region.

Fig. 4. Theoretical simulation. (a) Structural details of three NH3 molecules adsorbed on silanol nest. (b) Averaged NH3 adsorption energy (∆E(NH3)ads) of 1?3 NH3 molecules on four silanols. (c) Representative structure of reactant (R), transition state (TS), and product (P). (d) In the presence or absence of ammonia, geminal silanols, vicinal silanols and terminal silanols react with tetrahydroxysilicon to form the reaction potential energy surface of the Si?O?Si bond.

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富含氢键硅羟基的silicalite-1沸石纳米片应用于气相贝克曼重排:一步法合成与理论研究

Silicalite-1 zeolite nanosheets with rich H-bonded silanols for boosting vapor-phase Beckmann rearrangement: One-pot synthesis and theoretical investigation

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