利用择形分子筛异构化亚甲基二苯胺

doi:10.1016/S1872-2067(24)60071-9

催化学报 ›› 2024, Vol. 62: 124-130.DOI: 10.1016/S1872-2067(24)60071-9

利用择形分子筛异构化亚甲基二苯胺

Sam Van Minnebruggen^a, Ka Yan Cheung^a, Trees De Baerdemaeker^b, Niels Van Velthoven^a, Matthias Degelin^a, Galahad O’Rourke^a, Hiroto Toyoda^c, Andree Iemhoff^b, Imke Muller^b, Andrei-Nicolae Parvulescu^b, Torsten Mattke^b, Jens Ferbitz^b, 吴勤明^d, 肖丰收^d, Toshiyuki Yokoi^c, Nils Bottke^b, Dirk De Vos^a^,^*()

^a巴斯夫股份有限公司膜分离、吸附、催化和光谱学可持续解决方案中心(cMACS), 比利时
^b巴斯夫股份有限公司研究组, 德国
^c东京工业大学纳米空间催化研究所, 横滨, 日本
^d浙江大学化学系, 浙江杭州 310028, 中国

收稿日期:2024-04-03 接受日期:2024-06-05 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子信箱: Dirk.devos@kuleuven.be (D. De Vos).

Isomerization of methylenedianilines using shape-selective zeolites

Sam Van Minnebruggen^a, Ka Yan Cheung^a, Trees De Baerdemaeker^b, Niels Van Velthoven^a, Matthias Degelin^a, Galahad O’Rourke^a, Hiroto Toyoda^c, Andree Iemhoff^b, Imke Muller^b, Andrei-Nicolae Parvulescu^b, Torsten Mattke^b, Jens Ferbitz^b, Qinming Wu^d, Feng-Shou Xiao^d, Toshiyuki Yokoi^c, Nils Bottke^b, Dirk De Vos^a^,^*()

^aCentre for Membrane Separations, Adsorption, Catalysis and Spectroscopy for Sustainable Solutions (cMACS), BASF SE, KU Leuven, 3001 Leuven, Belgium
^bGroup research, BASF SE, 67056 Ludwigshafen, Germany
^cNanospace Catalysis Unit, Tokyo Institute of Technology, 226-8503 Yokohama, Japan
^dDepartment of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China

Received:2024-04-03 Accepted:2024-06-05 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: Dirk.devos@kuleuven.be (D. De Vos).

摘要/Abstract

摘要：

亚甲基二苯胺(MDA)被广泛用作生产聚氨酯和聚异氰脲酸酯的中间体. 然而, 当前MDA的生产工艺在控制(4,4’/(2,4’+2,2’))异构体比例方面还存在局限. 其中, 4,4’-MDA被认为是最有价值的异构体. 尽管2,4'-MDA在市场上也有一定的需求, 但如果能将其有效地转化为4,4'-MDA, 将能显著提升其附加值.

本文在使用苯胺的条件下, 利用β分子筛等催化剂, 通过双分子机制, 可以选择性地将2,4'-MDA异构化为4,4'-MDA. 尽管实验显示, 多种酸性沸石具有较高的异构化活性, 但MCM-68(具有MSE拓扑结构)的催化性能尤为出色, 它不仅展现出高异构化活性, 而且具有很好的选择性. MCM-68主要催化2,4'-MDA异构化为4,4'-MDA, 而2,2'-MDA和低聚物的形成则可以忽略不计. 本文还深入探讨了该择形作用的原因, 并详细研究了酸位置在MSE分子筛孔道限制中的关键作用.

关键词: 铝分布, 多相催化, 异构化, 亚甲基二苯胺, 聚氨酯, 择形

Abstract:

Methylenedianilines (MDA) are widely used as intermediates in the production of polyurethanes and polyisocyanurates. The current routes for the production of MDA offer only limited control of the isomer ratio (4,4’/(2,4’+2,2’)), with 4,4’-MDA being the most valuable isomer. While 2,4’-MDA is also marketed, significant added value could be unlocked upon further steering the production towards 4,4’-MDA. We here show that zeolites such as Beta can selectively isomerize 2,4’-MDA towards the desired 4,4’-MDA via a bimolecular mechanism, in an aniline background. While several acid zeolites were found to be active isomerization catalysts, MCM-68 (MSE topology) in particular combines high isomerization activity with efficient shape-selective suppression of the formation of unwanted 2,2’-MDA and oligomers. The origin of this shape-selectivity was studied, highlighting the crucial role of the acid site location in the pore confinement of MSE zeolites.

Key words: Aluminum distribution, Heterogeneous catalysis, Isomerization, Methylenedianiline, Polyurethane, Shape-selectivity

Sam Van Minnebruggen, Ka Yan Cheung, Trees De Baerdemaeker, Niels Van Velthoven, Matthias Degelin, Galahad O’Rourke, Hiroto Toyoda, Andree Iemhoff, Imke Muller, Andrei-Nicolae Parvulescu, Torsten Mattke, Jens Ferbitz, 吴勤明, 肖丰收, Toshiyuki Yokoi, Nils Bottke, Dirk De Vos. 利用择形分子筛异构化亚甲基二苯胺[J]. 催化学报, 2024, 62: 124-130.

Sam Van Minnebruggen, Ka Yan Cheung, Trees De Baerdemaeker, Niels Van Velthoven, Matthias Degelin, Galahad O’Rourke, Hiroto Toyoda, Andree Iemhoff, Imke Muller, Andrei-Nicolae Parvulescu, Torsten Mattke, Jens Ferbitz, Qinming Wu, Feng-Shou Xiao, Toshiyuki Yokoi, Nils Bottke, Dirk De Vos. Isomerization of methylenedianilines using shape-selective zeolites[J]. Chinese Journal of Catalysis, 2024, 62: 124-130.

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https://www.cjcatal.com/CN/Y2024/V62/I7/124

图/表 8

Scheme 1. Reaction network for the isomerization of 2,4’-MDA.

Fig. 1. Product distribution obtained in the solventless MDA isomerization for *BEA topology zeolites with different Si/Al mass ratio. Conditions: 50 mg zeolite, 250 mg 2,4’-MDA at 170 °C for 6 h.

Fig. 2. Product distribution obtained in the MDA isomerization for *BEA topology with varying aniline quantity. Mass ratio of Beta (Si/Al = 12.5):MDA:aniline = 0.2:1:x, with x = 0?8 at 170 °C for 24 h.

Fig. 3. Role of aniline in the isomerization of 2,4’-MDA using zeolite Beta. Conditions: 100 mg Beta (Si/Al = 12.5), 500 mg 2,4’-MDA and x mol L?1 aniline at 170 °C. The kinetic values represent respectively the following: kiso,1 (2,4’→ 4,4’), kiso,2 (2,4’→ 2,2’) and koligo (MDA → oligomer).

Fig. 4. Temperature dependence of the rate constant for isomerization of 2,4’- to 4,4’-MDA and derived apparent activation energies. Conditions: 100 mg zeolite Beta (Si/Al = 12.5), 500 mg 2,4’-MDA and 200 μL aniline at 140?200 °C.

Table 1 Kinetic parameters for different acid catalysts. Conditions: 100 mg zeolite, 500 mg 2,4’-MDA and 1.2 mL aniline at 170 °C.

Catalyst	Topology	Si/Al	k_iso,1 (10^‒6 s^‒1)^a	k_iso,-1 (10^‒6 s^‒1)	k_iso,2 (10^‒6 s^‒1)	k_iso,-2 (10^‒6 s^‒1)	k_oligo (10^‒7 s^‒1)
CF₃SO₃H^b	—	—	2.7	19.7^c	1.0	0.5	4.2
ZSM-5	MFI	15	0.4	0.6	0.2	0.5	0.4
Mordenite	MOR	10	0.6	0.6	0.3	0.5	0.4
Beta	*BEA	12.5	5.3	0.5	0.3	1.0	2.3
Faujasite	FAU	40	1.9	0.1	0.3	0.2	0.1
MCM-68	MSE	10.8	4.7	0.6	0.2	0.5	0.2
UZM-35	MSE	7.8	1.0	0.1	0.3	1.0	0.5
YNU-5	YFI	9.8	4.8	15.0	0.6	0.1	0.2
MCM-22	MWW	14	0.5	5.3	19.9	215	2.0

Fig. 5. Shape-selectivity in MDA isomerization, comparing zeolite Beta and MCM-68. Conditions: 100 mg zeolite, 500 mg MDA and 0.2 mL aniline at 170 °C. Beta (Si/Al = 12.5) in the isomerization of (a) 2,4’- and (b) 4,4’-MDA. MCM-68 in the isomerization of (c) 2,4’- and (d) 4,4’-MDA.

Fig. 6. Proposed origin of shape-selectivity in MCM-68. (a) Concept of 10-MR docked aniline reacting with a 4-NH2-benzylium cation at the intersection with 12-MR. (b,d) optimized structures for the reactants at the intersection, leading to resp. 4,4’- and 2,4’-MDA. (c,e) Optimized structures of the carbo-cationic intermediates at the intersection, leading to resp. 4,4’- and 2,4’-MDA.

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利用择形分子筛异构化亚甲基二苯胺

Isomerization of methylenedianilines using shape-selective zeolites

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