Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene

ZHANG Kairui; LIU Jianchao; TANG Qiong; LIU Lei; DONG Jinxiang

doi:10.11949/0438-1157.20260312

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Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene

更新时间：2026-07-09

- Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene
- CIESC Journal (2026)
- 作者机构：
  
  太原理工大学化学与化工学院，山西太原 030024
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260312
  CLC： TQ 426;TQ241.1
- Received：12 March 2026，
  
  Revised：2026-07-08，
  
  Accepted：09 July 2026，
- 稿件说明：
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ZHANG Kairui, LIU Jianchao, TANG Qiong, et al. Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene[J/OL]. CIESC Journal, 2026.
DOI：

ZHANG Kairui, LIU Jianchao, TANG Qiong, et al. Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260312.

摘要

仲丁基苯是生产苯酚和甲乙酮的重要中间体，其高效合成对酚酮联产具有重要意义。针对传统工业催化剂（固体磷酸、离子液体）存在的设备腐蚀、分离困难及环境污染等问题，本工作基于苯与丁烯烷基化反应，以沸石分子筛为绿色固体酸催化剂，系统比较了三种不同孔道结构的沸石——十元环MFI（HZSM-5）、十二元环BEA（Hβ）及带有十二元环超笼MWW（HMCM-22）——的催化性能，重点揭示了孔道拓扑结构与酸位可及性对烷基化行为的调控规律。结果表明，HZSM-5受限于十元环孔道及有限外表面酸位，扩散受阻，几乎没有催化活性；Hβ具有十二元环三维孔道，转化率提升至59.7%，但扩散路径长导致副反应增多，仲丁基苯选择性降至79.5%，且积碳严重；HMCM-22凭借其独特的十二元环超笼体系及外表面Brønsted酸位占比约45%的结构优势，在优化反应条件下，实现了80%以上的丁烯转化率和近100%的仲丁基苯选择性。提出了基于孔道结构与酸位分布差异化设计的催化剂设计策略，为烷基化催化剂的设计提供了理论参考。

Abstract

Sec-butylbenzene is an important intermediate for the production of phenol and methyl ethyl ketone

and its efficient synthesis is essential for the phenol–ketone co-production process. To overcome the inherent drawbacks of conventional industrial catalysts (solid phosphoric acid and ionic liquids)

such as equipment corrosion

difficult separation

and environmental pollution

this work employed zeolites as environmentally benign solid acid catalysts for the benzene/butene alkylation reaction. Three zeolites with distinct pore architectures—10 MR MFI (HZSM-5)

12 MR BEA (Hβ)

and 12 MR supercages MWW (HMCM-22)—were systematically compared. The study aims to elucidate the regulatory roles of pore topology and acid site accessibility on the alkylation performance. The results demonstrate that HZSM-5 exhibits negligible catalytic activity

attributable to the synergistic constraints of its 10 MR channels and the scarcity of accessible external surface acid sites

leading to diffusion limitations. Hβ

possessing a three‑dimensional 12 MR channel system

achieves a butene conversion of 59.7%; however

the extended diffusion pathways facilitate undesirable side reactions

resulting in a decreased sec‑butylbenzene selectivity of 79.5% and pronounced coke deposition. In contrast

HMCM-22 takes advantage of its unique 12 MR supercage architecture together with a substantial proportion of external surface Brønsted acid sites (approximately 45% of the total)

attaining over 80% butene conversion and nearly 100% sec‑butylbenzene selectivity under optimized reaction conditions. Based on these findings

a catalyst design strategy rooted in the differentiated engineering of pore architecture and acid site distribution is proposed

offering a theoretical framework for the rational design of alkylation catalysts.

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references

Khabarov Y G , Patrakeev A A , Veshnyakov V A , et al . One-step synthesis of picric acid from phenol [J ] . Organic Preparations and Procedures International , 2017 , 49 ( 2 ): 178 - 181 .

Perego C , de Angelis A , Pollesel P , et al . Zeolite-based catalysis for phenol production [J ] . Industrial & Engineering Chemistry Research , 2021 , 60 ( 18 ): 6379 - 6402 .

Gonfa M T , Shen S , Chen L , et al . Research progress on the heterogeneous photocatalytic selective oxidation of benzene to phenol [J ] . Chinese Journal of Catalysis , 2023 , 49 : 16 - 41 .

Liang X Y , Chi J J , Yang Z . The influence of the functional group on activated carbon for acetone adsorption property by molecular simulation study [J ] . Microporous and Mesoporous Materials , 2018 , 262 : 77 - 88 .

Halawy S A , Osman A I , Abdelkader A , et al . Boosting NiO catalytic activity by x wt % F-ions and K 2 O for the production of methyl ethyl ketone (MEK) via catalytic dehydrogenation of 2-butanol [J ] . ChemCatChem , 2021 , 13 ( 9 ): 2200 - 2214 .

窦悦珊 , 吕晓东 , 杨晨 , 等 . “十五五” 时期我国碳四资源转化和利用研究 [J ] . 当代石油石化 , 2025 , 33 ( 9 ): 6 - 9, 34 .

Dou Y S , Lv X D , Yang C , et al . Conversion and utilization of C4 in China during the 15th Five-Year Plan period [J ] . Petroleum & Petrochemical Today , 2025 , 33 ( 9 ): 6 - 9, 34 .

Sha J L , Liu C Y , Ma Z H , et al . Understanding the interfacial behaviors of benzene alkylation with butene using chloroaluminate ionic liquid catalyst: a molecular dynamics simulation [J ] . Chinese Journal of Chemical Engineering , 2023 , 54 : 44 - 52 .

陈巍 , 徐龙伢 , 谢素娟 , 等 . 丙烯与苯烷基化反应分子筛催化剂的研究进展 [J ] . 天然气化工 , 1999 , 24 ( 4 ): 39 - 44 .

Chen W , Xu L Y , Xie S J , et al . Research progress in sieve catalysts for alkylation of benzene with propylene [J ] . Natural Gas Chemical Industry , 1999 , 24 ( 4 ): 39 - 44 .

Degnan T F , Smith C M , Venkat C R . Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes [J ] . Applied Catalysis A: General , 2001 , 221 ( 1-2 ): 283 - 294 .

Perego C , Ingallina P . Recent advances in the industrial alkylation of aromatics: new catalysts and new processes [J ] . Catalysis Today , 2002 , 73 ( 1-2 ): 3 - 22 .

Kunieda T , Kim J H , Niwa M . Source of selectivity of p-xylene formation in the toluene disproportionation over HZSM-5 zeolites [J ] . Journal of Catalysis , 1999 , 188 ( 2 ): 431 - 433 .

Fraenkel D , Levy M . Comparative study of shape-selective toluene alkylations over HZSM-5 [J ] . Journal of Catalysis , 1989 , 118 ( 1 ): 10 - 21 .

Krtil J , Čejka J , Wichterlová B . Zeolite silylation for the enhancement of para-selectivity in toluene alkylation with ethylene [J ] . Collection of Czechoslovak Chemical Communications , 1997 , 62 ( 2 ): 337 - 346 .

Xing S Y , Liu K K , Wang T F , et al . Elucidation of the mechanism and structure–reactivity relationship in zeolite catalyzed alkylation of benzene with propylene [J ] . Catalysis Science & Technology , 2021 , 11 ( 8 ): 2792 - 2804 .

Kaeding W W , Holland R E . Shape-selective reactions with zeolite catalysts VI. Alkylation of benzene with propylene to produce cumene [J ] . Journal of Catalysis , 1988 , 109 ( 1 ): 212 - 216 .

Čejka J , Kotrla J , Krejčí A . Disproportionation of trimethyl benzenes over large pore zeolites: catalytic and adsorption study [J ] . Applied Catalysis A: General , 2004 , 277 ( 1-2 ): 191 - 199 .

黄鑫江 , 付凯妹 , 胡耀池 , 等 . Fe、La改性β沸石催化苯/正丁烯烷基化反应 [J ] . 化工学报 , 2009 , 60 ( 10 ): 2497 - 2502 .

Huang X J , Fu K M , Hu Y C , et al . Alkylation of benzene with 1-butylene over β-zeolite modified by Fe or La [J ] . Journal of the Chemical Industry and Engineering Society of China , 2009 , 60 ( 10 ): 2497 - 2502 .

Kokotailo G T , Lawton S L , Olson D H , et al . Structure of synthetic zeolite ZSM-5 [J ] . Nature , 1978 , 272 ( 5652 ): 437 - 438 .

Higgins J B , Lapierre R B , Schlenker J L , et al . The framework topology of zeolite beta [J ] . Zeolites , 1988 , 8 ( 6 ): 446 - 452 .

Leonowicz M E , Lawton J A , Lawton S L , et al . MCM-22: a molecular sieve with two independent multidimensional channel systems [J ] . Science , 1994 , 264 ( 5167 ): 1910 - 1913 .

Wang Y J , Cao J P , Ren X Y , et al . Synthesis of ZSM-5 using different silicon and aluminum sources nature for catalytic conversion of lignite pyrolysis volatiles to light aromatics [J ] . Fuel , 2020 , 268 : 117286 .

Tosheva L , Mihailova B , Valtchev V , et al . Zeolite beta spheres [J ] . Microporous and Mesoporous Materials , 2001 , 48 ( 1-3 ): 31 - 37 .

Pu T , Lu J N , Liu Z R , et al . Alkylation of benzene and 1-dodecene over cerium-silicate pillared MWW zeolite [J ] . Chinese Journal of Chemical Engineering , 2025 , 80 : 110 - 118 .

Zhang X F , Wang R J , Yang X X . Effect of alkaline treatment on pore structure and acidity of HZSM-5 in the synthesis of ethyl mercaptan [J ] . Catalysis Communications , 2015 , 60 : 32 - 36 .

Rivet Q , Meyet J , Rivallan M , et al . Characterization of the Brønsted acidity of PtSn/Al 2 O 3 surfaces by adsorption of 2, 6-di- tert -butylpyridine [J ] . New Journal of Chemistry , 2022 , 46 ( 16 ): 7557 - 7562 .

Corma A , Fornés V , Forni L , et al . 2, 6-di-tert-butyl-pyridine as a probe molecule to measure external acidity of zeolites [J ] . Journal of Catalysis , 1998 , 179 ( 2 ): 451 - 458 .

Al-Jubouri S M . Synthesis of hierarchically porous ZSM-5 zeolite by self-assembly induced by aging in the absence of seeding-assistance [J ] . Microporous and Mesoporous Materials , 2020 , 303 : 110296 .

Jiang H Y , Zhang Z , Li X , et al . Selective alkylation of phenol and tert -butanol using Zr-containing Beta zeolite [J ] . Journal of Materials Chemistry A , 2025 , 13 ( 11 ): 7882 - 7891 .

Huang H W , Zhu H , Zhang S H , et al . Effect of silicon to aluminum ratio on the selectivity to propene in methanol conversion over H-ZSM-5 zeolites [J ] . Journal of Fuel Chemistry and Technology , 2019 , 47 ( 1 ): 74 - 82 .

Rastegar S F , Sadovska G , Pilar R , et al . Analysis of decisive structural parameters of zeolites for alkylation of benzene with ethylene [J ] . Applied Catalysis A: General , 2020 , 591 : 117379 .

Liu R Z , Bian Y K , Dai W L . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: a combined probe-assisted 1H MAS NMR and NH 3 -TPD investigation [J ] . Chinese Journal of Structural Chemistry , 2024 , 43 ( 4 ): 100250 .

Liu R S , Fan B H , Zhi Y C , et al . Dynamic evolution of aluminum coordination environments in mordenite zeolite and their role in the dimethyl ether (DME) carbonylation reaction [J ] . Angewandte Chemie International Edition , 2022 , 61 ( 42 ): e202210658 .

Zholobenko V , Freitas C , Jendrlin M , et al . Probing the acid sites of zeolites with pyridine: Quantitative AGIR measurements of the molar absorption coefficients [J ] . Journal of Catalysis , 2020 , 385 : 52 - 60 .

Góra-Marek K , Tarach K , Choi M . 2, 6-di- tert- butylpyridine sorption approach to quantify the external acidity in hierarchical zeolites [J ] . The Journal of Physical Chemistry C , 2014 , 118 ( 23 ): 12266 - 12274 .

Saxena S K , Viswanadham N , Al-Muhtaseb A H . Effect of zeolite pore morphology on solvent-less alkylation of benzene with 1-hexene [J ] . Materials Today Chemistry , 2017 , 4 : 45 - 52 .

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