ZnZrOx-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯

doi:10.1016/S1872-2067(21)63975-X

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1156-1164.DOI: 10.1016/S1872-2067(21)63975-X

ZnZrO_x-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯

韩孝琴, 左佳昌, 温丹璐, 袁友珠^*()

固体表面物理化学国家重点实验室, 醇醚酯化工清洁生产国家工程实验室, 福建省嘉庚创新实验室, 厦门大学化学化工学院, 福建厦门361005

收稿日期:2021-09-05 接受日期:2021-09-05 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 袁友珠
基金资助:
国家重点研究和发展项目(2017YFA0206801);国家自然科学基金(21972113);中国高校创新研究团队项目(IRT_14R31)

Toluene methylation with syngas to para-xylene by bifunctional ZnZrO_x-HZSM-5 catalysts

Xiaoqin Han, Jiachang Zuo, Danlu Wen, Youzhu Yuan^*()

State Key Lab of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Tan Kah Kee Innovation Laboratory, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2021-09-05 Accepted:2021-09-05 Online:2022-03-05 Published:2022-03-01
Contact: Youzhu Yuan
Supported by:
National Key Research and Development Program of China(2017YFA0206801);National Natural Science Foundation of China(21972113);Program for Innovation Research Team in Chinese Universities(IRT_14R31)

摘要/Abstract

摘要：

作为重要的有机化工原料, 近些年来随着聚酯行业的高速发展, 对二甲苯(PX)需求量逐年增高. 目前, PX主要通过传统的石油路线生产, 例如石脑油催化重整、甲苯歧化和C₈芳烃异构化, 这些路线的后续精馏能耗较高. 甲醇作为碳源与甲苯烷基化制备PX有效提高了目标产物的选择性, 且已实现工业化. 然而, 由于甲醇生成甲氧基烷基化物种的能垒较高, 使反应温度较高, 促进了甲醇制烯烃(MTO)副反应的进行, 降低了甲醇利用率; 且由于积炭的形成, 催化剂容易失活. 合成气是非石油基资源如煤炭、天然气和生物质等利用的重要平台, 在转化为醇类、烯烃以及芳烃路径中将经过甲氧基中间体, 因此, 本文研发以合成气代替甲醇与甲苯烷基化制备PX的催化剂和催化过程.
基于本课题组关于CO₂加氢耦合甲苯烷基化制PX的研究基础, 本文将ZnZrO_x (ZZO)与ZSM-5 (Z5)混合制得双功能催化剂, 用于合成气转化耦合甲苯烷基化制PX. 研究结果表明, 通过优化催化剂的组成和烷基化反应条件, 调控CO加氢反应和甲苯烷基化反应的匹配性, 在甲苯转化率为10.3%时, 可获得64.8%的二甲苯选择性(不计水煤气变换反应), 其中PX占81.8%, 气态烃副产物的选择性为10.9%; 在相同条件下采用甲醇为烷基化试剂时, 二甲苯选择性仅38.5%, 其中PX占38.8%, 此时气态烃副产物的选择性达26.2%. 同位素效应实验结果表明, 二甲苯中新增甲基来自于合成气, 而非甲苯的歧化反应. 催化剂构效研究结果表明, PX的选择性与分子筛孔径、酸性强度以及Brönsted酸性位点有关; 原位红外结果也证实了该反应呈现逆同位素效应(k_H2/k_D2 = 0.92), 表明反应中甲酸盐物种(HCOO*)加氢可能是反应的决速步骤. 与传统的甲醇甲苯烷基化路径相比, 采用来源广泛和成本较低的合成气与甲苯进行烷基化反应的温度(340 °C)更低, 有效避免了MTO副反应的发生, 同时, 该催化剂可在100 h内保持良好稳定性. 综上, 本工作结果为高效制备高值芳烃PX提供了新思路.

关键词: 甲苯烷基化, 合成气转化, 对二甲苯, 双功能催化剂, ZnZrO_x-ZSM-5

Abstract:

Toluene methylation with methanol on H-ZSM-5 (Z5) zeolite for the directional transformation of toluene to xylene has been industrialized. However, great challenges remain because of the high energy barrier of methanol deprotonation to the methoxy group, the side reaction of methanol to olefins, coke formation, and the deactivation of zeolites. Herein, we report the toluene methylation coupled with CO hydrogenation to showcase an enhancement in para-xylene (PX) selectivity by employing a bifunctional catalyst composed of ZnZrO_x (ZZO) and modified Z5. The results showed that a PX selectivity of up to 81.8% in xylene and xylene selectivity of 64.8% in hydrocarbons at 10.3% toluene conversion can be realized over the bifunctional catalyst on a fixed-bed reactor. The selectivity of gaseous hydrocarbons decreased to 10.9%, and approximately half of that was observed in methanol reagent route where the PX selectivity in xylene was 38.8%. We observed that the acid strength, the quantity ratio of Brönsted and Lewis acid sites, and the pore size of zeolites were essential for the PX selectivity. The investigation of the H₂/D₂ kinetic isotope effect revealed that the newborn methyl group in xylene resulted from the hydrogenation of CO rather than toluene disproportionation. Furthermore, the catalyst showed no evident deactivation within the 100 h stability test. The findings offer a promising route for the production of value-added PX with high selectivity via toluene methylation coupled with syngas conversion.

Key words: Toluene methylation, Syngas conversion, Para-xylene, Bifunctional catalyst, ZnZrO_x-ZSM-5

韩孝琴, 左佳昌, 温丹璐, 袁友珠. ZnZrO_x-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯[J]. 催化学报, 2022, 43(4): 1156-1164.

Xiaoqin Han, Jiachang Zuo, Danlu Wen, Youzhu Yuan. Toluene methylation with syngas to para-xylene by bifunctional ZnZrO_x-HZSM-5 catalysts[J]. Chinese Journal of Catalysis, 2022, 43(4): 1156-1164.

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图/表 12

Fig. 1. Catalytic performance of toluene methylation with syngas over ZZO-nSZ5 (a) and ZZO-3SZ5 (b) with different ZZO mass percentages. Reaction conditions: T = 340 °C, P = 3.0 MPa, H2/CO = 2 (V/V), GHSV = 12000 mL g-1h-1, WHSVtoluene = 0.9 h-1, and time on stream (TOS) = 15 h. Xyl.: xylene, C1-C5: gaseous hydrocarbons, Benz.: benzene, PX: PX in xylene, ET: 4-ethyltoluene, TMB: 1,2,4-trimethylbenzene, C9+: other aromatics, Conv.: toluene conversion.

Fig. 2. Comparison of CO hydrogenation and CH3OH routes. (a) Catalytic performance; (b) Apparent activation energy. Reaction conditions: T = 340 °C, P = 3.0 MPa, and TOS = 15 h. CO hydrogenation route: H2/CO = 2 (V/V), ZZO-3SZ5 mass ratio = 3/7, GHSV = 12000 mL g-1h-1, and WHSVtoluene = 0.9 h-1. CH3OH route: H2/N2 = 3/2 (V/V), GHSV = 12000 mL g-1h-1, WHSVtoluene = 0.9 h-1, and C7H8/CH3OH = 6 (mol/mol).

Fig. 3. Catalytic performance of ZZO and 3SZ5 in different intimacy modes. Reaction conditions: T = 340 °C, P = 3.0 MPa, H2/CO = 2 (V/V), ZZO-3SZ5 mass ratio = 3/7, GHSV = 12000 mL g-1h-1, WHSVtoluene = 0.9 h-1, and TOS = 15 h.

Fig. 4. (a) H2/D2 kinetic isotope effect of toluene methylation with CO + H2 (D2) over ZZO-3SZ5. Reaction conditions: T = 340 °C, P = 3.0 MPa, H2/CO = 2 (V/V), ZZO-3SZ5 mass ratio = 3/7, GHSV = 12000 mL g-1h-1, and WHSVtoluene = 0.9 h-1. Mass spectra in H/D exchange reaction: (b) toluene; (c) xylene.

Fig. 5. SEM images of 3SZ5 (a) and ZZO-3SZ5 (b).

Fig. 6. XRD patterns of ZZO, Z5, and ZZO-nSZ5.

Fig. 7. Pore width distribution of nSZ5 based on the nonlocal density functional theory method.

Fig. 8. (a) Py-FTIR spectra of ZZO-nSZ5; (b) NH3-TPD profiles of nSZ5.

Fig. 9. CO-TPD profiles of ZZO, 3SZ5, and ZZO-3SZ5.

Fig. 10. In situ DRIFTS spectra of ZZO exposed to CO + H2 and then changed to CO + D2 (a), ZZO-3SZ5 exposed to CO + H2 + C7H8 and then changed to CO + D2 + C7H8 (b).

Fig. 11. A possible reaction mechanism for syngas conversion coupled with toluene methylation over the bifunctional catalyst ZZO-nSZ5.

Fig. 12. Stability of ZZO-3SZ5. Reaction conditions: T = 340 °C, P = 3.0 MPa, H2/CO = 2 (V/V), ZZO-3SZ5 mass ratio = 3/7, GHSV = 12000 mL g-1h-1, and WHSVtoluene = 0.9 h-1.

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ZnZrO_x-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯

Toluene methylation with syngas to para-xylene by bifunctional ZnZrO_x-HZSM-5 catalysts

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ZnZrOx-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯

Toluene methylation with syngas to para-xylene by bifunctional ZnZrOx-HZSM-5 catalysts

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ZnZrO_x-HZSM-5双功能催化剂催化甲苯与合成气烷基化制对二甲苯

Toluene methylation with syngas to para-xylene by bifunctional ZnZrO_x-HZSM-5 catalysts