ZnCeZrOx/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应

doi:10.1016/S1872-2067(25)64668-7

催化学报 ›› 2025, Vol. 73: 174-185.DOI: 10.1016/S1872-2067(25)64668-7

ZnCeZrO_x/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应

庹杰^a, 盛振腾^a, 龚贤晨^a, 杨琪^a, 吴鹏^a^,^b(), 徐浩^a^,^b()

^a华东师范大学化学与分子工程学院, 石油化工分子转化与反应工程全国重点实验室, 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
^b崇明生态研究院, 上海 202162

收稿日期:2024-12-31 接受日期:2025-02-11 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: hxu@chem.ecnu.edu.cn (徐浩), pwu@chem.ecnu.edu.cn (吴鹏).
基金资助:
国家自然科学基金(22222201);国家自然科学基金(22272054);国家重点研发计划(2023YFB3810602);国家重点研发计划(2021YFA1501401)

Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst

Jie Tuo^a, Zhenteng Sheng^a, Xianchen Gong^a, Qi Yang^a, Peng Wu^a^,^b(), Hao Xu^a^,^b()

^aState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
^bInstitute of Eco-Chongming, Shanghai 202162, China

Received:2024-12-31 Accepted:2025-02-11 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: hxu@chem.ecnu.edu.cn (H. Xu), pwu@chem.ecnu.edu.cn (P. Wu).
Supported by:
National Natural Science Foundation of China of China(22222201);National Natural Science Foundation of China of China(22272054);National Key Research and Development Program of China(2023YFB3810602);National Key Research and Development Program of China(2021YFA1501401)

摘要/Abstract

摘要：

对二甲苯(PX)作为高附加值化工原料, 在对苯二甲酸及高端聚合物生产领域具有重要应用价值. 近年来, 基于金属氧化物-分子筛双功能催化剂的CO₂加氢耦合甲苯甲基化反应为合成二甲苯及PX提供了新策略. 此外, CO₂转化为高附加值的芳烃不仅可以实现CO₂的减排, 还可以提供一条制备化学品的非石油路线. 然而, 已报道的ZSM-5分子筛与金属氧化物构筑的催化体系反应温度高(> 633 K), 导致能耗高、CO选择性偏高及CO₂利用效率低等问题. 因此, 开发新型催化体系以实现低温条件下CO₂加氢耦合甲苯甲基化反应, 对提升二甲苯及PX合成效率具有重要意义.

本文使用ZnCeZrO_x固溶体与MCM-22分子筛构建了双功能催化体系(ZnCeZrO_x/MCM-22)用于催化CO₂加氢耦合甲苯甲基化反应. 首先研究了反应温度对ZnCeZrO_x/MCM-22催化性能的影响, 在603 K时二甲苯和PX的时空收率(STY)最大, 分别为222.6和49.2 mg·h^-1·g_cat^-1. 在相同反应温度下, 催化性能明显优于ZSM-5分子筛构筑的催化剂, 这是由于MCM-22独特的超笼结构为体积较大的反应中间体提供了更开阔的反应空间. 然而由于PX容易在分子筛外表面发生异构化和深度烷基化反应, 导致PX在二甲苯中的比例(PX/X)仅有24.3%. 因此, 进一步使用化学液相沉积法对MCM-22分子筛进行硅沉积改性. 发现随着正硅酸四乙酯(TEOS)量的增加, 二甲苯选择性从36.0%增加至92.4%, PX/X从24.3%提升至67%, 而三甲苯选择性从59.2%显著降至7.5%. 此外, 随着硅沉积次数的增加, 二甲苯选择性和PX/X也显著增加. 其中, 样品MS13-2显示了最优的催化性能, 二甲苯选择性为92.4%、PX/X值为67%、CO₂转化率为7.7%、甲苯转化率为23.6%, 并具有高的STY_xylene (302.0 mg·h^-1·g_cat^-1)与STY_PX (201.6 mg·h^-1·g_cat^-1). 值得注意的是, 此处反应温度较低, 因此CO选择性仅为11.6%, 明显低于文献报道的其他催化体系. 随后, 对使用不同量TEOS改性的MCM-22分子筛进行了表征(代表样品MCM-22, MS4-2, MS8-2, MS13-2), 研究了催化性能与分子筛结构之间的构效关系. N₂/Ar吸脱附曲线证明了随着TEOS用量的增加, MCM-22分子筛的孔径明显减小, 这也许会增加分子筛的择形能力. 进一步使用间二甲苯(MX)作为探针分子, 通过MX脱附红外光谱研究了其在四个样品上的脱附行为. 发现随着TEOS用量的增加, MX的脱附速度明显降低, 证明了硅沉积降低分子筛孔径有效提高了MCM-22的择形选择性. 此外, 本研究还对改性后样品的酸性进行了分析, 大分子2,6-二叔丁基吡啶吸附红外光谱表明, TEOS硅沉积可以有效去除MCM-22分子筛外表面的酸性, 从而抑制了过度烷基化和异构化反应. 此外, 反应后催化剂中有机物分析结果表明硅沉积可以抑制分子筛孔道内积碳前驱体的形成. 最后, 使用原位漫反射红外光谱技术研究了ZnCeZrO_x/MS13-2催化剂上的反应中间体, 证明了ZnCeZrO_x表面上生成的甲氧基/甲醇为关键中间体, 转移到MCM-22分子筛上发生甲基化反应生成二甲苯和PX.

综上所述, 本研究成功构建了ZnCeZrO_x/MCM-22双功能催化体系, 在低温(< 603 K)下高效催化CO₂加氢耦合甲苯甲基化制对二甲苯反应. 通过硅沉积改性MCM-22分子筛, 实现了缩小其分子筛孔道尺寸(增强择形效应)及消除表面酸性位(抑制异构化/深度甲基化等副反应)的目的, 进而提升了二甲苯及PX的选择性. 该工作为催化CO₂耦合甲苯制对二甲苯提供了新型双功能催化剂.

关键词: MCM-22分子筛, CO₂加氢, 甲苯甲基化, 串联反应, 对二甲苯

Abstract:

Selective synthesis of value-added xylenes and para-xylene (PX) by CO₂ hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO₂. Herein, modified MCM-22 zeolite combined with ZnCeZrO_x solid solution is reported to catalyze the tandem CO₂ hydrogenation and toluene methylation reaction at a relatively low temperature (< 603 K), showing xylene selectivity of 92.4% and PX selectivity of 62% (PX/X, 67%) in total aromatics at a CO₂ conversion of 7.7%, toluene conversion of 23.6% and low CO selectivity of 11.6%, as well as giving high STY of xylene (302.0 mg·h^-1·g_cat^-1) and PX (201.6 mg·h^-1·g_cat^-1). The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22, which promoted zeolite shape-selectivity and suppressed secondary reactions.

Key words: MCM-22 zeolite, CO₂ hydrogenation, Toluene methylation, Tandem reaction, Para-xylene

庹杰, 盛振腾, 龚贤晨, 杨琪, 吴鹏, 徐浩. ZnCeZrO_x/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应[J]. 催化学报, 2025, 73: 174-185.

Jie Tuo, Zhenteng Sheng, Xianchen Gong, Qi Yang, Peng Wu, Hao Xu. Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst[J]. Chinese Journal of Catalysis, 2025, 73: 174-185.

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图/表 7

Fig. 1. XRD pattern (a), SEM image (b) and TEM images (c,d) of ZnCeZrOx solid solution.

Fig. 2. (a) Catalytic performances for the tandem CO2 hydrogenation and toluene methylation reaction over ZnCeZrOx/MCM-22 catalysts after the modification of MCM-22. (b) The xylenes distribution over different catalysts. (c) The CO2 carbon usage over different catalysts. Reaction conditions: catalyst mass 0.25 g, ZnCeZrOx/zeolite mass ratio 1:1, reduction temperature 673 K, reaction temperature 603 K, pressure 3 MPa, the gas flow rate (H2/CO2 volume ratio = 3:1) 50 mL·min-1, WHSV of toluene 1.2 h-1, reaction time 15 h. (d) Toluene and CO2 conversion, as well as xylenes selectivity, PX selectivity in xylenes, and PX productivity with TOS over the physical mixed composite catalyst of ZnCeZrOx/MS13-2. Reaction conditions: catalyst mass 0.25 g, ZnCeZrOx/MS13-2 mass ratio 1:1, reduction temperature 673 K, reaction temperature 603 K, pressure 3 MPa, the gas flow rate (H2/CO2 volume ratio = 3:1) 50 mL·min-1, WHSV of toluene 1.2 h-1.

Fig. 3. (a) XRD patterns of MCM-22 and MS13-2. TEM images of MCM-22 (b) and MS13-2 (c).

Fig. 4. Ar sorption isotherms and corresponding pore width distribution (insert) of different MCM-22 zeolites.

Fig. 5. (a) p-, m-, o-Xylene desorption FTIR spectra over the MS13-2 zeolite. (b) The residual percentage of xylene isomers according to the peak-intensity changes (signal at 2929 cm?1) over the MS13-2 zeolite at different desorption times (data calculated from Table S7). (c) m-Xylene desorption FTIR spectra over different MCM-22 zeolites. (d) The residual percentage of m-xylene according to the peak-intensity changes (signal at 2929 cm?1) over different MCM-22 zeolites at different desorption time (data calculated from Table S8).

Fig. 6. 2,6-Ditertbutylpyridine-adsorbed IR spectra of MCM-22 and the modified zeolites.

Fig. 7. (a) STY of xylenes (green) and PX (red) at different temperatures over modified MCM-22 (pentagram symbols) and ZSM-5 zeolites in tandem toluene methylation and CO2 hydrogenation, where the data of ZSM-5 are adopted from the representative literatures from the reference as shown in Table S4. (b) Proposed PX synthesis strategy over modified MCM-22. (c) In-situ DRIFTS with the TOS for CO2 hydrogenation reaction over ZnCeZrOx solid solution under the CO2/H2 flow (50 mL·min-1) at 603 K and 0.1 Mpa. (d) In-situ DRIFTS with TOS over the composite catalyst of ZnCeZrOx/MS13-2 in CO2/H2 flow (50 mL·min-1) at 603 K and 0.1 Mpa. The spectra were recorded at intervals of 1 min from 0 to 30 min after reduction of the sample with H2 (30 mL·min-1) for 2 h at 673 K and purged with He (30 mL·min-1) for 0.5 h at 603 K. (e) In-situ DRIFTS with the TOS for toluene methylation in the presence of CO2/H2 (50 mL·min-1) over ZnCeZrOx/MS13-2 at 603 K and 0.1 Mpa. The spectra were recorded at intervals of 1 minute from 0 to 30 min after reduction of the sample with H2 (30 mL·min-1) for 2 h at 673 K and purged with He (30 mL·min-1) for 0.5 h at 603 K. Then toluene was continuously introduced into in-situ chamber in CO2/H2 flow at 603 K.

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ZnCeZrO_x/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应

Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst

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ZnCeZrOx/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应

Shape-selective synthesis of para-xylene through tandem CO2 hydrogenation and toluene methylation over ZnCeZrOx/MCM-22 catalyst

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ZnCeZrO_x/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应

Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst