苯与合成气在ZnAlCrO x &HZSM-5双功能催化剂上一步法制甲苯/二甲苯

doi:10.16085/j.issn.1000-6613.2021-2635

化工进展 ›› 2022, Vol. 41 ›› Issue (S1): 247-259.DOI: 10.16085/j.issn.1000-6613.2021-2635

苯与合成气在ZnAlCrO _x &HZSM-5双功能催化剂上一步法制甲苯/二甲苯

石轩¹(), 杨东元², 胡浩斌³, 王焦飞⁴, 张壮壮⁵, 贺建勋¹, 代成义¹(), 马晓迅¹^,³()

^1.西北大学化工学院，陕西西安 710069
^2.陕西延长石油（集团）有限责任公司，陕西西安 710065
^3.陇东学院化学化工学院，甘肃庆阳 745000
^4.宁夏大学化学化工学院，省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^5.延安大学化学与化工学院，陕西延安 716000

收稿日期:2021-12-27 修回日期:2022-03-30 出版日期:2022-10-20 发布日期:2022-11-10
通讯作者: 代成义,马晓迅
作者简介:石轩（1995—），男，硕士研究生，研究方向为合成气催化转化。E-mail：1043790750@qq.com。
基金资助:
陕西省重点研发计划(2020ZDLGY11-06);陕西省技术创新引导专项(2022QFY07-02);国家自然科学基金(22168042);甘肃省高等学校产业支撑引导项目(2019C-08);省部共建煤炭高效利用与绿色化工国家重点实验室开放课题(2021-K52)

One-step preparation of toluene/xylene from benzene and syngas over ZnAlCrO _x &HZSM-5 bifunctional catalyst

SHI Xuan¹(), YANG Dongyuan², HU Haobin³, WANG Jiaofei⁴, ZHANG Zhuangzhuang⁵, HE Jianxun¹, DAI Chengyi¹(), MA Xiaoxun¹^,³()

^1.School of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, China
^2.Shaanxi Yanchang Petroleum (Group) Co. , Ltd. , Xi'an 710065, Shaanxi, China
^3.College of Chemistry and Chemical Engineering, Longdong University, Qingyang 745000, Gansu, China
^4.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^5.School of Chemistry & Chemical Engineering, Yan'an University, Yan'an 716000, Shaanxi, China

Received:2021-12-27 Revised:2022-03-30 Online:2022-10-20 Published:2022-11-10
Contact: DAI Chengyi, MA Xiaoxun

摘要/Abstract

摘要：

与传统的甲醇和苯烷基化反应相比，合成气和苯一步法制甲苯/二甲苯具有苯转化率高，催化剂稳定性好，经济性高等优点。本研究将系列Zn基的金属氧化物与H-ZSM-5分子筛组成双功能催化剂，实现了合成气与苯高效转化为甲苯/二甲苯，并筛选出最优的双功能催化剂为ZnAlCrO _x &H-ZSM-5。原位红外实验发现，单独的合成气在催化剂上的转化较弱，但加入苯之后，苯与甲氧基等中间体的烷基化反应可以有效拉动合成气的转化。这表明，双功能催化剂中金属组分和分子筛组分间的协同作用拉动了该反应的高效进行。通过Zn、Mg、Ga等元素改性H-ZSM-5分子筛，使得分子筛B酸酸量与L酸酸量的比值降低，发现比值的降低有助于苯的转化。其中Zn改性后B酸与L酸的比值降低最为显著，苯转化率增加的也最多。调变反应温度、原料空速、合成气氢碳比可以控制苯的烷基化程度，调节苯烷基化各产物的选择性。ZnAlCrO _x &H-ZSM-5双功能催化剂在压力3MPa、温度400℃的反应条件下，兼具高的苯转化率（90.6%）和甲苯/二甲苯选择性（74.3%），同时CO有效利用率为33.7%。

关键词: 苯, 合成气, 烷基化, 双功能催化剂, 固定床

Abstract:

Compared with the traditional alkylation reaction of methanol and benzene, the one-step process of syngas and benzene to toluene/xylene has the advantages of high benzene conversion, good catalyst stability, and high economic efficiency. In this study, a series of Zn-based metal oxides were coupled with H-ZSM-5 zeolite to form bifunctional catalysts for the efficient conversion of syngas and benzene into toluene and xylene, and the optimal bifunctional catalyst was ZnAlCrO _x &H-ZSM-5. In-situ FT-IR analysis showed that the conversion of syngas alone on the catalyst was weak, but after the addition of benzene, the alkylation reaction of benzene with methoxy species can effectively prompt the conversion of syngas, indicating the synergy between the metal components and zeolite components in bifunctional catalyst. The modifying of H-ZSM-5 zeolite with Zn, Mg, Ga elements to reduce the ratio of B acid to L acid in zeolite was found to contribute to the conversion of benzene. Among them, the ratio of B acid to L acid was the lowest after Zn modification, and the conversion of benzene was also the highest. The degree of benzene alkylation can be controlled by adjusting the reaction temperature, the space velocity of raw materials, and the H₂/CO ratio of in syngas, and the product selectivity can be adjusted. Under the reaction conditions of pressure 3MPa and temperature 400℃, ZnAlCrO _x &H-ZSM-5 bifunctional catalyst gives both high benzene conversion (90.6%) and toluene/xylene selectivity (74.3%), and the effective utilization rate of CO is 33.7%.

Key words: benzene, syngas, alkylation, bifunctional catalysts, fixed bed

中图分类号:

O643.3

石轩, 杨东元, 胡浩斌, 王焦飞, 张壮壮, 贺建勋, 代成义, 马晓迅. 苯与合成气在ZnAlCrO _x &HZSM-5双功能催化剂上一步法制甲苯/二甲苯[J]. 化工进展, 2022, 41(S1): 247-259.

SHI Xuan, YANG Dongyuan, HU Haobin, WANG Jiaofei, ZHANG Zhuangzhuang, HE Jianxun, DAI Chengyi, MA Xiaoxun. One-step preparation of toluene/xylene from benzene and syngas over ZnAlCrO _x &HZSM-5 bifunctional catalyst[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 247-259.

图/表 17

图1 催化剂的XRD图

图2 催化剂的SEM图

图3 催化剂的微观分析

图4 ZSM-5及其改性后的FT-IR图

图5 合成气与甲醇做甲基化原料的对比[反应条件：①合成气：400℃，3MPa，H2/CO比例为5∶3，GHSV=4800mL/(gcat·h)，苯的空速0.5h-1，催化剂为ZnAlCrO x &H-ZSM-5双功能催化剂；②甲醇：400℃，0.1MPa，苯的空速0.5h-1，甲醇/苯摩尔比为1.2，催化剂为H-ZSM-5分子筛]

图6 不同路线催化剂积碳分析

图7 ZnAlCrO x &H-ZSM-5双功能催化剂的原位红外光谱(测试条件：400℃，101.325kPa和H2/CO比例为5∶3)

表1 金属氧化物&HZSM-5催化剂上合成气与苯烷基化性能

催化剂	苯的转化率/%	选择性/%				总选择性^①
催化剂	苯的转化率/%	甲苯	二甲苯	乙苯	C₉₊芳烃	总选择性^①
ZnAlCrO _x &H-ZSM-5	90.6	22.3	52.0	2.1	23.6	74.3
ZnAl₂O₄&H-ZSM-5	70.5	38.8	41.7	3.6	16.0	80.5
ZnMn₂O₄&H-ZSM-5	44.8	60.9	24.6	9.5	5.0	85.5

图8 母体H-ZSM-5和不同金属改性后ZSM-5的吡啶红外谱图

图9 金属改性分子筛对催化性能的影响[反应条件：400℃，3MPa，H2/CO比例为5∶3，GHSV=4800mL/(gcat·h)，苯的空速1h-1]

图10 分子筛B酸与L酸比值与苯转化率的关系[反应条件：400℃，3MPa，H2/CO=5∶3，GHSV=4800mL/( gcat·h)，苯的空速1h-1]

表2 合成气与苯烷基化催化剂的性能比较

催化剂	温度/℃	压力/MPa	气体空速/mL·g_cat^-1·h^-1	苯体积空速/h^-1	苯转化率/%	甲苯、二甲苯总选择性/%	参考文献
Pt/H-ZSM-5	500	3	12000	3	9.04	82.85	［19］
Pt-11Ce/H-ZSM-5	500	3	12000	3	34.2	96.7	［20］
Cu-Mn-Al₂O₃/ZSM-5	350	1.5	1885	1.25	16.7	84.5	［21］
Zr/H［Zn］5ZSM-5	400	3.3	3600	1	31	89	［22］
ZnAlCrO _x &H-ZSM-5	400	3	4800	0.57 1.14	90.6 64.9	74.3 82.4	本文研究

图11 反应温度对催化性能的影响[反应条件：3MPa，H2/CO比例为5∶3，GHSV=4800mL/(gcat·h)，苯的空速0.5h-1]

图12 进料H2/CO对催化性能的影响[反应条件：400℃，3MPa，GHSV=4800mL/(gcat·h)，苯的空速0.5h-1]

图13 气体空速对催化性能的影响[反应条件：400℃，3MPa，H2/CO比例为5∶3，苯的空速0.5h-1]

图14 苯的空速对催化性能的影响[反应条件：400℃，3MPa，H2/CO比例为5∶3，GHSV=4800mL/(gcat·h)]

图15 催化剂稳定性测试[反应条件：400℃，3MPa，H2/CO比例为5∶3，GHSV=4800mL/(gcat·h)，苯的空速0.5h-1]

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苯与合成气在ZnAlCrO _x &HZSM-5双功能催化剂上一步法制甲苯/二甲苯

One-step preparation of toluene/xylene from benzene and syngas over ZnAlCrO _x &HZSM-5 bifunctional catalyst

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