三元尖晶石与孪晶ZSM-5分子筛在苯与二氧化碳甲基化中的应用

doi:10.16085/j.issn.1000-6613.2024-0133

摘要/Abstract

摘要：

将三元尖晶石型锌镓铝金属氧化物和孪晶ZSM-5分子筛制备成双功能催化剂用于苯与二氧化碳甲基化反应。结果表明，相对于二元锌铝或锌镓金属氧化物和常规形貌ZSM-5分子筛组成的双功能催化剂，三元锌镓铝尖晶石可提高催化剂的活性，孪晶分子筛可有效增加产物中对二甲苯的含量。结合各种表征发现，三元锌镓铝尖晶石所具有的更多氧空位强化了二氧化碳的吸附，能够产生更多的甲基化中间体；同时，孪晶分子筛较少的表面酸性位点和较低的(010)晶面暴露程度有效抑制了分子筛表面二甲苯的异构化反应并凸显了对二甲苯的扩散优势，使产物中对二甲苯含量超过了热力学平衡组成。优化后的催化剂在425℃、3MPa的反应条件下表现出高达39.2%的苯转化率和37.1%的二氧化碳转化率，产物中甲苯、二甲苯总选择性为91.2%，且对二甲苯在二甲苯中的比例高达55.6%，催化性能相比二元尖晶石和常规ZSM-5组成的双功能催化剂有显著提升。

关键词: 二氧化碳, 氢, 苯, 分子筛, 复合材料, 催化

Abstract:

Ternary spinel-type ZnGaAl metal oxide and twinned ZSM-5 zeolite were integrated to prepare bifunctional catalyst which were then applied in the methylation of benzene with carbon dioxide. Experimental results revealed that the ternary spinel effectively promoted the activity and the twinned ZSM-5 increased the para-xylene content in the products, compared with the bifunctional catalyst made from the binary ZnAl or ZnGa spinel and conventional ZSM-5 counterparts. This phenomenon can be attributed to the higher concentration of oxygen vacancies provided by the ternary ZnGaAl spinel which enhanced the adsorption towards carbon dioxide and therefore generated more intermediates to react with benzene. Besides, the weak surface acidities as well as the low exposure degree of (010) surface of twinned ZSM-5 efficiently suppressed the isomerization of xylene on zeolite surface and magnified the diffusion advantages of para-xylene. The optimal bifunctional catalyst at 425℃ and 3.0MPa exhibited a benzene conversion of 39.2% and a CO₂ conversion of 37.1%, with a total toluene and xylene selectivity of 91.2% and 55.6% of all the xylene isomers being para-xylene, which is significantly better than the bifunctional catalyst composed of binary spinel and conventional ZSM-5 zeolite.

Key words: carbon dioxide, hydrogen, benzene, molecular sieve, composites, catalysis

中图分类号:

O643.36

杨帆, 赵溢涛, 朱学栋, 王达锐. 三元尖晶石与孪晶ZSM-5分子筛在苯与二氧化碳甲基化中的应用[J]. 化工进展, 2025, 44(2): 856-866.

YANG Fan, ZHAO Yitao, ZHU Xuedong, WANG Darui. Application of ternary spinel and twined ZSM-5 zeolite in methylation of benzene with carbon dioxide[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 856-866.

图/表 16

表1 不同二元尖晶石与常规ZSM-5分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的液相产物组成

催化剂	苯转化率/%	产物选择性/%					芳环收率/%
催化剂	苯转化率/%	甲苯	二甲苯	乙苯	C₉₊重芳烃	对二甲苯/二甲苯	芳环收率/%
ZG/CZ5	37.1	75.5	18.4	2.5	3.6	25.1	97.1
ZA/CZ5	35.3	75.7	18.3	2.3	3.7	24.5	95.2
ZY/CZ5	22.5	89.4	8.4	1.3	0.9	26.2	95.8
ZC/CZ5	9.5	75.6	9.1	3.7	11.6	25.4	97.2
ZI/CZ5	1.2	51.7	37.2	0.8	10.3	27.2	98.6
ZF/CZ5	13.2	19.1	0.5	68.1	12.3	28.8	93.4
MG/CZ5	10.2	70.1	22.6	2.3	5.0	24.5	96.4
MA/CZ5	14.6	60.4	31.3	3.0	5.3	26.8	97.0

表2 不同二元尖晶石与常规ZSM-5分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的气相产物组成

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZY/CZ5	30.0	69.1	8.1	2.3	19.1	97.3
ZC/CZ5	40.0	81.6	3.3	6.6	5.3	99.7
ZI/CZ5	21.1	87.2	9.1	1.3	1.6	92.3
ZF/CZ5	37.7	43.4	34.0	22.3	1.3	95.8
MG/CZ5	13.4	66.8	1.3	9.6	20.4	100.5
MA/CZ5	17.0	61.5	1.2	11.7	24.2	99.2

表2 不同二元尖晶石与常规ZSM-5分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的气相产物组成

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZY/CZ5	30.0	69.1	8.1	2.3	19.1	97.3
ZC/CZ5	40.0	81.6	3.3	6.6	5.3	99.7
ZI/CZ5	21.1	87.2	9.1	1.3	1.6	92.3
ZF/CZ5	37.7	43.4	34.0	22.3	1.3	95.8
MG/CZ5	13.4	66.8	1.3	9.6	20.4	100.5
MA/CZ5	17.0	61.5	1.2	11.7	24.2	99.2

图1 不同尖晶石的XRD谱图

表3 不同尖晶石的组成和织构性质

样品	比表面积/cm²·g^-1	平均孔径/nm	总孔体积/cm³·g^-1	体相组成（摩尔比）	表面组成（摩尔比）
ZA	184	8.72	0.40	Zn∶Al=1∶2.09	Zn∶Al=1∶1.88
ZGA	165	16.83	0.64	Zn∶Ga∶Al=1∶0.94∶0.96	Zn∶Ga∶Al=1∶0.91∶0.92
ZG	157	15.77	0.62	Zn∶Ga=1∶1.92	Zn∶Ga=1∶1.78

图2 不同尖晶石在不同激发波长下的拉曼光谱

图3 不同尖晶石的TEM照片

图4 不同金属氧化物样品的氧空位含量分析

图5 不同尖晶石的CO2-TPD曲线

图6 不同ZSM-5分子筛的XRD图谱

图7 不同ZSM-5分子筛的SEM图

图8 标准温度和压力下不同ZSM-5分子筛的氮气吸脱附曲线

表4 不同ZSM-5分子筛的组成与织构性质

样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	Si/Al
CZ5	357	148	0.28	0.11	151.2
TZ5	336	157	0.21	0.13	153.6

图9 不同分子筛的酸性表征

表5 不同尖晶石金属氧化物与不同分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的液相产物组成

催化剂	苯转化率/%	产物选择性/%					芳环收率/%
催化剂	苯转化率/%	甲苯	二甲苯	乙苯	C₉₊重芳烃	对二甲苯/二甲苯	芳环收率/%
ZA/CZ5	35.3	75.7	18.3	2.3	3.7	24.5	95.2
ZGA/CZ5	42.4	72.0	22.4	1.5	4.1	25.6	95.6
ZG/CZ5	37.1	75.5	18.4	2.5	3.6	25.1	97.1
ZGA/TZ5	39.2	67.8	23.4	5.9	2.9	55.6	96.3

表6 不同尖晶石金属氧化物与不同分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的气相产物组成

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZGA/CZ5	35.1	54.2	2.1	11.2	32.6	100.7
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZGA/TZ5	37.1	49.3	13.1	11.1	26.6	96.6

表6 不同尖晶石金属氧化物与不同分子筛组成的双功能催化剂在苯与二氧化碳甲基化反应中的气相产物组成

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZGA/CZ5	35.1	54.2	2.1	11.2	32.6	100.7
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZGA/TZ5	37.1	49.3	13.1	11.1	26.6	96.6

图10 ZGA/TZ5催化剂在苯与二氧化碳甲基化反应中的稳定性

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