固相外延生长法制备ZSM-5@Silicalite-1分子筛及其CO<sub>2</sub>加氢耦合甲苯烷基化反应的影响

贾艺敏; 牛鹏宇; 贾丽涛; 林明桂; 郭荷芹; 肖勇; 侯博; 李德宝

doi:10.19906/j.cnki.JFCT.2024012

固相外延生长法制备ZSM-5@Silicalite-1分子筛及其CO₂加氢耦合甲苯烷基化反应的影响

doi: 10.19906/j.cnki.JFCT.2024012

贾艺敏^{1, 2,},
牛鹏宇^1, ,,
贾丽涛^1, ,,
林明桂^1,,
郭荷芹^1,,
肖勇^1,,
侯博^1,,
李德宝^{1, 3,}

1.
中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
中国科学院洁净能源创新研究院, 辽宁大连 116023

基金项目: 山西省重点研发计划 (202102090301003)资助

详细信息

通讯作者:
Tel: 0351-4040428, E-mail: niupy@sxicc.ac.cn

jialitao910@163.com

中图分类号: O643
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出版历程
- 收稿日期: 2024-01-22
- 修回日期: 2024-02-27
- 录用日期: 2024-02-28
- 网络出版日期: 2024-03-30

Effect of ZSM-5@Silicalite-1 zeolites prepared by solid phase epitaxial growth method on CO₂ hydrogenation and toluene alkylation reactions

JIA Yimin^{1, 2
,},
NIU Pengyu^{1
, ,},
JIA Litao^{1
, ,},
LIN Minggui^1
,,
GUO Heqin^1
,,
XIAO Yong^1
,,
HOU Bo^1
,,
LI Debao^{1, 3
,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Dalian National Laboratory of Clean Energy, Dalian 116023, China

Funds: The project was supported by the Basic Research Program of Shanxi key research project (202102090301003).

摘要

摘要: CO₂加氢合成高附加值的芳烃对于缓解CO₂排放引起的能源气候问题具有重要意义。本研究采用固相法在ZSM-5表面外延生长Silicalite-1，制备出ZSM-5@Silicalite-1分子筛。同时制备高活性氧化物ZnZrO_x，并与ZSM-5@Silicalite-1物理混合组成ZnZrO_x/ ZSM-5@Silicalite-1双功能催化剂，研究了CO₂加氢耦合甲苯烷基化催化性能。相比于ZnZrO_x/ZSM-5催化剂，分子筛改性后的双功能催化剂提高了对二甲苯（PX）选择性。研究了晶化条件（硅源、晶化过程、晶化次数）对ZSM-5外延生长Silicalite-1的影响，以及Silicalite-1钝化层厚度对CO₂加氢耦合甲苯烷基化反应性能的影响。在400 ℃、3 MPa反应条件下，ZZO/1:3.5Z5-Na-SiO₂催化剂的甲苯转化率为12.0%，二甲苯选择性为77.4%，在二甲苯中对二甲苯选择性为73.4%。通过SEM、XRD、N₂吸附-脱附、XPS、NH₃-TPD、Py-FTIR等表征，研究了分子筛的结构和酸性质。结果表明，通过固相外延生长，延长ZSM-5的孔道，增加间二甲苯（MX）、邻二甲苯（OX）的扩散阻力，同时钝化外表面的酸性，可以有效提高对二甲苯（PX）的选择性。固相外延生长法改性ZSM-5分子筛，摒弃了以往堵塞孔以缩小孔口改性分子筛的缺点，在保证催化剂活性的同时提高了产物选择性。
- MFI型分子筛 /
- 外延生长 /
- 对二甲苯 /
- 固相法 /
- CO₂加氢耦合甲苯烷基化
Abstract: CO₂ hydrogenation to synthesize high value-added aromatics is of great significance to alleviate the energy climate problem caused by CO₂ emission. It is generally believed that the reaction course of CO₂ hydrogenation of toluene coupled with alkylation to produce xylenes is as follows: firstly, CO₂ reacts with H₂ to produce methanol intermediates, and then the methanol intermediates react with toluene on zeolite catalysts to produce para-xylene (PX) by alkylation. According to the reaction pathway, it is necessary to construct a bifunctional catalyst with synergistic matching of the two process conditions to simultaneously realize the hydrogenation of CO₂ to methanol intermediate and the alkylation of the intermediate and toluene to generate para-xylene. The ZnZrO_x/ZSM-5 catalytic system, in which the ZnZrO_x has strong thermal stability and CO₂ activation ability, and the ZSM-5 has a good morphology selectivity for PX, is considered to be a promising CO₂ hydrogenated toluene coupled alkylation catalyst. However, this system still suffers from low PX selectivity, mainly due to the presence of non-selective acidic sites on the outer surface of the zeolite or near the pore orifice, which leads to the generation of side reactions, such as deep methylation and toluene isomerization, and reduces the selectivity. In this paper, ZSM-5@Silicalite-1 zeolites were prepared by epitaxial growth of Silicalite-1 on the surface of ZSM-5 using solid-phase synthesis. At the same time, the highly active oxide ZnZrO_x was prepared and physically mixed with ZSM-5@Silicalite-1 to form a ZnZrO_x/ ZSM-5@Silicalite-1 bifunctional catalyst to study the catalytic performance of CO₂ hydrogenation coupled with toluene alkylation. Compared with the ZnZrO_x/ZSM-5 catalyst, the modified zeolite improved the para-xylene (PX) selectivity. The effect of crystallization conditions (silicon source, crystallization process, and number of crystallizations) on the epitaxial growth of Silicalite-1 from ZSM-5 was investigated, as well as the effect of the thickness of the Silicalite-1 passivation layer on the performance of the reaction between carbon dioxide hydrogenation and toluene alkylation. The ZZO/1:3.5Z5-Na-SiO₂ catalyst showed a toluene conversion of 12.0%, a xylene selectivity of 77.4%, and a PX selectivity of 73.4% in xylene under 400 ℃ and 3 MPa reaction conditions. The structure and acid properties of the zeolites were investigated in detail by SEM, XRD, N₂ adsorption-desorption, XPS, NH₃-TPD and Py-FTIR characterization, and the results show that the selectivity of para-xylene (PX) can be effectively improved by solid-phase epitaxial growth to extend the pore channels of ZSM-5, increase the diffusion resistance of m-xylene (MX) and o-xylene (OX), and passivate the acidity of the outer surface at the same time. This method abandons the disadvantage of previous modification of molecular sieves by blocking the pores to narrow the orifice, and upgrades the product selectivity while ensuring the catalyst activity.
- MFI-type zeolites /
- epitaxial growth /
- para-xylene /
- solid phase synthesis /
- CO₂ hydrogenation and toluene alkylation

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图 1 样品（a）ZSM-5、S1:1Z5-Na-SiO₂-1、S1:1Z5-TEOS-1、S1:1Z5-NH₃-SiO₂-1、S1:1Z5-SiO₂-1，（b）S1:1Z5-Na-SiO₂-2、S1:1Z5-TEOS-2、S1:1Z5-NH₃-SiO₂-2、S1:1Z5-SiO₂-2，（c）D1:1Z5-Na-SiO₂、D1:1Z5-TEOS、D1:1Z5-NH₃-SiO₂、D1:1Z5-SiO₂的XRD谱图；（d）ZSM-5、S1:1Z5-Na-SiO₂-1、S1:1Z5-TEOS-1、S1:1Z5-NH₃-SiO₂-1、S1:1Z5-SiO₂-1的N₂吸附-脱附等温线

Figure 1 (a) XRD patterns of ZSM-5, S1:1Z5-Na-SiO₂-1, S1:1Z5-TEOS-1, S1:1Z5-NH₃-SiO₂-1, and S1:1Z5-SiO₂-1; (b) XRD patterns of S1:1Z5-Na-SiO₂-2, S1:1Z5-TEOS-2, S1:1Z5-NH₃-SiO₂-2, and S1:1Z5-SiO₂-2; (c) XRD patterns of D1:1Z5-Na-SiO₂, D1:1Z5-TEOS, D1:1Z5-NH₃-SiO₂, and D1:1Z5-SiO₂; and (d) N₂ adsorption-desorption isotherms of ZSM-5, S1:1Z5-Na-SiO₂-1, S1:1Z5-TEOS-1, S1:1Z5-NH₃-SiO₂-1, and S1:1Z5-SiO₂-1

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图 2 样品（a）ZSM-5,（b1-e1）S1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂-1，（b2-e2）S1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂-2，（b3-e3）D1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂的SEM图像

Figure 2 SEM images of samples (a) ZSM-5, (b1-e1) S1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂-1, (b2-e2) S1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂-2, and (b3-e3) D1:1Z5-Na-SiO₂/TEOS/NH₃-SiO₂/SiO₂

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图 3 ZSM-5、S1:1Z5-Na-SiO₂-1、S1:1Z5-TEOS-1、S1:1Z5-NH₃-SiO₂-1、S1:1Z5-SiO₂-1的（a）XPS Al 2p谱图，（b）NH₃-TPD曲线，（c）350 ℃的Py-FTIR谱图和（d）ZSM-5、S1:1Z5-Na-SiO₂-2、S1:1Z5-TEOS-2、S1:1Z5-NH₃-SiO₂-2和S1:1Z5-SiO₂-2的350 ℃ Py-FTIR谱图

Figure 3 (a) XPS Al 2p spectra, (b) NH₃-TPD curves and (c) Py-FTIR spectra at 350°C for ZSM-5, S1:1Z5-Na-SiO₂-1, S1:1Z5-TEOS-1, S1:1Z5-NH3-SiO₂-1, S1:1Z5-SiO₂-1, and (d) 350°C Py-FTIR spectra of ZSM-5, S1:1Z5-Na-SiO₂-2,S1:1Z5-TEOS-2, S1:1Z5-NH₃-SiO₂-2, and S1:1Z5-SiO₂-2

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图 4 ZSM-5、1:1Z5-Na-SiO₂、1:2Z5-Na-SiO₂、1:3Z5-Na-SiO₂、1:3.5Z5-Na-SiO₂和1:4Z5-Na-SiO₂的（a）XRD谱图和（b）N₂吸附-脱附等温线

Figure 4 (a) XRD patterns and (b) N₂ adsorption-desorption isotherms of ZSM-5, 1:1Z5-Na-SiO₂, 1:2Z5-Na-SiO₂,1:3Z5-Na-SiO₂, 1:3.5Z5-Na-SiO₂ and 1:4Z5-Na-SiO₂

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图 5 催化剂的SEM图像

Figure 5 SEM images of catalysts

(a) ZSM-5; (b) 1:1Z5-Na-SiO₂; (c) 1:2Z5-Na-SiO₂; (d) 1:3Z5-Na-SiO₂; (e) 1:3.5Z5-Na-SiO₂; (f) 1:4Z5-Na-SiO₂

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图 6 ZSM-5、1:1Z5-Na-SiO₂、1:2Z5-Na-SiO₂、1:3Z5-Na-SiO₂、1:3.5Z5-Na-SiO₂和1:4Z5-Na-SiO₂的（a）NH₃-TPD曲线和（b）350 ℃的Py-FTIR谱图

Figure 6 (a) NH₃-TPD curves and (b) Py-FTIR spectra of ZSM-5, 1:1Z5-Na-SiO₂, 1:2Z5-Na-SiO₂, 1:3Z5-Na-SiO₂,1:3.5Z5-Na-SiO₂ and 1:4Z5-Na-SiO₂ at 350°C

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图 7 ZnZrO_x的（a）SEM图像，（b）XRD谱图，（c）Raman谱图和（d）N₂吸附-脱附等温线

Figure 7 (a) SEM image, (b) XRD patterns, (c) Raman spectra and (d) N₂ adsorption-desorption isotherms of ZnZrO_x

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图 8 ZnZrO_x的（a）H₂-TPR谱图，（b）XPS O 1s 谱图，（c）EPR谱图，（d）CO₂-TPD谱图和（e）H₂-TPD谱图

Figure 8 (a) H₂-TPR curve, (b) XPS O 1s spectra, (c) EPR spectra, (d) CO₂-TPD curve and (e) H₂-TPD curve of ZnZrO_x

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图 9 CO₂加H₂与甲苯烷基化反应（a）在不同硅源制备的ZSM-5@Silicalite-1和ZnZrO_x的双功能催化剂上的液相产物选择性，（b）气相产物选择性，（c）不同晶化次数的ZSM-5@Silicalite-1和ZnZrO_x的双功能催化剂上的液相产物选择性和（d）不同钝化层厚度分子筛和ZnZrO_x的双功能催化剂上的液相产物选择性，反应条件：400 ℃，3 MPa，H₂/CO₂为3∶1，GHSV为9000 h⁻¹，甲苯LHSV为2 h⁻¹

Figure 9 CO₂ hydrogenation and toluene alkylation reactions (a) liquid-phase product selectivity over bifunctional catalysts of ZSM-5@Silicalite-1 and ZnZrO_x prepared with different silicon sources, (b) gas-phase product selectivity, (c) liquid-phase product selectivity over bifunctional catalysts of ZSM-5@Silicalite-1 and ZnZrO_x with different numbers of crystallizations and (d) liquid-phase product selectivity over bifunctional catalysts of zeolites with different shell thicknesses and ZnZrO_x. Reaction conditions: 400 ℃, 3 MPa, H₂/CO₂=3/1, GHSV=9000 h⁻¹, and LHSV of toluene = 2 h⁻¹.

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表 1 ZSM-5和S1:1Z5@Silicalite-1分子筛的织构性质

Table 1 Textural properties of ZSM-5 and S1:1Z5@Silicalite-1 zeolite

Catalyst	Relative crystallinity/%	BET surface area S/(m²·g⁻¹)	Pore volume v/(cm³·g⁻¹)	Pore size d/nm
ZSM-5	100	364	0.15	1.92
S1:1Z5-SiO₂-1	87	325	0.13	3.96
S1:1Z5-SiO₂-2	84	443	0.18	5.68
S1:Z5- Na-SiO₂-1	95	337	0.11	3.21
S1:1Z5-Na-SiO₂-2	82	324	0.14	4.95
S1:1Z5-NH₃-SiO₂-1	96	258	0.10	3.41
S1:1Z5-NH₃-SiO₂-2	73	253	0.10	5.09
S1:1Z5-TEOS-1	96	413	0.17	2.17
S1:1Z5-TEOS-2	97	360	0.15	1.96

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表 2 350 ℃下从Py-FTIR得到的ZSM-5和S1:1Z5@Silicalite-1分子筛的B酸和L酸量

Table 2 Amounts of Brønsted and Lewis acids of ZSM-5 and S1:1Z5@Silicalite-1 zeolite from Py-FTIR at 350°C

Catalyst	L/(μmol·g⁻¹)	B+L/(μmol·g⁻¹)	B/(μmol·g⁻¹)	B/L	Total/(μmol·g⁻¹)
ZSM-5	2.8	29.6	15.2	5.4	47.5
S1:1Z5-Na-SiO₂-1	1.2	25.1	5.7	4.75	32.0
S1:1Z5-Na-SiO₂-2	0.8	26.0	9.2	11.5	36.0
S1:1Z5-TEOS-1	3.3	57.5	33.5	10.2	94.3
S1:1Z5-TEOS-2	2.2	35.6	25.6	11.6	63.3
S1:1Z5-NH₃-SiO₂-1	2.2	25.6	10.1	4.6	37.9
S1:1Z5-NH₃-SiO₂-2	0.7	30.5	11.7	16.7	43.0
S1:1Z5-SiO₂-1	1.2	24.8	11.0	9.2	37.0
S1:1Z5-SiO₂-2	1.0	28.5	15.5	15.5	45.0

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表 3 不同钝化层厚度ZSM@Silicalite-1分子筛的织构性质

Table 3 Textural properties of ZSM@Silicalite-1 zeolites with different shell thicknesses

Catalyst	BET surface area S/(m²·g⁻¹)	Pore volume v/(cm³·g⁻¹)	Pore size d/nm
ZSM-5	383	0.14	1.63
1:1Z5- Na-SiO₂	337	0.11	3.21
1:2Z5- Na-SiO₂	202	0.05	5.13
1:3Z5- Na-SiO₂	165	0.04	5.18
1:3.5Z5- Na-SiO₂	139	0.03	6.5
1:4Z5- Na-SiO₂	143	0.03	6.6

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表 4 350 ℃下从Py-FTIR得到的不同钝化层厚度分子筛的B酸和L酸量

Table 4 Amounts of Brønsted and Lewis acids of zeolite with different shell thicknesses from Py-FTIR at 350 ℃

Catalyst	L/(μmol·g⁻¹)	B+L/(μmol·g⁻¹)	B/(μmol·g⁻¹)	B/L	Total/(μmol·g⁻¹)
ZSM-5	2.8	29.6	15.2	5.4	47.5
1:1Z5-Na-SiO₂	1.2	23.1	9.8	8.2	34.1
1:2Z5-Na-SiO₂	0.8	7.5	4.3	5.4	12.6
1:3Z5-Na-SiO₂	0.8	3.9	2.7	3.4	7.5
1:3.5Z5-Na-SiO₂	0.6	3.8	1.9	3.2	6.3
1:4Z5-Na-SiO₂	1.9	2.5	3.8	2	8.2

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表 5 ZnZrO_x的织构性质

Table 5 Textural properties of ZnZrO_x

Catalyst	BET surface area S/(m²·g⁻¹)	Pore volume v/(cm³·g⁻¹)	Pore size d/nm
ZnZrO_x	29	0.03	3

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表 6 不同晶化条件催化剂上CO₂加氢耦合甲苯烷基化反应气相产物分析

Table 6 Gas-phase products analysis of CO₂ hydrogenation and toluene alkylation over catalysts with different crystallization conditions

Catalyst	CO₂ conv./%	C₁−C₅	CO	S_methy
ZZO/Z5	18.6	33.1	59.9	7.0
ZZO/S1:1Z5-TEOS-1	15.5	17.9	75.4	6.7
ZZO/S1:1Z5-Na-SiO₂-1	11.3	29.4	59.9	10.7
ZZO/S1:1Z5-NH₃-SiO₂-1	15.4	53.1	39.5	7.4
ZZO/S1:1Z5-SiO₂-1	10.1	26.7	61.7	11.6

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表 7 不同晶化条件催化剂上CO₂加氢耦合甲苯烷基化反应液相产物分析

Table 7 Liquid phase product analysis of CO₂ hydrogenation and toluene alkylation over catalysts with different crystallization conditions

Catalyst	Conv. T/%	Selectivity/%				PX/X
Catalyst	Conv. T/%	PX	MX	OX	other	PX/X
ZZO/Z5	32.4	28.4	33.6	18.4	19.6	35.3
ZZO/S1:1Z5-TEOS-1	36.3	27.1	33.9	18.2	20.8	34.2
ZZO/S1:1Z5-TEOS-2	29.0	33.9	30.2	18.4	17.5	41.1
ZZO/D1:1Z5-TEOS	29.3	20.4	41.0	18.4	20.2	25.5
ZZO/S1:1Z5-SiO₂-1	26.5	34.7	24.2	13.8	27.3	47.7
ZZO/S1:1Z5-SiO₂-2	29.5	23.8	35.2	17.3	23.7	28.4
ZZO/D1:1Z5-SiO₂	29.1	18.8	34.7	12.7	33.8	17.4
ZZO/S1:1Z5-NH₃-SiO₂-1	23.3	40.4	21.1	13.3	25.2	54.0
ZZO/S1:1Z5-NH₃-SiO₂-2	25.5	30.5	32.5	15.1	21.9	39.0
ZZO/D1:1Z5-NH₃-SiO₂	12.7	29.7	28.8	27.9	13.6	34.4
ZZO/S1:1Z5-Na-SiO₂-1	23.9	41.9	19.9	13.2	25.0	55.8
ZZO/S1:1Z5-Na-SiO₂-2	10.1	34.9	26.8	14.7	23.6	45.7
ZZO/D1:1Z5-Na-SiO₂	1.3	23.1	14.0	24.1	38.8	26.2

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