不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比

李洪涛; 盛路阳; 展俊岭; 房伟贤; 梁翌; 张钰

doi:10.1016/S1872-5813(21)60035-X

不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比

doi: 10.1016/S1872-5813(21)60035-X

李洪涛^1,,
盛路阳²,
展俊岭^{2, 3},
房伟贤²,
梁翌²,
张钰^2, ,

1.
吉林化工学院材料科学与工程学院，吉林吉林132022
2.
吉林化工学院石油化工学院，吉林吉林132022
3.
吉林大学化学学院，吉林长春 130012

基金项目: 吉林省科技发展计划项目（20200401029GX, 20180201101GX）资助

详细信息

作者简介:
李洪涛：1445568181@qq.com

通讯作者:
Tel：0432-62185139，E-mail：zhang99yu@hotmail.com

中图分类号: TQ203.2
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-10
- 修回日期: 2021-01-24
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-06-30

Comparative study on the catalytic performance of zeolite catalysts with different topologies in 1-methylnaphthalene isomerization-transalkylation coupling reaction

1.
Jilin Institute of Chemical Technology, College of Materials Science and Engineering, Jilin 132022， China
2.
Jilin Institute of Chemical Technology, College of Petrochemical Technology, Jilin 132022, China
3.
Jilin University, College of Chemistry, Changchun 130012, China

Funds: The project was supported by the Science and Technology Development Foundation of Jilin Province (20200401029GX, 20180201101GX)

摘要

摘要: 以1-甲萘和均三甲苯为原料经固体酸催化的异构化-烷基转移耦合反应制备2-甲萘及二甲基萘。对MWW、BEA、FAU、MFI拓扑结构分子筛的催化性能进行对比研究，对反应机理进行探讨。采用XRD、BET、SEM、NH₃-TPD、Py-FTIR及ICP等方法对催化剂结构物性进行了表征。与具有十元环特征孔道的MFI分子筛相比，具有十二元环特征孔道的MWW、BEA、FAU分子筛表现出更好的催化活性。BEA结构分子筛具有较高的二甲基萘选择性，而MWW结构分子筛具有较高的2-甲萘选择性并表现出优异的催化稳定性。在MWW结构分子筛中，HMCM-22的1-甲萘转化率达到70.27%，2-甲萘收率达到66.69%。而HMCM-56上则同时获得35.74%的2-甲萘收率和19.00%的二甲基萘收率。该研究为以中国丰富的碳十资源为原料制备高端聚酯单体2,6-二甲基萘开辟了颇具潜力的技术路线。
- 分子筛 /
- 1-甲萘 /
- 异构化 /
- 烷基转移 /
- 2,6-二甲基萘
Abstract: The isomerization-transalkylation coupling reaction between 1-methylnaphthalene and 1,3,5-trimethylbenzene was studied over zeolite catalysts to produce 2-methylnaphthalene and dimethylnaphthalene. The catalytic performance of zeolites with MWW, BEA, FAU and MFI topological structure was investigated and the reaction mechanism was discussed. The properties of zeolites were characterized by XRD, N₂ adsorption-desorption, SEM, NH₃-TPD, Py-FTIR and ICP. Compared with MFI zeolite with 10-membered ring channel, MWW, BEA and FAU zeolite with 12-membered ring channel showed better catalytic activity. BEA zeolite exhibited higher selectivity to dimethylnaphthalene, while MWW zeolites showed higher selectivity to 2-methylnaphthalene and the best catalytic stability. As a branch of MWW zeolites, HMCM-22 showed a 1-methylnaphthalene conversion of 70.27% and a 2-methylnaphthalene yield of 66.69%. It was worth noting that a relatively high yield of 2-methylnaphthalene (35.74%) and dimethylnaphthalene (19.00%) were obtained on HMCM-56 at the same time. This research has opened up a promising route using C₁₀aromatics as raw materials for the preparation of 2,6-dimethylnaphthalene, an important polyester monomer.
- molecular sieve /
- 1-methylnaphthalene /
- isomerization /
- transalkylation /
- 2,6-dimethylnaphthalene

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FIG. 729. FIG. 729.

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图 1 样品的XRD谱图

Figure 1 XRD patterns of the samples

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图 2 样品的氮气吸附-脱附等温线

Figure 2 N₂ adsorption-desorption isotherms of the samples

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图 3 样品的SEM照片

Figure 3 SEM images of the samples

(a): HZSM-5; (b): HY; (c): HBeta; (d): HMCM-22; (e): HMCM-49; (f): HMCM-56

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图 4 样品的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of the samples

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图 5 样品的Py-FTIR谱图

Figure 5 Py-FTIR spectra of the samples

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图 6 分子筛催化异构化-烷基转移耦合反应催化稳定性

Figure 6 Catalytic stability of zeolites in the isomerization-transalkylation of 1-methylnaphthalene with 1,3,5-trimethylbenzene

(reaction conditions: t = 400 ℃, WHSV_1-MN = 0.5 h⁻¹, n_1-MN/n_TMB = 1/3, p = 0.2 MPa)

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图 7 1-MN与1,3,5-TMB异构化-烷基转移耦合反应产物的质谱图

Figure 7 Mass spectrometric analysis of the coupling reaction of 1-MN and 1,3,5-TMB isomerization-transalkylation

1: benzene; 2: toluene; 3–4: dimethylbenzene; 5: 1-ethyl-2-methylbenzene; 6: 1,3,5-trimethylbenzene; 7: 1,2,3-TMB (1,2,3-trimethylbenzene); 8: 1,2,4-TMB (1,2,4-trimethylbenzene; 9–12: tetramethylbenzene; 13: naphthalene; 14: 2-methylnaphthalene; 15: 1-methylnaphthalene;16: dimethylnaphthalene; 17: trimethylnaphthalene; 18: polymethyl naphthalene

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图 8 1-甲萘与均三甲苯异构化-烷基转移耦合反应机理

Figure 8 Mechanism diagram of the isomerization-transalkylation coupling reaction of 1-methylnaphthalene with 1,3,5-trimethylbenzene

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表 1 样品的孔结构参数

Table 1 Textural properties of the samples

Sample	A_BET/ (m²∙g⁻¹)	A_ext / (m²∙g⁻¹)	v_total/ (cm³∙g⁻¹)	v_mic/ (cm³∙g⁻¹)	v_mes/ (cm³∙g⁻¹)	A_ext/ A_BET
HZSM-5	326	87	0.24	0.09	0.10	0.48
HBeta	580	160	0.50	0.19	0.32	0.27
HY	635	138	0.47	0.40	0.08	0.21
HMCM-22	444	106	0.68	0.14	0.56	0.24
HMCM-49	447	86	0.76	0.15	0.64	0.19
HMCM-56	499	177	1.32	0.13	1.23	0.36

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表 2 元素组成、NH₃-TPD和Py-FTIR测试

Table 2 Element composition, NH₃-TPD and Py-FTIR results

Sample	SiO₂/Al₂O₃^a	Desorption peak area of NH₃-TPD^b			R^c	Acidity /(μmol∙g⁻¹)		Brønsted/Lewis
Sample	SiO₂/Al₂O₃^a	A₁(100−250 ℃)	A₂(250−400 ℃)	A₃(400−550 ℃)	R^c	Brønsted	Lewis	Brønsted/Lewis
HZSM-5	24.2	1345	570	1039	0.5	−	−	−
HY	5.1	886	1383	600	0.7	−	−	−
HBeta	17.8	805	1692	−	0.7	63	118	0.5
HMCM-22	13.1	368	906	−	0.7	124	61	2.0
HMCM-49	9.6	958	1673	−	0.6	287	103	2.8
HMCM-56	11.8	1227	1230	−	0.5	209	67	3.1
^a: measured by ICP method; ^b: calculated by Gaussian fitting method; ^c: (A₂ + A₃) to (A₁ + A₂ + A₃) ratio

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表 3 分子筛催化异构化-烷基转移耦合反应催化性能^a

Table 3 Catalytic performance of isomerization-transalkylation of 1-MN with 1,3,5-TMB over zeolites ^a

Catalysts	HZSM-5	HMCM-22	HMCM-49	HMCM-56	HBeta	HY
Conversion x/%
1-MN	77.56	70.27	78.04	80.70	93.34	89.71
1,3,5-TMB	28.14	63.53	69.58	76.88	80.63	50.93
Distribution^b s/%
2-MN	91.16	94.46	89.28	55.54	13.74	29.00
DMNs	5.56	2.53	5.28	29.52	42.76	35.95
TMNs	1.20	2.14	1.85	7.39	32.53	15.63
NP	2.08	0.87	3.59	7.55	10.97	19.42
Yield^c w/%
2-MN	37.05	66.34	57.66	35.74	7.53	16.70
DMNs	2.26	1.82	3.41	19.00	23.41	20.69
2,6-DMN/DMNs	0.55	0.37	0.41	0.35	0.38	0.34
Yield^d w/%
2-MN	5.58	66.69	55.95	52.69	53.18	52.29
DMNs	2.04	0.93	2.46	9.23	5.32	6.15
2,6-DMN/DMNs	0.50	0.46	0.38	0.36	0.41	0.37
^a: t = 400 ℃, WHSV_1-MN = 0.5 h⁻¹, n_1-MN/n_TMB = 1/3, p = 0.2 MPa, T.O.S = 1 h ^b: Mole of specific product×100/mole of 1-MN derivatives, including NP (naphthalene), 2-MN (2-methylnaphthalene), DMNs (dimethyl naphthalene) and TMNs (trimethyl naphthalene) ^c: Mole of 2-MN (or DMNs) in product×100/mole of 1-MN in raw materials，T.O.S = 1 h ^d: T.O.S = 6 h

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