Mg-La-HY-SBA-15分子筛催化甲醇烷基化反应

李艳歌; 刘羽顺; 沈健; 孙悦

Mg-La-HY-SBA-15分子筛催化甲醇烷基化反应

李艳歌¹,
刘羽顺²,
沈健¹,
孙悦^1, ,

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
镇海炼化有限公司, 浙江宁波 315200

详细信息

中图分类号: TQ426.6
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出版历程
- 收稿日期: 2018-06-20
- 修回日期: 2018-09-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-12-10

Alkylation of phenol with methanol over Mg-La-HY-SBA-15 zeolite

1.
College of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Sinopec Zhenhai Refining & Chemical Company, Ningbo 315200, China

More Information

Corresponding author: SUN Yue, Tel: 13842357621, E-mail: sunyue19791980@126.com

摘要

摘要: 用两步浸渍法制备了Mg-La-HY-SBA-15复合分子筛，在小型固定床反应器上考察了苯酚甲醇烷基化性能；通过SEM-EDS、Py-FTIR等表征手段分析了Mg-La-HY-SBA-15分子筛的孔结构和酸性。结果表明，Mg负载到HY-SBA-15分子筛上且未改变其微介孔结构；Mg改性后降低了载体的总酸量，增加了总Lewis酸，提高了邻甲酚的选择性和收率。
- Mg-La-HY-SBA-15 /
- 微介孔 /
- 苯酚 /
- 烷基化 /
- 邻甲酚
Abstract: Mg-La-HY-SBA-15 zeolite prepared by separate-step impregnation method was used to catalyze alkylation of phenol with methanol. The porous structure and acid property were characterized by SEM-EDS, Py-FTIR and others.The results found that Mg was successfully supported on La-HY-SBA-15 zeolite. Mg-La-HY-SBA-15 had micro-mesoporous structures. Compared with mono-mental modification, bimental modification reduced the amount of total acid and gained more total Lewis acid. At the same time, the selectivity and yield of o-cresol were increased.
- Mg-La-HY-SBA-15 /
- micro-mesoporous /
- phenol /
- alkylation /
- o-cresol

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图 1 样品的NH₃-TPD谱图

Figure 1 NH₃-TPD profiles of the samples

a: HY-SBA-15; b: 10%La-HY-SBA-15; c: 2%Mg-10%La-HY-SBA-15; d: 5%Mg-10%La-HY-SBA-15; e: 8%Mg-10%La-HY-SBA-15

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图 2 样品的大角XRD谱图

Figure 2 XRD patterns of the supports

a: HY; b: HY-SBA-15; c: 10%La-HY-SBA-15; d: 2%Mg-10%La-HY-SBA-15; e: 5%Mg-10%La-HY-SBA-15; f: 8%Mg-10%La-HY-SBA-15

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图 3 样品的N₂吸附-脱附谱图

Figure 3 N₂ adsorption-desorption isotherms of the samples

a: HY-SBA-15; b: 10%La-HY-SBA-15; c: 2%Mg-10%La-HY-SBA-15; d: 5%Mg-10%La-HY-SBA-15; e: 8%Mg-10%La-HY-SBA-15

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图 4 样品的SEM照片

Figure 4 SEM images of the samples

(a): SBA-15; (b): HY; (c): HY-SBA-15; (d): 10%La-HY-SBA-15; (e, f): 5%Mg-10%La-HY-SBA-15

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图 5 5%Mg-10%La-HY-SBA-15样品的EDS谱图

Figure 5 EDS images of 5%Mg-10%La-HY-SBA-15 samples

(a): EDS spectrum of 5%Mg-10%La-HY-SBA-15 sample; (b): EDS mapping of 5%Mg-10%La-HY-SBA-15 sample

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图 6 样品的NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of the samples

a: 10%La-HY-SBA-15; b: 2%Mg-10%La-HY-SBA-15; c: 5%Mg-10%La-HY-SBA-15; d: 8%Mg-10%La-HY-SBA-15

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图 7 100 ℃脱附后样品的Py-FTIR谱图

Figure 7 Py-FTIR spectra of the samples collected after treatment at 100 ℃ under vacuum

a: 10%La-HY-SBA-15; b: 2%Mg-10%La-HY-SBA-15; c: 5%Mg-10%La-HY-SBA-15; d: 8%Mg-10%La-HY-SBA-15

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图 8 不同脱附温度下5%Mg-10%La-HY-SBA-15样品的Py-FTIR谱图

Figure 8 Py-FTIR spectra of 5%Mg-10%La-HY-SBA-15 sample at different desorption temperatures

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图 9 5%Mg-10%La-HY-SBA-15分子筛反应的稳定性

Figure 9 Stability test of 5%Mg-10%La-HY-SBA-15 sample

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表 1 不同样品的孔结构性质

Table 1 Textural properties of different samples

Sample	A_BET/(m²·g^-1)	v_t/(cm³·g^-1)	d/nm
30%HY-SBA-15	643	0.864	5.51
10%La-HY-SBA-15	396	0.705	5.34
2%Mg-10%La-HY-SBA-15	375	0.535	5.37
5%Mg-10%La-HY-SBA-15	342	0.501	5.42
8%Mg-10%La-HY-SBA-15	301	0.453	5.49

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表 2 样品的酸量

Table 2 Acid amount of the sample

Sample	Acid amount /(mmol·g^-1)
Sample	T	TL	TB	SL	SB	ML	MB	WL	WB
10%La-HY-SBA-15	2.34	1.47	0.60	0.11	0.08	1.36	0.52	0.12	0.05
2%Mg-10%La-HY-SBA-15	1.94	1.70	0.14	0.10	0.05	1.42	0.05	0.18	0.04
5%Mg-10%La-HY-SBA-15	1.87	1.78	0.09	0.08	0.02	1.50	0.04	0.20	0.03
8%Mg-10%La-HY-SBA-15	1.37	1.23	0.15	0.05	0.02	0.82	0.05	0.36	0.08
T: total acid; TL: total L acid; TB: total B acid; SL: strong L acid; SB: strong B acid; ML: moderate L acid; MB: moderate B acid; WL: weak L acid; WB: weak B acid

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表 3 催化剂的烷基化性能

Table 3 Alkylation properties of the zeolites

Sample	x/%	s/%						w/%
Sample	x/%	o-cresol	p-cresol	m-cresol	xylenol	anisole	others	w/%
HY-SBA-15	58.2	76.6	5.2	3.5	4.4	4.7	5.6	44.58
10%La-HY-SBA-15	87.8	80.5	3.9	2.6	3.3	4.4	5.3	70.68
2%Mg-10%La-HY-SBA-15	84.2	88.3	2.2	0.8	1.6	2.5	4.6	74.35
5%Mg-10%La-HY-SBA-15	81.5	93.1	1.4	0.3	1.0	1.9	2.3	75.88
8%Mg-10%La-HY-SBA-15	65.3	84.6	2.9	1.7	2.4	3.6	4.8	55.24
reaction conditions: t=440 ℃，n(phenol)/n(methanol)=1：4，WHSV=2 h^-1; x: conversion of phenol; s: selectivity of product; w: yield of o-cresol

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