碱改性ZSM-5分子筛及其甲醇芳构化性能

李君华; 谢锦印; 张丹; 刘琳; 邢锦娟

doi:10.1016/S1872-5813(21)60016-6

碱改性ZSM-5分子筛及其甲醇芳构化性能

doi: 10.1016/S1872-5813(21)60016-6

李君华^1,,
谢锦印²,
张丹^1, ,,
刘琳²,
邢锦娟²

1.
辽宁石油化工大学石油化工学院，辽宁抚顺 113001
2.
渤海大学化学与化工学院，辽宁锦州 121013

基金项目: 国家自然科学基金（21606117）和辽宁省创新团队项目（2018-479-14, LT2015001）资助

详细信息

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Tel：13940698270，E-mail：bestzhangdan@163.com

中图分类号: O643；TQ246
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出版历程
- 收稿日期: 2020-10-09
- 修回日期: 2020-11-23
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Effect of alkali modification to ZSM-5 zeolite on the aromatization of methanol

1.
School of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China
2.
School of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013, China

Funds: The project was supported by the National Natural Science Foundation of China (21606117) and Innovation Team Project of Liaoning Province (2018-479-14, LT2015001)

摘要

摘要: 利用乙酸钠和柠檬酸钠对ZSM-5分子筛进行脱硅改性处理，并通过XRD、SEM、NH₃-TPD、²⁷Al MAS NMR、吡啶吸附红外光谱和N₂吸附-脱附等表征手段对ZSM-5分子筛结构、酸量、比表面积及孔体积等物化性质进行表征分析。结果表明，碱改性使分子筛的孔径增加且形成合适的微-介孔结构，同时，使L酸量和B酸量明显降低。当乙酸钠溶液浓度为0.5 mol/L时，改性的分子筛在形成大量介孔结构的同时具有合适的B/L值，使催化剂的寿命延长并展现出最优的催化性能。与微孔ZSM-5相比，使用寿命由20 h延长到74 h，芳烃最高产率从20.97%提高到40.05%。
- ZSM-5分子筛 /
- 碱改性 /
- 介孔 /
- 甲醇芳构化
Abstract: ZSM-5 zeolites were modified by desilication with sodium acetate and sodium citrate. The physicochemical properties of ZSM-5 zeolites, such as crystal structure, acid content, surface area and pore volume, were characterized by XRD, SEM, NH₃-TPD, ²⁷Al MAS NMR, pyridine adsorption infrared spectroscopy and N₂ adsorption-desorption isotherms. The results indicate that pore size of the zeolite increases and mesoporous structures are formed by alkali modification, and the amount of Lewis and Brönsted acid contents decreases obviously. When the concentration of sodium acetate solution is 0.5 mol/L, the modified zeolite has a suitable B/L value for the aromatization of methanol while forming a large number of mesoporous structures. Compared with microporous ZSM-5, the catalyst life is increased from 20 h to 74 h, and the highest yield of aromatics is increased from 20.97% to 40.05%.
- ZSM-5 zeolite /
- alkali modified /
- mesoporous /
- aromatization of methanol

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图 1 碱改性前后ZSM-5分子筛的XRD谱图

Figure 1 XRD patterns of ZSM-5 zeolites before and after alkali modification

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图 2 碱改性前后ZSM-5分子筛的SEM((a)、(c)、(e))照片和TEM((b)、(d)、(f))照片

Figure 2 SEM and TEM images of the ZSM-5 zeolite before and after alkali modification ZSM-5 ((a), (b)), SA-ZSM-5-0.5 ((c), (d)) and SC-ZSM-5-0.5 ((e), (f))

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图 3 碱改性前后ZSM-5的氮气吸附-脱附曲线(a)和孔径分布曲线(b)

Figure 3 Nitrogen adsorption-desorption curve (a) and pore size distribution curve (b) of ZSM-5 zeolites before and after alkali modification

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图 4 碱改性前后ZSM-5分子筛的 ²⁷Al MAS NMR谱图

Figure 4 ²⁷Al MAS NMR spectra of ZSM-5 zeolites before and after alkali modification

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图 5 碱改性前后ZSM-5分子筛的NH₃-TPD谱图

Figure 5 NH₃-TPD spectra of ZSM-5 zeolites before and after alkali modification

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图 6 碱改性前后ZSM-5分子筛的Py-FTIR谱图

Figure 6 Py-FTIR spectra of ZSM-5 zeolites before and after alkali modification (a−d): SA-ZSM-5-0.1, 0.2, 0.5, 1.0; e: SC-ZSM-5-0.5

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图 7 不同碱浓度改性ZSM-5分子筛的甲醇转化率随时间的变化

Figure 7 Methanol conversion of ZSM-5 modified with different alkali concentration changes with time

reaction conditions: t = 420 ℃; the flow of N₂ = 20 mL/min; WHSV = 4.74 h⁻¹; p = 0.1 MPa

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图 8 不同碱浓度改性ZSM-5分子筛的芳烃收率随时间的变化

Figure 8 Aromatics yield of ZSM-5 modified with different alkali concentration changes with time

reaction conditions: t = 420 ℃; the flow of N₂ = 20 mL/min; WHSV = 4.74 h⁻¹; p = 0.1 MPa

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图 9 不同碱液改性ZSM-5分子筛的甲醇转化率随时间的变化

Figure 9 Methanol conversion of ZSM-5 modified with different alkali changes with time

reaction conditions: t = 420 ℃; the flow of N₂ = 20 mL/min; WHSV = 4.74 h⁻¹; p = 0.1 MPa

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表 1 ZSM-5分子筛样品的相对结晶度和硅铝比

Table 1 Relative crystallinity and n(SiO₂)/n(Al₂O₃) of ZSM-5 zeolite samples

Sample	Relative crystallinity /%	n(SiO₂)/n(Al₂O₃)
SC-ZSM-5-0.5	99.61	70
SA-ZSM-5-1.0	99.66	65
SA-ZSM-5-0.5	99.58	73
SA-ZSM-5-0.2	99.99	78
ZSM-5	100	81

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表 2 ZSM-5分子筛样品的结构性质

Table 2 Structural properties of ZSM-5 zeolite samples

Catalyst	S_BET/ (m²·g⁻¹)	S_exter/ (m²·g⁻¹)	v_total/ (cm³·g⁻¹)	v_micro/ (cm³·g⁻¹)
SC-ZSM-5-0.5	348	89	0.25	0.11
SA-ZSM-5-1.0	351	86	0.28	0.08
SA-ZSM-5-0.5	359	94	0.26	0.09
SA-ZSM-5-0.2	341	82	0.22	0.11
ZSM-5	321	54	0.20	0.12

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表 3 ZSM-5分子筛样品的酸性和酸量分布

Table 3 Acidity and acidity distribution of ZSM-5 zeolite samples

Catalyst	Relative acid amounts		Acid amounts/(mmol·g⁻¹)		B/L
Catalyst	strong acidity	weak acidity	L	B	B/L
SC-ZSM-5-0.5	0.628	0.712	0.24	1.19	4.96
SA-ZSM-5-1.0	0.666	0.733	0.30	1.14	3.80
SA-ZSM-5-0.5	0.684	0.718	0.27	1.31	4.85
SA-ZSM-5-0.2	0.745	0.773	0.41	1.97	4.81
ZSM-5	1	1	3.35	5.37	1.60
note：the relative acid amount was obtained from the NH₃-TPD curve; the acid amount data were obtained from a Py-FTIR spectrum at 200 ℃

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