ZSM-5分子筛催化甲醇制汽油反应中的晶粒粒径效应研究

邵娟; 付廷俊; 常江伟; 万威利; 齐瑞岳; 李忠

ZSM-5分子筛催化甲醇制汽油反应中的晶粒粒径效应研究

太原理工大学煤科学与技术教育部和山西省重点实验室, 山西太原 030024

基金项目:

国家自然科学基金 21606160

山西省科技基础平台建设项目 2015091009

太原理工大学人才资助项目 tyut-rc201454a

详细信息

通讯作者:
李忠, Tel/Fax:0351-6018526, E-mail:lizhong@tyut.edu.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2016-06-06
- 修回日期: 2016-08-24
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Effect of ZSM-5 crystal size on its catalytic properties for conversion of methanol to gasoline

Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China

Funds:

National Natural Science Foundation of China 21606160

Science and Technology Infrastructure Plat form Construction Program of Shanxi Procince 2015091009

the Qualified Personnel Foundation of Taiyuan University of Technology tyut-rc201454a

摘要

摘要: 通过调控水热合成ZSM-5凝胶液中H₂O/Si物质的量比，实现了粒径为70、200、400和650 nm四种单分散ZSM-5的可控合成。采用XRD、TEM、BET和NH₃-TPD等多种表征对其微观结构进行分析，结合催化性能评价，考察了晶粒粒径对其催化甲醇制汽油反应性能的影响机制。结果表明，整体上随着ZSM-5晶粒粒径的增加，其外比表面积减小，结晶度提高，酸量呈现出先增加后基本不变的趋势。但外表面附着小晶粒的粒径为650 nm的分子筛体现出了大的外表面积和强的酸性。ZSM-5晶粒粒径的增加整体上降低了其催化MTG反应的寿命和最高收率。晶粒粒径为70 nm时，ZSM-5体现出了96 h的催化寿命和30.8%的最高收率。晶粒粒径为650 nm样品由于其大的外比表面积和较强的表面酸性，也体现出91 h的寿命。在大晶粒ZSM-5外表面附着生长小晶粒ZSM-5，是一种制备高性能催化剂的新方法。
- ZSM-5分子筛 /
- 水硅物质的量比 /
- 晶粒粒径 /
- 扩散性能 /
- 催化性能
Abstract: Four-sized monodispersed ZSM-5 crystals, being 70, 200, 400 and 650 nm, were hydrothermally synthesized by changing the H₂O/Si molar ratio in the synthesis gel, and characterized with XRD, TEM, BET and NH₃-TPD techniques. The crystal size effect of ZSM-5 on its catalytic performance for conversion of methanol to gasoline (MTG) was investigated. It was shown that the external surface area of the sample decreased with its crystal size, while the acid site amount firstly increased, and then kept almost constant. Nevertheless, 650 nm ZSM-5 crystals attaching small particles exhibit large external surface area and strong acidity. The catalytic stability and the liquid hydrocarbon yield decreased with increasing crystal size. The sample with a crystal size of 70 nm shows a catalytic lifetime of 96 h and a gasoline yield of 30.8%. The large external surface area and relatively strong acidity endow the sample with a crystal size of 650 nm also has a catalytic lifetime of 91 h, indicating that synthesis of large ZSM-5 crystals with small crystallites adhered to their surface could be a potential way to improve the catalytic performance.
- ZSM-5 /
- H₂O/Si molar ratio /
- crystal size effect /
- diffusion property /
- MTG catalytic performance

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图 1 固定床催化剂评价装置示意图

Figure 1 Diagram of MTG reaction set-up

1: pressure gauge; 2: pressure reducing value; 3: globe value; 4: gas flowmeter; 5: stock tank; 6: filter; 7: micro tube pump; 8: preheater; 9: reactor; 10: condensate recirculating tank; 11: condensator; 12: liquid storage tank; 13: wet gas flowmeter; 14: gas chromatography (Agilent GC); 15: computer

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图 2 不同催化剂的XRD谱图

Figure 2 XRD patterns of different-sized ZSM-5 samples

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图 3 不同催化剂的TEM照片

Figure 3 TEM images of ZSM-5 zeolites

(a), (a′): ZY5-70; (b), (b′): ZY5-200; (c), (c′): ZY5-400; (d), (d′): ZY5-650

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图 4 分子筛晶粒粒径与H₂O/Si物质的量比关系图

Figure 4 Relationship between the crystal size of ZSM-5 and the H₂O/Si molar ratio in its synthesis gel

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图 5 不同催化剂的N₂吸附-脱附谱图

Figure 5 N₂ adsorption-desorption isotherms of different-sized ZSM-5 samples

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图 6 不同ZSM-5催化剂的孔径分布

Figure 6 Pore size distributions of different-sized ZSM-5 samples

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图 7 不同催化剂的NH₃-TPD谱图

Figure 7 NH₃-TPD profiles of different-sized ZSM-5 samples

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图 8 不同ZSM-5催化剂上液烃收率随时间的变化

Figure 8 Liquid hydrocarbon yield obtained on the different-sized ZSM-5 samples as a function of reaction time

reaction condition: p=1.0 MPa, t=405 ℃, WHSV=4.74 h^-1

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图 9 不同ZSM-5催化剂上液烃产品分布柱状图

Figure 9 Hydrocarbon distributions in the products obtained on different ZSM-5 samples

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图 10 ZY5-650催化剂上产物分布随时间变化产品分布柱状图

Figure 10 Hydrocarbon distribution in the product obtained on the ZY5-650 at different time

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表 1 不同催化剂的相对结晶度

Table 1 Relative crystallinity of different-sized ZSM-5 samples

Catalyst	ZY5-70	ZY5-200	ZY5-400	ZY5-650
Relative crystallinity^a/%	56	63	70	100
^a: the crystallinity of samples was calculated by comparing the intensity of diffraction peaks between 20.0° and 25.0° with that of ZY5-650

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表 2 不同催化剂的结构性质

Table 2 Textural properties of different-sized ZSM-5 samples

Catalyst	Crystal size d/nm	A_BET^a/(m²·g^-1)	A_ext^b/(m²·g^-1)	v_micro^b/(cm³·g^-1)	v_meso^c/(cm³·g^-1)
ZY5-70	70	401	136	0.12	0.88
ZY5-200	200	401	69	0.16	0.31
ZY5-400	400	421	58	0.16	0.22
ZY5-650	650	397	62	0.17	0.23
^a: derived from the BET model, ^b: by t-plod method, ^c: using the BJH method by desorption, A_ext: mesopore surface area, v_micro: micropore volume, v_meso: mesopore volume

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表 3 不同催化剂的酸性质

Table 3 Acid site amount of different-sized ZSM-5 samples

Sample	Distribution of acid sites /(mmol·g^-1)
Sample	total	weak (120-250 ℃)	medium (250-350 ℃)	strong (350-550 ℃)
ZY5-70	0.20	0.04	0.11	0.05
ZY5-200	0.50	0.15	0.10	0.25
ZY5-400	0.47	0.15	0.08	0.24
ZY5-650	0.49	0.12	0.08	0.29

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表 4 不同催化剂的活性

Table 4 Catalytic results of different-sized ZSM-5 samples

Sample	Liquid hydrocarbon		Catalyst lifetime t/h
Sample	production^a/(g·g_zeolite)	yield at steady stage w/%	Catalyst lifetime t/h
ZY5-70	102	30.8	96
ZY5-200	85	28.8	86
ZY5-400	67	27.6	78
ZY5-650	92	29.8	91

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