Mg与聚乙二醇协同改性对ZSM-5催化剂裂解甘蔗渣性能的影响

doi:10.16085/j.issn.1000-6613.2022-0391

摘要/Abstract

摘要：

采用水热合成法，在制备ZSM-5的过程中添加Mg或/和聚乙二醇（PEG），制备了一系列原位改性的ZSM-5催化剂，并运用XRD、SEM、EDS-Mapping、BET、NH₃-TPD等大型仪器对所制备的催化剂进行表征分析。结果表明：改性后的ZSM-5催化剂在孔径、孔容、酸量和酸强度方面均有不同程度的提高。进一步将改性的ZSM-5催化剂用于甘蔗渣催化裂解反应。评价结果显示，相较于甘蔗渣直接裂解，催化裂解可以显著提高2,3-二氢苯并呋喃产物的选择性，而金属Mg的引入、酸型、孔径和孔容是影响2,3-二氢苯并呋喃生成的主要因素。同时，金属Mg和聚乙二醇之间存在一定的协同作用。金属Mg和聚乙二醇协同改性的ZSM-5催化剂催化裂解甘蔗渣得到的生物油中呋喃类选择性高达40.12%，其中2,3-二氢苯并呋喃的选择性达到23.16%。

关键词: 催化剂, 热解, 分子筛, 生物质, 2,3-二氢苯并呋喃

Abstract:

A series of in-situ modified ZSM-5 catalysts were prepared by hydrothermal synthesis method through adding Mg or/and polyethylene glycol. The catalysts were characterized by XRD, SEM, EDS-Mapping, BET and NH₃-TPD. The results showed that the modified ZSM-5 catalysts had improved pore size, pore volume, acid content and acid strength. The modified catalysts were further used for catalytic cracking of bagasse. The catalytic cracking had significantly improved the selectivity of 2,3-dihydrobenzofuran product as compared with direct pyrolysis of bagasse, and the introduction of metal Mg, acid type, and the pore size and volume are the main factors affecting the formation of 2,3-dihydrobenzofuran. At the same time, there was a synergistic effect between Mg and polyethylene glycol. The selectivity of furans in bio-oil from bagasse pyrolysis was 40.12%, and the selectivity of 2,3-dihydrobenzofurans was 23.16%.

Key words: catalyst, pyrolysis, molecular sieves, biomass, 2,3-dihydrobenzofuran

中图分类号:

TQ352.79

鞠亚楠, 程向炜, 杨霞珍, 霍超, 刘化章. Mg与聚乙二醇协同改性对ZSM-5催化剂裂解甘蔗渣性能的影响[J]. 化工进展, 2022, 41(S1): 221-228.

JU Yanan, CHENG Xiangwei, YANG Xiazhen, HUO Chao, LIU Huazhang. Effects of Mg and polyethylene glycol modification of ZSM-5 catalyst on cracking bagasse[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 221-228.

图/表 12

参考文献 22

1	JUNG S, LEE J, PARK Y K, et al. Bioelectrochemical systems for a circular bioeconomy[J]. Bioresource Technology, 2020, 300: 122748.
2	GARCÍA T, VESES A, LÓPEZ J M, et al. Determining bio-oil composition via chemometric tools based on infrared spectroscopy[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(10): 8710-8719.
3	AHMAD M S, LIU C G, NAWAZ M, et al. Elucidating the pyrolysis reaction mechanism of Calotropis procera and analysis of pyrolysis products to evaluate its potential for bioenergy and chemicals[J]. Bioresource Technology, 2021, 322: 124545.
4	DAI Leilei, WANG Yunpu, LIU Yuhuan, et al. A review on selective production of value-added chemicals via catalytic pyrolysis of lignocellulosic biomass[J]. The Science of the Total Environment, 2020, 749: 142386.
5	KIM Eunjung, GIL Hyungbae, PARK Sangwon, et al. Bio-oil production from pyrolysis of waste sawdust with catalyst ZSM-5[J]. Journal of Material Cycles and Waste Management, 2017, 19(1): 423-431.
6	QIU Bingbing, TAO Xuedong, WANG Hao, et al. Biochar as a low-cost adsorbent for aqueous heavy metal removal: a review[J]. Journal of Analytical and Applied Pyrolysis, 2021, 155: 105081.
7	Güray YILDIZ, PRONK Marty, DJOKIC Marko, et al. Validation of a new set-up for continuous catalytic fast pyrolysis of biomass coupled with vapour phase upgrading[J]. Journal of Analytical and Applied Pyrolysis, 2013, 103: 343-351.
8	BRIDGWATER A V. Review of fast pyrolysis of biomass and product upgrading[J]. Biomass and Bioenergy, 2012, 38: 68-94.
9	QIU Bingbing, YANG Chenhao, SHAO Qianni, et al. Recent advances on industrial solid waste catalysts for improving the quality of bio-oil from biomass catalytic cracking: a review[J]. Fuel, 2022, 315: 123218.
10	张妮娜, 裴婷, 张媛, 等. 多级孔ZSM-5分子筛的合成及其金属改性研究进展[J]. 山东化工, 2020, 49(14): 44-46.
	ZHANG Nina, PEI Ting, ZHANG Yuan, et al. Research progress on synthesis and metal modification of hierarchical ZSM-5 zeolite[J]. Shandong Chemical Industry, 2020, 49(14): 44-46.
11	SHEN Yanfeng, QIN Zhengxing, ASAHINA Shunsuke, et al. The inner heterogeneity of ZSM-5 zeolite crystals[J]. Journal of Materials Chemistry A, 2021, 9(7): 4203-4212.
12	LI Yingkai, NISHU, YELLEZUOME Dominic, et al. Deactivation mechanism and regeneration effect of bi-metallic Fe-Ni/ZSM-5 catalyst during biomass catalytic pyrolysis[J]. Fuel, 2022, 312: 122924.
13	HOU Jinyu, ZHONG Daoxu, LIU Wuxing. Catalytic co-pyrolysis of oil sludge and biomass over ZSM-5 for production of aromatic platform chemicals[J]. Chemosphere, 2022, 291(Pt 3): 132912.
14	CORONAS Joaquín. Present and future synthesis challenges for zeolites[J]. Chemical Engineering Journal, 2010, 156(2): 236-242.
15	CHAI Meiyun, LIU Ronghou, HE Yifeng. Effects of SiO₂/Al₂O₃ ratio and Fe loading rate of Fe-modified ZSM-5 on selection of aromatics and kinetics of corn stalk catalytic pyrolysis[J]. Fuel Processing Technology, 2020, 206: 106458.
16	STEFANIDIS S D, KARAKOULIA S A, KALOGIANNIS K G, et al. Natural magnesium oxide (MgO) catalysts: a cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil[J]. Applied Catalysis B: Environmental, 2016, 196: 155-173.
17	常贵环, 曹吉林, 郭宏飞. 聚乙二醇对合成ZSM-5分子筛形貌影响的研究[J]. 人工晶体学报, 2012, 41(5): 1357-1361, 1375.
	CHANG Guihuan, CAO Jilin, GUO Hongfei. Influence of polyethylene glycol(PEG) on the morphology of ZSM-5 zeolite synthesis[J]. Journal of Synthetic Crystals, 2012, 41(5): 1357-1361, 1375.
18	CHEN Xueshuai, JIANG Rongli, HOU Huilin, et al. Facile synthesis of an Mg-incorporated ZSM-5 zeolite from dual silicon sources and its application for conversion of methanol to olefins[J]. ChemistrySelect, 2021, 6(28): 7056-7061.
19	PALIZDAR A, SADRAMELI S M. Catalytic upgrading of beech wood pyrolysis oil over iron- and zinc-promoted hierarchical MFI zeolites[J]. Fuel, 2020, 264: 116813.
20	DAI Leilei, WANG Yunpu, LIU Yuhuan, et al. Catalytic fast pyrolysis of torrefied corn cob to aromatic hydrocarbons over Ni-modified hierarchical ZSM-5 catalyst[J]. Bioresource Technology, 2019, 272: 407-414.
21	NI S, LIU Ronghou, RAHMAN Md Maksudur, et al. Catalytic pyrolysis of microcrystalline cellulose extracted from rice straw for high yield of hydrocarbon over alkali modified ZSM-5[J]. Fuel, 2021, 285: 119038.
22	SZOSTAK R, THOMAS T L. Reassessment of zeolite and molecular sieve framework infrared vibrations[J]. Journal of Catalysis, 1986, 101(2): 549-552.

催化剂	晶胞参数^①				元素质量分数^②/%
催化剂	2θ/(°)	晶面	d^③/nm	D^④/nm	Al	Mg
ZSM-5	23.15	（501）	0.1961	12.60	4.59	—
Mg-ZSM-5	23.04	（501）	0.1970	14.41	4.21	1.21
ZSM-5-PEG	23.12	（501）	0.1963	14.88	4.33	—
Mg-ZSM-5-PEG	23.02	（501）	0.1972	14.73	3.41	1.51

催化剂	晶胞参数^①				元素质量分数^②/%
催化剂	2θ/(°)	晶面	d^③/nm	D^④/nm	Al	Mg
ZSM-5	23.15	（501）	0.1961	12.60	4.59	—
Mg-ZSM-5	23.04	（501）	0.1970	14.41	4.21	1.21
ZSM-5-PEG	23.12	（501）	0.1963	14.88	4.33	—
Mg-ZSM-5-PEG	23.02	（501）	0.1972	14.73	3.41	1.51

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
ZSM-5	337	0.04	3.38
Mg-ZSM-5	301	0.08	4.37
ZSM-5-PEG	310	0.07	5.27
Mg-ZSM-5-PEG	289	0.12	5.79

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
ZSM-5	337	0.04	3.38
Mg-ZSM-5	301	0.08	4.37
ZSM-5-PEG	310	0.07	5.27
Mg-ZSM-5-PEG	289	0.12	5.79

催化剂	酸量^①/mmol·g ^-¹			酸型^②/mmol·g ^-¹
催化剂	总酸量	弱酸量	强酸量	B酸	L酸	B/L
ZSM-5	0.17	0.16	0.01	0.12	0.05	2.40
Mg-ZSM-5	0.36	0.18	0.18	0.08	0.28	0.29
ZSM-5-PEG	0.51	0.29	0.22	0.28	0.23	1.22
Mg-ZSM-5-PEG	0.52	0.30	0.22	0.10	0.42	0.24