Fe-Zn共改性ZSM-5催化作用下生物质快速热解特性研究

doi:10.11949/0438-1157.20190854

化工学报 ›› 2020, Vol. 71 ›› Issue (4): 1637-1645.DOI: 10.11949/0438-1157.20190854

• 催化、动力学与反应器 • 上一篇下一篇

Fe-Zn共改性ZSM-5催化作用下生物质快速热解特性研究

方书起^1,^2,³(),石崇^1,²,李攀^1,^2,³(),白净^1,²,常春^1,^2,³

^1.郑州大学机械与动力工程学院，河南郑州 450001
^2.生物质炼制技术与装备河南省工程实验室，河南郑州 450001
^3.河南省杰出外籍科学家工作室，河南郑州 450001

收稿日期:2019-07-25 修回日期:2019-08-12 出版日期:2020-04-05 发布日期:2020-04-05
通讯作者: 李攀
作者简介:>方书起（1964—），男，教授，fangsq@zzu.edu.cn
基金资助:
中国博士后科学基金面上项目(2018M632800);河南省重点研发与推广专项项目(192102210080);河南省高等学校重点科研项目(19A470009);河南省杰出外籍科学家工作室项目(GZS2018004)

Study on rapid pyrolysis characteristics of biomass catalyzed by Fe-Zn co-modified ZSM-5

Shuqi FANG^1,^2,³(),Chong SHI^1,²,Pan LI^1,^2,³(),Jing BAI^1,²,Chun CHANG^1,^2,³

^1.School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.Engineering Laboratory of Henan Province for Biorefinery Technology and Equipment, Zhengzhou 450001, Henan, China
^3.Outstanding Foreign Scientists’ Workroom, Zhengzhou 450001, Henan, China

Received:2019-07-25 Revised:2019-08-12 Online:2020-04-05 Published:2020-04-05
Contact: Pan LI

摘要/Abstract

摘要：

选取木屑和花生壳作为原料进行生物质热解，研究有机产物分布，催化剂使用Fe、Zn两种金属元素进行改性。通过X射线衍射（XRD）、扫描电镜（SEM）、傅里叶红外（FT-IR）、比表面积测试（BET）对Fe-Zn改性的ZSM-5进行分析。使用闪速裂解-气质联用仪（PY-GC/MS）对原料进行热解，探究生物质催化热解的产物分布变化。催化剂的使用使得芳烃类产物产率获得较大提升，在木屑热解中，Fe负载的分子筛催化获得了酚类的最高产率，比ZSM-5催化热解产率提升18.30%。金属改性催化剂在花生壳热解中，大幅提升了芳烃类产物产率，其中Zn负载催化剂芳烃类产物产率最高，Zn负载催化热解比直接热解的酚类产率降低了18.92%。Zn负载催化获得了最低的酮类产率，与直接热解相比酮类产率降低19.74%，显示出较强的脱羟基效果。此外Zn负载催化和Fe-Zn双金属负载催化在花生壳热解中都大幅降低了酸类产物产率，与直接热解相比酸类产率分别降低了30.46%、36.71%。

关键词: 生物质, 催化剂, 热解, 分子筛, 产物特性

Abstract:

In this study, wood chips and peanut shells were used as raw materials for biomass pyrolysis, and the distribution of organic products was studied. The catalyst was modified by two metal elements, Fe and Zn. The Fe-Zn modified ZSM-5 was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared, and specific surface area test (BET). Biomass was pyrolyzed using a pyrolysis-mass spectrometer (PY-GC/MS) to investigate changes in product distribution of biomass catalytic pyrolysis. Under the action of the catalyst, the yield of the aromatic hydrocarbon product is greatly improved. In the pyrolysis process of wood chips, the Fe-supported molecular sieve catalyzed the highest yield of phenols, which was 18.30% higher than the catalytic pyrolysis yield of ZSM-5. The single-metal supported catalytic pyrolysis of Fe and Zn yielded the lowest yield of acid products, which was 50.66% lower than that of direct pyrolysis. The metal modified catalyst greatly increases the yield of aromatic products in the pyrolysis of peanut shells. The Zn modified catalyst has the highest yield of aromatic hydrocarbon products, and the Zn modified catalytic pyrolysis is 18.92% lower than that of direct pyrolysis. The lowest ketone yield was obtained by Zn modification, and the ketone yield was reduced by 19.74% compared with direct pyrolysis, showing a strong dehydroxylation effect. In addition, Zn modification catalysis and Fe-Zn bimetallic modification catalyzed the yield of acid products in the pyrolysis of peanut shells, and the acid yield decreased by 30.46% and 36.71% compared with direct pyrolysis. It was found that both Fe or Zn modified ZSM-5 molecular sieves have an inhibitory effect on the acid in the pyrolysis product and reduce the corrosivity of the product. The Fe modified (6%(mass)) ZSM-5 molecular sieve catalyst has a higher yield on the aromatic hydrocarbon product than Zn. The effect of equal mass content of Fe-Zn on the promotion of phenolic products is obvious. In addition, changes in pore volume and pore size distribution occurred on Fe-modified ZSM-5 catalysts, and this change was positively correlated with BTX yield in wood chips pyrolysis. The Fe loading forms a new mesoporous structure on the surface of the molecular sieve, which promotes the formation of aromatic hydrocarbons and phenolic compounds. Compared with the pyrolysis products of peanut shells, the 120—150 molecular weight of the wood chips pyrolysis products is more, which can be used as an intermediate product of cracking, and has a promoting effect on the formation of phenol and BTX. It indicates that different biomass materials, in direct pyrolysis, the molecular weight distribution of the product also affects the catalytic upgrading effect. Under the condition of single metal catalytic pyrolysis, compared with the catalytic effect of Zn-loaded ZSM-5 catalyst, the catalytic effect of Fe-modified catalyst on biomass pyrolysis products is significant.

Key words: biomass, catalyst, pyrolysis, molecular sieves, product characteristics

中图分类号:

TK 6

方书起, 石崇, 李攀, 白净, 常春. Fe-Zn共改性ZSM-5催化作用下生物质快速热解特性研究[J]. 化工学报, 2020, 71(4): 1637-1645.

Shuqi FANG, Chong SHI, Pan LI, Jing BAI, Chun CHANG. Study on rapid pyrolysis characteristics of biomass catalyzed by Fe-Zn co-modified ZSM-5[J]. CIESC Journal, 2020, 71(4): 1637-1645.

图/表 9

表1 生物质原料的工业分析和元素分析

Table 1 Proximate analysis and ultimate analysis of biomass

原料	工业分析 /%				元素分析 /%
原料	M	A	V	FC^①	N	C	H	S	O^①
杨木木屑	6.31	0.69	79.25	13.75	0.12	47.39	6.32	0.15	46.02
花生壳	8.24	2.40	68.07	21.29	1.04	43.31	5.83	0.23	49.59

表2 金属改性ZSM-5催化剂命名缩写

Table 2 Abbreviation for catalyst nomenclature

总金属量	缩写
6%(质量)Fe	6Fe
6%(质量)Zn	6Zn
3%(质量)Fe+3%(质量)Zn	3Fe3Zn

图1 石英管中生物质与催化剂堆填示意图

Fig.1 Schematic diagram of biomass and catalyst packing in quartz tubes

表3 催化剂比表面积、孔隙及粒径

Table 3 Catalyst specific surface area, pore size and particle size

催化剂样品		S_BET/ (m²/g)	孔体积/ (ml/g)	平均孔径/ nm	D₅₀/ μm
未经处理的ZSM-5		222.44	0.17	3.05	8.61
金属负载的ZSM-5	6Fe	201.26	0.24	4.79	8.54
	6Zn	165.91	0.13	3.22	8.89
	3Fe3Zn	181.81	0.15	3.32	10.72

图2 金属改性催化剂XRD谱图

Fig.2 XRD patterns of metal modified catalyst

图3 金属改性催化剂SEM图

Fig.3 SEM images of metal modified catalyst

图4 热解产物组分分布

Fig.4 Composition distribution of pyrolysis product

图5 产物产率峰面积与孔径的相关性

Fig.5 Correlation between product yield peak area and pore size

图6 各分子量区间产物分布

Fig.6 Product distribution in each molecular weight range

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Fe-Zn共改性ZSM-5催化作用下生物质快速热解特性研究

Study on rapid pyrolysis characteristics of biomass catalyzed by Fe-Zn co-modified ZSM-5

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