脱碱赤泥催化剂制备及对秸秆催化热解生物油成分的影响

doi:10.16085/j.issn.1000-6613.2021-2356

化工进展 ›› 2022, Vol. 41 ›› Issue (9): 4723-4732.DOI: 10.16085/j.issn.1000-6613.2021-2356

脱碱赤泥催化剂制备及对秸秆催化热解生物油成分的影响

韩轩¹(), 王丽红¹^,²^,³(), 柏雪源¹^,²^,³, 易维明²^,³, 李永军¹^,²^,³, 李志合¹^,²^,³, 张安东¹^,²^,³

^1.山东理工大学农业工程与食品科学学院，山东淄博 255000
^2.山东省清洁能源工程技术研究中心，山东淄博 255000
^3.省部共建木本油料资源利用国家重点实验室分实验室，山东淄博 255000

收稿日期:2021-11-17 修回日期:2022-01-06 出版日期:2022-09-25 发布日期:2022-09-27
通讯作者: 王丽红
作者简介:韩轩（1997—），男，硕士研究生，研究方向为生物质热解。E-mail: 1203582978@qq.com。
基金资助:
国家重点研发计划(2019YFD1100600);国家自然科学基金(52130610);山东省自然科学基金(ZR2020ME185)

Preparation of dealkalized red mud catalysts and its effect on bio-oil composition of corn straw catalytic pyrolysis

HAN Xuan¹(), WANG Lihong¹^,²^,³(), BAI Xueyuan¹^,²^,³, YI Weiming²^,³, LI Yongjun¹^,²^,³, LI Zhihe¹^,²^,³, ZHANG Andong¹^,²^,³

^1.School of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, Shandong, China
^2.Shandong Clean Energy Engineering Technology Research Center, Zibo 255000, Shandong, China
^3.State Key Laboratory of Woody Oilseed Resources Utilization Sub-laboratories, Zibo 255000, Shandong, China

Received:2021-11-17 Revised:2022-01-06 Online:2022-09-25 Published:2022-09-27
Contact: WANG Lihong

摘要/Abstract

摘要：

赤泥含有具有催化作用的元素，同时含有一定的孔，可用作催化剂。赤泥的强碱性导致催化剂表面烧结、酸性不足等问题。该研究采用柠檬酸交换钠及焙烧制备了脱碱赤泥催化剂，赤泥的脱碱率达到96%。表征发现脱碱赤泥结构更稳定，硅铝酸盐聚合度降低，Al、Fe、Ti等具有催化作用的元素含量增加、比表面积增加、中强酸酸性位点增多等。用于催化秸秆热解，产物生物油中醛类、酚类、呋喃类变化明显，其中2,3-二氢呋喃含量增加了15.9倍。脱碱赤泥对生物油的产率影响较小，不可冷凝气体、生物炭产率变化明显。推断与脱碱赤泥促进了脱羟和脱羰基反应、葡萄糖脱水重排，强化了脱甲基和脱甲氧基反应有关。

关键词: 热解, 催化剂, 赤泥, 脱碱, 生物质

Abstract:

Red mud contains catalytic elements and certain pores, which can be used as catalysts. Its strong alkalinity leads to sintering of the catalyst surface and inadequate acidity. In this study, dealkalized red mud catalysts were prepared by exchange of sodium citrate and calcination. The dealkalization rate reached 96%. Characterization found that the dealkalized red mud was more stable. Polymerization degree of aluminosilicate decreased and the content of Al, Fe, Ti and other catalytic elements increased in dealkalized red mud. The specific surface area and the medium strong acid sites were increased. When the dealkalized red mud was used to catalyze the straw pyrolysis, the aldehydes, phenols and furans in the bio-oil products changed significantly. The content of 2,3-dihydrofuran increased by 15.9 times. The dealkalized red mud had little effect on the production rate of bio-oil, with significant changes in non-condensable gas and biochar production rate. It was inferred that the dealkalized red mud promoted the de-hydroxylation and de-carbonylation reactions,and the dehydration rearrangement of glucose, and strengthened the demethylation and de-methoxy reactions. The research would provide an important reference for the efficient preparation of liquid fuels and fine chemicals by the catalytic pyrolysis of biomass.

Key words: pyrolysis, catalysis, red mud, dealkylation, biomass

中图分类号:

韩轩, 王丽红, 柏雪源, 易维明, 李永军, 李志合, 张安东. 脱碱赤泥催化剂制备及对秸秆催化热解生物油成分的影响[J]. 化工进展, 2022, 41(9): 4723-4732.

HAN Xuan, WANG Lihong, BAI Xueyuan, YI Weiming, LI Yongjun, LI Zhihe, ZHANG Andong. Preparation of dealkalized red mud catalysts and its effect on bio-oil composition of corn straw catalytic pyrolysis[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4723-4732.

图/表 11

图1 赤泥脱碱实验流程

图2 催化热解装置示意图1—气体流量计；2—管式炉；3—石英舟；4—冷阱；5—恒温水浴槽；6—温度控制系统；7—氮气瓶

图3 脱碱因素对赤泥脱碱率的影响关系

图4 脱碱赤泥催化剂颜色特征(a)—为原始赤泥；(b)—黑色脱碱赤泥；(c)—棕黄色脱碱率最高的脱碱赤泥

表1 玉米秸秆的工业分析和元素分析

工业分析 $w d / %$					元素分析 $w d / %$
M	A	V	FC		C	H	O	N
8.31%	9.25%	66.19%	16.25%		45.05%	4.4%	49.53%	1.02%

表1 玉米秸秆的工业分析和元素分析

工业分析 $w d / %$					元素分析 $w d / %$
M	A	V	FC		C	H	O	N
8.31%	9.25%	66.19%	16.25%		45.05%	4.4%	49.53%	1.02%

表2 赤泥中的主要化学成分

样品	质量分数/%
样品	Al₂O₃	Na₂O	Fe₂O₃	TiO₂	CaO	SiO₂
RM	27.44	10.76	35.06	4.89	2.06	17.50
ACRM	26.84	0.44	51.92	6.85	0.21	12.21
BRM	25.29	4.46	41.35	5.71	0.99	20.48

图5 三种催化剂理化性质分析

图6 脱碱前后赤泥SEM图

图7 三种催化剂的催化特性分析

图8 玉米秸秆热解产物分布

图9 不同赤泥催化热解生物油成分分析

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脱碱赤泥催化剂制备及对秸秆催化热解生物油成分的影响

Preparation of dealkalized red mud catalysts and its effect on bio-oil composition of corn straw catalytic pyrolysis

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