Ce-Zr-Al-O催化剂催化烟梗热解的分析

doi:10.16085/j.issn.1000-6613.2019-1482

化工进展 ›› 2020, Vol. 39 ›› Issue (6): 2430-2439.DOI: 10.16085/j.issn.1000-6613.2019-1482

Ce-Zr-Al-O催化剂催化烟梗热解的分析

李文斌¹^,²(), 郑云武², 李水荣³, 刘志华¹, 刘灿¹^,², 郑志锋¹^,²^,³()

^1.云南省烟草化学重点实验室，云南昆明 650000
^2.林业生物质资源高效利用技术国家地方联合工程研究中心，西南地区生物基功能材料创新示范平台，西南地区林业生物质资源高效利用国家林业和草原局重点实验室，西南林业大学材料科学与工程学院，云南昆明 650224
^3.厦门市现代农业生物质高值化技术重点实验室（厦门;大学），福建省生物质高值化技术工程研究中心（厦门大学），厦门大学能源学院，福建厦门 361102

出版日期:2020-06-05 发布日期:2020-06-16
通讯作者: 郑志锋
作者简介:李文斌（1995—），男，硕士研究生，研究方向为生物质催化转化制备化学品。E-mail:allenwb@yeah.net。
基金资助:
国家自然科学基金(31670599);云南省烟草化学重点实验室开放基金

Analysis of Ce-Zr-Al-O catalyst for pyrolysis of tobacco stem

Wenbin LI¹^,²(), Yunwu ZHENG², Shuirong LI³, Zhihua LIU¹, Can LIU¹^,², Zhifeng ZHENG¹^,²^,³()

^1.Yunnan Key Laboratory of Tobacco Chemistry, Kunming 650000, Yunnan, China
^2.National Local Joint Engineering Research Center for efficient Utilization of forestry Biomass Resources; Innovation Demonstration Platform of Bio-based Functional Materials in Southwest China; Key Laboratory for Highly-Efficient Utilization of Forest Biomass Resources in the Southwest China, National Forestry and Grassland Administration, College of Materials Science & Engineering, Southwest Forestry University, Kunming 650224, Yunnan, China
^3.Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass (Xiamen University); Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass; College of Energy, Xiamen University, Xiamen 361102, Fujian, China

Online:2020-06-05 Published:2020-06-16
Contact: Zhifeng ZHENG

摘要/Abstract

摘要：

以活性组分的盐溶液为前体，通过共沉淀法制备CeO₂、Ce-Zr-O（CZ）和Ce-Zr-Al-O（CZA）催化剂，利用固定床热解器研究烟梗在催化剂参与下的催化热解过程及产物分布。采用N₂吸附-脱附、X射线衍射（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、程序升温脱附（NH₃-TPD）和X光射线电子能谱（XPS）等手段对催化剂的比表面积、孔结构、形貌特性以及催化剂表面酸性分布进行表征。结果表明，Al的加入增加了催化剂的比表面积，增加了催化剂的弱酸和中强酸，降低了强酸。烟梗慢速热解产物中含氮类化合物含量最高，达35.2%，其次为碳氢化合物和酚类。催化剂抑制了酚类、酯类和含氮类的生成，而对酮类和呋喃类的影响并不明显。催化剂明显促进了碳氢化合物的生成，其含量分别达到了45.24%（CeO₂）、55.35%（CZ）和52.07%（CZA）。芳香烃在碳氢化合物中占比最大，其中甲苯、二甲苯和乙苯在CZA、CZ和CeO₂催化下分别达到21.01%、10.04%和8.64%。CZA抗积炭能力极强，连续使用3次后，产物中碳氢化合物含量有所降低，但再生后能完全恢复。

关键词: 烟梗, 催化热解, Ce-Zr-Al-O, 催化转化, 活性, 再生性

Abstract:

CeO₂, Ce-Zr-O (CZ) and Ce-Zr-Al-O (CZA) catalysts were prepared by co-precipitation using salt solution of active components as precursor. A fixed-bed pyrolyzer was used to study the catalytic pyrolysis process and product distribution of tobacco stems in the presence of catalysts. N₂ adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), temperature programmed desorption (NH₃-TPD) and X-ray photolectron spectroscope (XPS) were used to characterize the specific surface area, pore structure, morphology and acidic distribution of the catalyst surface. The results showed that the addition of Al increased the specific surface area, enhanced the weak and medium-strong acid, and decreased the strong acid of the catalyst. The content of nitrogen compounds in the slow pyrolysis product of tobacco stem was the highest, reaching 35.2%, followed by hydrocarbons and phenols. The catalysts inhibited the production of phenols, esters and nitrogen compounds, but the effects on ketones and furans were not obvious. The catalysts significantly promoted the formation of hydrocarbons, reaching 45.24% (CeO₂), 55.35% (CZ) and 52.07% (CZA), respectively. Aromatic hydrocarbons account for the largest proportion of hydrocarbons, of which the content of toluene, xylene, ethylbenzene reached 21.01%, 10.04% and 8.64% in the presence of CZA, CZ and CeO₂, respectively CZA had a very strong ability to resist carbon deposits. After three consecutive uses, the hydrocarbon content in the products was reduced, but it can be completely recovered after regeneration.

Key words: tobacco stem, catalytic pyrolysis, Ce-Zr-Al-O, catalytic conversion, reactivity, regeneration

中图分类号:

TQ35

李文斌, 郑云武, 李水荣, 刘志华, 刘灿, 郑志锋. Ce-Zr-Al-O催化剂催化烟梗热解的分析[J]. 化工进展, 2020, 39(6): 2430-2439.

Wenbin LI, Yunwu ZHENG, Shuirong LI, Zhihua LIU, Can LIU, Zhifeng ZHENG. Analysis of Ce-Zr-Al-O catalyst for pyrolysis of tobacco stem[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2430-2439.

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Ce-Zr-Al-O催化剂催化烟梗热解的分析

Analysis of Ce-Zr-Al-O catalyst for pyrolysis of tobacco stem

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