活性炭催化热解纤维素协同制备酚类和合成气

doi:10.11949/0438-1157.20210416

化工学报 ›› 2021, Vol. 72 ›› Issue (10): 5206-5217.DOI: 10.11949/0438-1157.20210416

• 催化、动力学与反应器 • 上一篇下一篇

活性炭催化热解纤维素协同制备酚类和合成气

苏银海¹(),张书平²(),刘凌沁¹,熊源泉³()

^1.南京理工大学新能源学院，江苏江阴 214443
^2.南京理工大学能源与动力工程学院，江苏南京 210094
^3.能源热转换及其过程测控教育部重点实验室，东南大学能源与环境学院，江苏南京 210096

收稿日期:2021-03-24 修回日期:2021-07-08 出版日期:2021-10-05 发布日期:2021-10-05
通讯作者: 张书平,熊源泉
作者简介:苏银海（1990—），男，博士，讲师，susilversea@163.com
基金资助:
国家重点研发计划“绿色宜居村镇技术创新” 重点专项(2019YFD1100602);国家自然科学基金青年项目(51906110);江苏省自然科学基金青年项目(BK20190465);中国博士后科学基金面上资助项目(2019M650097);中国博士后科学基金特别资助项目(2020T130096)

Synergetic production of phenols and syngas from the catalytic pyrolysis of cellulose on activated carbon

Yinhai SU¹(),Shuping ZHANG²(),Lingqin LIU¹,Yuanquan XIONG³()

^1.School of New Energy, Nanjing University of Science and Technology, Jiangyin 214443, Jiangsu, China
^2.School of Energy and Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China
^3.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China

Received:2021-03-24 Revised:2021-07-08 Online:2021-10-05 Published:2021-10-05
Contact: Shuping ZHANG,Yuanquan XIONG

摘要/Abstract

摘要：

苯酚和合成气均为工业生产中重要的基础化工原料。以自制的活性炭为催化剂，以纤维素为原料实现了催化热解液相产物中苯酚和气相产物中CO的同时富集。实验发现，生物质灰分中的钾、热解过程中催化剂/纤维素质量比和热解温度均对气液相产物的品质有着不同程度的影响。研究表明：钾的存在不利于热解产物品质的提高。钾虽然提高了生物油中苯酚的富集度，但降低了实际产率。而热解气中CO的浓度和产率均下降。对催化热解条件的研究表明热解温度450℃，催化剂比例为1∶1时可获得最佳的热解产物。此时，生物油中酚类物质占可检测有机物相对含量的62.31%，其中苯酚为45.37%，产率为1.78%（质量）。热解气中CO的浓度和产率分别为69.21%（体积）和 169.95 ml/g，热值为12.93 MJ/m³。

关键词: 生物质, 活性炭, 热解, 生物油, 合成气

Abstract:

Both phenols and syngas are important basic chemical raw materials in industrial production. In this paper, self-made activated carbon was used as a catalyst, and cellulose was used as a raw material to achieve the simultaneous enrichment of phenol in the liquid phase product of catalytic pyrolysis and CO in the gas phase product. It was found that all of the potassium in ash, the mass ratio of catalyst/cellulose and the catalytic temperature affected the quality of gas and liquid products. Results showed that the presence of potassium was against the improvement of pyrolysis products quality. Although, the relative content of phenols in bio-oil was increased, but its actual yield was decreased. Meantime, both the concentration and yield of CO in pyrolytic gas decreased. The optimum products were obtained at the pyrolysis temperature of 450℃ with the catalyst/cellulose mass ratio of 1∶1. At this time, the phenolic substances in the bio-oil accounted for 62.31% of the relative content of the detectable organic matter, of which phenol was 45.37%, and the yield was 1.78%(mass). Besides, the concentration and yield of CO in pyrolytic gas were 69.21%(vol) and 169.95 ml/g, with the calorific value of 12.93 MJ/m³.

Key words: biomass, activated carbon, pyrolysis, bio-oil, syngas

中图分类号:

TK 6

苏银海,张书平,刘凌沁,熊源泉. 活性炭催化热解纤维素协同制备酚类和合成气[J]. 化工学报, 2021, 72(10): 5206-5217.

Yinhai SU,Shuping ZHANG,Lingqin LIU,Yuanquan XIONG. Synergetic production of phenols and syngas from the catalytic pyrolysis of cellulose on activated carbon[J]. CIESC Journal, 2021, 72(10): 5206-5217.

图/表 11

表1 纤维素和杨木粉的燃料特性分析

Table 1 Fuel characteristics analysis of cellulose and poplar wood

样品	工业分析/(%(质量), 干燥基)			元素分析/(%(质量), 干燥无灰基)						热值/(MJ/kg)
样品	灰分	挥发分	固定碳	C	H	O	N	O/C	H/C	热值/(MJ/kg)
纤维素	0.03±0.01	94.08±0.18	5.89±0.19	43.07±0.24	6.47±0.09	50.46±0.33	—	0.87±0.001	1.80±0.008	17.433±0.536
杨木粉	0.38±0.05	85.51±0.21	14.11±0.26	50.98±0.32	6.08±0.27	42.80±0.64	0.14±0.05	0.63±0.009	1.43±0.038	17.811±0.389

图1 催化热解实验装置示意图

Fig.1 Schematic diagram of experimental equipment for catalytic pyrolysis

图2 活性炭催化剂的表征

Fig.2 Characterization of activated carbon catalyst

图3 钾对纤维素催化热解产物质量分布的影响(a)及典型离子色谱图(b)

Fig.3 Effects of potassium on mass distribution of catalytic pyrolysis products from cellulose(a) and typical ion chromatograms (b)

图4 钾对纤维素热解油组分的影响

Fig.4 Effects of potassium on the bio-oil composition of cellulose

图5 钾对纤维素热解气组分的影响

Fig.5 Effects of potassium on the syngas composition

图6 催化剂/原料质量比对纤维素催化热解的影响

Fig.6 Effects of catalyst/feedstock mass ratio on catalytic pytolysis of cellulose

图7 催化剂/原料质量比对纤维素热解气组分的影响

Fig.7 Effects of catalyst/feedstock mass ratio on the syngas composition

图8 热解温度对纤维素催化热解的影响

Fig.8 Effects of pyrolysis temperature on catalytic pytolysis of cellulose

图9 热解温度对纤维素热解气组分的影响

Fig.9 Effects of pyrolysis temperature on the syngas composition

图10 活性炭催化热解纤维素制备苯酚和CO机理

Fig.10 Mechanism of preparing of phenol and CO by the catalytic pyrolysis of cellulose with phosphoric activated carbon

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活性炭催化热解纤维素协同制备酚类和合成气

Synergetic production of phenols and syngas from the catalytic pyrolysis of cellulose on activated carbon

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