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过程工程学报 ›› 2021, Vol. 21 ›› Issue (5): 609-616.DOI: 10.12034/j.issn.1009-606X.220097

• 环境与能源 • 上一篇    

纤维素热解生物油分子尺寸分布特性

王亚思1,2， 张开银2， 刘慧利2*， 丁宝平2， 郑 敏2   

  1. 1. 昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室，云南 昆明 650093 2. 昆明理工大学冶金节能减排教育部工程研究中心，云南 昆明 650093
  • 收稿日期:2020-03-22 修回日期:2020-06-19 出版日期:2021-05-22 发布日期:2021-06-01
  • 通讯作者: 刘慧利 lhlqwer@163.com
  • 基金资助:
    国家自然科学基金资助项目;云铜预研基金资助项目;云南省科技领军人才基金资助项目

Molecular size distribution characteristics of cellulose pyrolysis bio-oil

Yasi WANG1,2,  Kaiyin ZHANG2,  Huili LIU2*,  Baoping DING2,  Min ZHENG2   

  1. 1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, Yunnan 650093, China 2. Engineering Research Center of Metallurgical Energy Conservation & Emission Reduction, Ministry of Education, Kunming University of Science and Technology, Kunming, Yunnan 650093, China
  • Received:2020-03-22 Revised:2020-06-19 Online:2021-05-22 Published:2021-06-01

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摘要： 分子筛催化剂的孔径与生物油分子尺寸之间的差异造成分子筛催化剂的择形选择性。分子筛的孔径数据来自晶体结构分析，而生物油的分子尺寸数据很难获得，对生物油的分子尺寸进行估算十分必要。采用热裂解气质联用技术(Py-GC/MS)研究了纤维素热解生物油的组成成分，以Joback基团贡献法为基础计算了纤维素热解生物油各组成成分的动力学直径，分析了纤维素热解生物油的分子尺寸分布特性。结果表明，纤维素在350~600℃热解产生生物油的主要成分为脱水糖、呋喃衍生物和酮类化合物，生物油各组成成分的动力学直径主要分布在[0.500, 0.600) nm。当热解温度由350℃升至600℃时，动力学直径位于[0.550, 0.600) nm的生物油各组成成分的峰面积百分比由88.72%降至64.53%，位于[0.500, 0.550) nm的生物油各组成成分的峰面积百分比则由2.88%升至21.95%。纤维素催化裂解制备高品质液体燃料可选用ZSM-5, ZSM-11和IM-5等孔径尺寸0.500~0.600 nm的分子筛催化剂。

关键词: 纤维素, 生物油, 动力学直径, 基团贡献法, 择形催化

Abstract: The shape selectivity of molecular sieve catalyst is caused by the difference between the pore size of molecular sieve catalyst and the molecular size of bio-oil. The data of the pore size of molecular sieve catalysts are derived from crystal structural analysis, while the data of the molecular size of bio-oil are rather difficult to obtain. It is very necessary to estimate the molecular size of bio-oil. The pyrolysis of cellulose was carried out by prolysis-gas chromatography/mass spectrometry (Py-GC/MS), and the variation of the composition of cellulose pyrolysis bio-oil with the temperature was studied. The kinetic diameter of the components of cellulose pyrolysis bio-oil were calculated on the basis of Joback group contribution method, and the characteristics of molecular size distribution were analyzed. The results showed that cellulose pyrolysis bio-oil was mainly composed of anhydrosugars, furan derivatives and ketone compounds in the temperature range from 350℃ to 600℃. The kinetic diameter of cellulose pyrolysis bio-oil were mainly distributed in the range of [0.500, 0.600) nm. When the pyrolysis temperature increased from 350℃ to 600℃, the peak area of bio-oil molecules with the kinetic diameters in the range of [0.550, 0.600) nm decreased from 88.72% to 64.53%, and the peak area of bio-oil molecules with the kinetic diameters in the range of [0.500, 0.550) nm increased from 2.88% to 21.95%. For the preparation of high-quality liquid fuels by catalytic cracking of cellulose, molecular sieve catalysts ZSM-5, ZSM-11 and IM-5 with pore size of 0.500 to 0.600 nm can be selected.

Key words: cellulose, bio-oil, kinetic diameter, group-contribution method, shape selective catalysis