化工进展 ›› 2017, Vol. 36 ›› Issue (09): 3329-3335.DOI: 10.16085/j.issn.1000-6613.2017-0045

• 工业催化 • 上一篇    下一篇

碱处理HZSM-5催化纤维素热裂解制备芳烃

程浩1,3, 周峰2, 陈皓3, 傅杰3, 陈可泉1, 乔凯2, 欧阳平凯1,3   

  1. 1 南京工业大学生物与制药工程学院, 江苏 南京 211800;
    2 中国石油化工股份有限公司抚顺石油化工研究院, 辽宁 抚顺 113001;
    3 浙江大学化学工程与生物工程学院生物质化工教育部重点实验室, 浙江 杭州 310027
  • 收稿日期:2017-01-09 修回日期:2017-03-21 出版日期:2017-09-05 发布日期:2017-09-05
  • 通讯作者: 傅杰,副教授,博士生导师,研究方向为生物质定向化学转化。
  • 作者简介:程浩(1991-),男,硕士研究生,从事生物质催化热裂解制备芳烃方面的研究

Preparation of aromatics from fast catalytic pyrolysis of cellulose over alkali-treated HZSM-5

CHENG Hao1,3, ZHOU Feng2, CHEN Hao3, FU Jie3, CHEN Kequan1, QIAO Kai2, OUYANG Pingkai1,3   

  1. 1 Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211800, Jiangsu, China;
    2 Sinopec Fushun Research Institute of Petroleum and Petrochemical, Fushun 113001, Liaoning, China;
    3 Key Laboratory of Biomass Chemical Engineering, Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 31007, Zhejiang, China
  • Received:2017-01-09 Revised:2017-03-21 Online:2017-09-05 Published:2017-09-05

摘要: 使用不同浓度的NaOH溶液(0.2~1.0mol/L)对不同硅铝比的HZSM-5沸石进行碱处理制备多级孔HZSM-5,研究了NaOH浓度对碱处理制备多级孔HZSM-5的影响规律以及多级孔HZSM-5在纤维素催化热裂解中的催化性能。采用N2吸附-脱附、XRD、TEM和NH3-TPD对催化剂进行表征:XRD结果显示HZSM-5碱处理后,多级孔HZSM-5依然有MFI结构特征峰;N2吸附-脱附和TEM表征结果表明碱处理后的ZSM-5晶体内有明显的介孔孔道,形成多级孔结构;NH3-TPD结果表明随着NaOH浓度的增加,多级孔HZSM-5的强酸量呈现先增加后减少的趋势,在0.4mol/L处达到最高值。在微型裂解仪与气相色谱-质谱联用装置中研究多级孔HZSM-5对纤维素催化热裂解制备芳烃的催化性能,结果显示硅铝比为25、38、50的HZSM-5芳烃产率分别从碱处理前的33.5%、35.6%和32.2%,最高增加至37.1%、38.5%和34.0%(0.4mol/L NaOH碱处理);焦炭产率分别由碱处理前的33.1%、31.5%和33.8%降低至29.1%、25.8%和29.8%。结果表明,通过有效调控碱处理条件能够提高纤维素催化热裂解过程中的芳烃产率,同时降低焦炭产率。

关键词: 碱处理, HZSM-5, 沸石, 催化, 催化剂, 热裂解, 芳烃

Abstract: Hierarchical HZSM-5 were obtained by alkali treatment of commercial HZSM-5 zeolites(SiO2/Al2O3 radios of 25,38 and 50)using NaOH solutions of different concentrations (0.2-1.0mol/L)and exchanged with NH4Cl. The catalytic performance of the obtained hierarchical HZSM-5 in fast catalytic pyrolysis of cellulose was studied. The catalysts were characterized by N2-BET,XRD,TEM and NH3-TPD. The XRD patterns showed that the desilicated ZSM-5 structure was still maintained. The results of N2-BET and TEM image indicated that the mesopores were created after alkali treatment indicating the formation of hierarchical structure. The NH3-TPD results showed that the acidity increased first and then decreased as the alkali concentration increased. The Py-GCMS was used to test the catalytic activity of fast pyrolysis of cellulose. The yields of aromatic over Z25, Z38,and Z50 were 33.5%,35.6% and 32.2%,respectively,and increased to 37.1%,38.5% and 34.0% after treated with 0.4mol/L NaOH solution. The coke yield also decreased to 29.1%,25.8% and 29.8% respectively after alkali treatment. The results indicated that controlled desilication of zeolite could increase the conversion of cellulose to aromatic hydrocarbons and inhibited the formation of coke.

Key words: alkali treatment, HZSM-5, zeolite, catalysis, catalyst, pyrolysis, aromatic

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