碱处理HZSM-5催化纤维素热裂解制备芳烃

doi:10.16085/j.issn.1000-6613.2017-0045

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

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 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 Hao^1,3, ZHOU Feng², CHEN Hao³, FU Jie³, CHEN Kequan¹, QIAO Kai², OUYANG Pingkai^1,3

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/Abstract

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

中图分类号:

TQ032.4

程浩, 周峰, 陈皓, 傅杰, 陈可泉, 乔凯, 欧阳平凯. 碱处理HZSM-5催化纤维素热裂解制备芳烃[J]. 化工进展, 2017, 36(09): 3329-3335.

CHENG Hao, ZHOU Feng, CHEN Hao, FU Jie, CHEN Kequan, QIAO Kai, OUYANG Pingkai. Preparation of aromatics from fast catalytic pyrolysis of cellulose over alkali-treated HZSM-5[J]. Chemical Industry and Engineering Progress, 2017, 36(09): 3329-3335.

参考文献

[1] 孔德金,杨为民.芳烃生产技术进展[J].化工进展,2011,30(1):16-25. KONG J B,YANG W M.Advance in technology for production of aromatic hydrocarbons[J].Chemical Industry and Engineering Progress,2011,30(1):16-25.
[2] 董丽.生物质制芳烃技术进展与发展前景[J].化工进展,2013,32(7):1526-1533. DONG L.Development of aromatics production from biomass[J]. Chemical Industry and Engineering Progress,2013,32(7):1526-1533.
[3] 郑云武,杨晓琴,王霏,等. 生物质催化裂解制备芳烃化合物的研究进展[J].林产化学与工业,2015,35(5):149-158. ZHENG Y W,YANG X Q,WANG F,et al.Research progress of aromatics production from catalytic pyrolysis of biomass[J]. Chemistry and Industry of Forest Products,2015,35(5):149-158.
[4] ALONSO D M, BOND J Q,DUMESIC J A.Catalytic conversion of biomass to biofuels[J]. Green Chemistry,2010,12(9):1493-1513.
[5] HUBER G W,IBORRA S,CORMA A.Synthesis of transportation fuels from biomass:chemistry,catalysts,and engineering[J]. Chemical Reviews,2006,106(9):4044-4098.
[6] LI X,SU L,WANG Y,et al.Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons[J]. Frontiers of Environmental Science & Engineering,2012,6(3):295-303.
[7] VICHAPHUND S,AHT-ONG D,SRICHAROENCHAIKUL V,et al.Production of aromatic compounds from catalytic fast pyrolysis of Jatropha residues using metal/HZSM-5 prepared by ion-exchange and impregnation methods[J].Renewable Energy,2015,79:28-37.
[8] WANG K,ZHANG J,SHANKS B H,et al.Catalytic conversion of carbohydrate-derived oxygenates over HZSM-5 in a tandem micro-reactor system[J]. Green Chemistry,2015,17(1):557-564.
[9] WANG K G,KIM K H,BROWN R C.Catalytic pyrolysis of individual components of lignocellulosic biomass[J]. Green Chemistry,2014,16(2):727-735.
[10] CARLSON T R,TOMPSETT G A,CONNER W C,et al.Aromatic production from catalytic fast pyrolysis of biomass-derived feedstocks[J].Topics in Catalysis,2009,52(3):241-252.
[11] JAE J,TOMPSETT G A,FOSTER A J,et al.Investigation into the shape selectivity of zeolite catalysts for biomass conversion[J]. Journal of Catalysis,2011,279(2):257-268.
[12] CHEN N Y,DEGNAN T F,KOENIG L R.Liquid fuel from carbohydrates[J].Chemtech,1986,16(8):506-511.
[13] FABBRI D,TORRI C,BARAVELLI V.Effect of zeolites and nanopowder metal oxides on the distribution of chiral anhydrosugars evolved from pyrolysis of cellulose:an analytical study[J].Journal of Analytical and Applied Pyrolysis,2007,80(1):24-29.
[14] FOSTER A J,JAE J,CHENG Y T,et al.Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5[J].Applied Catalysis A:General,2012,423:154-161.
[15] KELKAR S,SAFFRON C M,LI Z,et al.Aromatics from biomass pyrolysis vapour using a bifunctional mesoporous catalyst[J].Green Chemistry,2014,16(2):803-812.
[16] GROEN J C,ZHU W,BROUWER S,et al.Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desilication[J].Journal of the American Chemical Society,2007,129(2):355-360.
[17] SADOWSKA K,GÓRA-MAREK K,DROZDEK M,et al.Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide[J].Microporous and Mesoporous Materials,2013,168:195-205.
[18] LI J,LI X,ZHOU G,et al.Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions[J].Applied Catalysis A:General,2014,470:115-122.
[19] 韩伟,潘相米,谭亚南,等.Na₂CO₃处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能[J]. 化工进展,2016,35(s2):174-178. HAN W,PAN X M,TAN Y N,et al.Preparation of hierarchical ZSM-5 zeolites treated by Na₂CO₃ and its catalytic performance for propane dehydrogenation to propylene[J].Chemical Industry and Engineering Progress,2016,35(s2):174-178.
[20] GONG S,SHINPZAKI A,QIAN E W.Role of support in hydrotreatment of jatropha oil over sulfided NiMo catalysts[J]. Industrial & Engineering Chemistry Research,2012,51(43):13953-13960.
[21] LIU C,WANG H,KARIM A M,et al.Catalytic fast pyrolysis of lignocellulosic biomass[J].Chemical Society Reviews,2014,43(22):7594-7623.
[22] CHEN H,WANG Q,ZHANG X,et al.Quantitative conversion of triglycerides to hydrocarbons over hierarchical ZSM-5 catalyst[J]. Applied Catalysis B:Environmental,2015,166:327-334.

碱处理HZSM-5催化纤维素热裂解制备芳烃

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

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