Catalytic pyrolysis of biomass model compounds to olefins and aromatic hydrocarbons

doi:10.11949/j.issn.0438-1157.20150637

Abstract

Abstract:

Catalytic pyrolysis of guaiacol, as a model compound of biomass, was conducted over ZSM-5 in a fixed-bed reactor. The effects of temperature, weight hourly space velocity and partial pressure on the yield and the selectivity of product were investigated and the coked ZSM-5 were characterized. The results indicated that the main products of guaiacol catalytic pyrolysis were phenolic compounds, followed by aromatic hydrocarbons. Temperature has a significant influence on the product distribution. A certain amount of coke deposition on the catalyst is useful in improving the yield of olefins and aromatic hydrocarbons. Based on the product distribution, the catalytic reaction pathway was speculated to be the removal methoxy group to form phenols with further aromatization to form aromatic hydrocarbons. The results provide a theoretical basis for the research of the mechanism of biomass catalytic pyrolysis.

Key words: biomass, fixed-bed, guaiacol, catalytic pyrolysis, product distribution, coke deposition

摘要：

采用愈创木酚作为生物质模型化合物,以ZSM-5为催化剂,在固定床反应器中研究了反应温度、质量空速以及分压对热解产物产率、选择性的影响,并考察了催化剂的积炭情况。结果表明,愈创木酚催化热解的主要产物为酚类,其次是芳香烃。温度对产物分布有显著影响。催化剂适量的积炭有利于提高烯烃和芳香烃的产率。根据愈创木酚催化热解反应产物分布,推测其主要反应为脱除甲氧基形成酚类,进一步芳构化形成芳香烃。本文研究结果为研究生物质催化热解反应机理提供了理论依据。

关键词: 生物质, 固定床, 愈创木酚, 催化热解, 产物分布, 积炭

CLC Number:

WANG Yun, SHAO Shanshan, ZHANG Huiyan, XIAO Rui. Catalytic pyrolysis of biomass model compounds to olefins and aromatic hydrocarbons[J]. CIESC Journal, 2015, 66(8): 3022-3028.

王芸, 邵珊珊, 张会岩, 肖睿. 生物质模化物催化热解制取烯烃和芳香烃[J]. 化工学报, 2015, 66(8): 3022-3028.

References 22

[1]	Hua Ben(华贲). Resources and energy trends of petrochemical industry in low carbon era [J]. CIESC Journal (化工学报), 2013, 64 (1): 76-83.
[2]	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.
[3]	Gallezot P. Conversion of biomass to selected chemical products [J]. Chemical Society Reviews, 2012, 41 (4): 1538-1558.
[4]	Carlson T R, Cheng Y T, Jae J, Huber G W. Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust [J]. Energy & Environmental Science, 2011, 4 (1): 145-161.
[5]	Yaman S. Pyrolysis of biomass to produce fuels and chemical feedstocks [J]. Energy Conversion and Management, 2004, 45 (5): 651-671.
[6]	Gayubo A G, Aguayo A T, Atutxa A, Valle B, Bilbao J. Undesired components in the transformation of biomass pyrolysis oil into hydrocarbons on an HZSM-5 zeolite catalyst [J]. Journal of Chemical Technology & Biotechnology, 2005, 80 (11): 1244-1251.
[7]	Guo Xiaoya(郭晓亚), Yan Yongjie(颜涌捷), Ren Zhengwei (任铮伟). The using and forecast of catalyst in bio-oil upgrading [J]. Acta Energiae Solaris Sinica(太阳能学报), 2003, 24 (2): 206-212.
[8]	Mihalcik D J, Mullen C A, Boateng A A. Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components [J]. Journal of Analytical and Applied Pyrolysis, 2011, 92 (1): 224-232.
[9]	Mortensen P M, Grunwaldt J D, Jensen P A, Knudsen K G, Jensen A D. A review of catalytic upgrading of bio-oil to engine fuels [J]. Applied Catalysis A: General, 2011, 407 (1-2): 1-19.
[10]	Guisnet M, Magnoux P. Organic chemistry of coke formation [J]. Applied Catalysis A: General, 2001, 212 (1/2): 83-96.
[11]	Valle B, Castaño P, Olazar M, Bilbao J, Gayubo A G. Deactivating species in the transformation of crude bio-oil with methanol into hydrocarbons on a HZSM-5 catalyst [J]. Journal of Catalysis, 2012, 285 (1): 304-314.
[12]	Chen D, Rebo H P, Moljord K, Holmen A. Influence of coke deposition on selectivity in zeolite catalysis [J]. Industrial & Engineering Chemistry Research, 1997, 36 (9): 3473-3479.
[13]	Zheng A Q, Zhao Z L, Chang S, Huang Z, Wu H X, Wang X B, He F, Li H B. Effect of crystal size of ZSM-5 on the aromatic yield and selectivity from catalytic fast pyrolysis of biomass [J]. Journal of Molecular Catalysis A: Chemical, 2014, 383: 23-30.
[14]	Dai Nan(戴楠), Yang Zhen(杨珍), Huang Yaobing(黄耀兵), Fu Yao(傅尧). Preparation of liquid fuel from lignin phenolic monomers [J]. Journal of Fuel Chemistry and Technology(燃烧化学学报), 2015, 43 (1): 48-53.
[15]	de Wild P, van der Laan R, Kloekhorst A, Heeres E. Lignin valorisation for chemicals and (transportation) fuels via (catalytic) pyrolysis and hydrodeoxygenation [J]. Environmental Progress & Sustainable Energy, 2009, 28 (3): 461-469.
[16]	Graça I, Lopes J M, Ribeiro M F, Ramôa Ribeiro F, Cerqueira H S, de Almeida M B B. Catalytic cracking in the presence of guaiacol [J]. Applied Catalysis B: Environmental, 2011, 101 (3/4): 613-621.
[17]	Zakzeski J, Bruijnincx P C A, Jongerius A L, Weckhuysen B M. The catalytic valorization of lignin for the production of renewable chemicals [J]. Chemical Reviews, 2010, 110 (6): 3552-3599.
[18]	Runnebaum R C, Nimmanwudipong T, Block D E, Gates B C. Catalytic conversion of compounds representative of lignin-derived bio-oils: a reaction network for guaiacol, anisole, 4-methylanisole, and cyclohexanone conversion catalysed by Pt/g-Al2O3 [J]. Catal. Sci. Technol., 2012, 2 (1): 113-118.
[19]	Elkasabi Y, Mullen C A, Pighinelli A L M T, Boateng A A. Hydrodeoxygenation of fast-pyrolysis bio-oils from various feedstocks using carbon-supported catalysts [J]. Fuel Processing Technology, 2014, 123: 11-18.
[20]	Shao S, Zhang H, Xiao R, Shen D, Zheng J. Comparison of catalytic characteristics of biomass derivates with different structures over ZSM-5 [J]. Bio. Energy Research, 2013, 6 (4): 1173-1182.
[21]	Chia D A, Trimm D L. The effect of pre-coking on the activity and selectivity of the catalytic cracking of squalane [J]. Journal of Chemical Technology & Biotechnology, 2005, 80 (3): 353-355.
[22]	Kim Y H, Lee K H, Lee J S. The effect of pre-coking and regeneration on the activity and stability of Zn/ZSM-5 in aromatization of 2-methyl-2-butene [J]. Catalysis Today, 2011, 178 (1): 72-78.