Pyrolysis study of bamboo Phyllostachys edulis pretreated with ionic liquids mixtures

doi:10.11949/j.issn.0438-1157.20141494

Abstract

Abstract: The pyrolysis study of the ionic liquid (IL)-H₂O mixtures pretreated bamboo (Phyllostachys edulis) was investigated. 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl)-H₂O, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄)-H₂O and 1-butyl-3-methyl pyrrolidinium chloride ([Bmpy]Cl)-H₂O with or without solid acid catalyst (Nafion^®NR50) were used in the pretreatment process. The composition analysis result of untreated bamboo and pretreated bamboo were compared. XRD and SEM result were analyzed to explain the effect of ILs mixture on cellulose crystalline structures and surface structures. According to the result of TG-DTA and GC-TCD, the sample pretreated with [Bmim]Cl-H₂O mixture was used in the pyrolysis process to produce more gaseous products and low char. About 0.12 g gaseous products and 0.19 g char were produced from 1.0 g sample pretreated with [Bmim]Cl-H₂O mixture and added solid acid catalyst, different from the result of untreated sample, 0.04 g gaseous products and 0.24 g char. The potential and problems of IL-H₂O mixture pretreatment used in thermal chemical conversion methods were discussed.

Key words: ionic liquids, mixture solvent, biomass, pretreatment, pyrolysis

摘要： 使用1-丁基-3-甲基咪唑氯化盐([Bmim]Cl)、1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF₄)和1-丁基-1-甲基吡咯烷氯化物([Bmpy]Cl)与水并添加固体酸催化剂Nafion^®NR50组成的混合溶剂对孟宗竹进行预处理比较研究,分析了处理后孟宗竹的成分含有量、结晶结构和表面形貌等变化。把处理后的孟宗竹应用于热解研究中,通过TG-DTA和GC-TCD的分析,发现[Bmim]Cl离子液体的混合溶剂处理后的孟宗竹更易于热解反应;此外热解产物更多地从焦炭转化成气体产物;其中添加固体酸的混合溶剂预处理后的1.0 g孟宗竹样品中,在热解反应后焦炭含量为0.19 g,低于未处理样品的0.24 g;生成约0.12 g气体产物大于未处理样品的0.04 g。并探讨了离子液体混合溶剂作为一种新型前处理溶剂应用于生物质热解研究中的潜力和问题。

关键词: 离子液体, 混合溶剂, 生物质, 预处理, 热解

CLC Number:

TQ027

CHEN Qiyu, WANG Qingyue. Pyrolysis study of bamboo Phyllostachys edulis pretreated with ionic liquids mixtures[J]. CIESC Journal, 2015, 66(5): 1874-1882.

陈启宇, 王青跃. 离子液体混合溶剂预处理后孟宗竹的热解[J]. 化工学报, 2015, 66(5): 1874-1882.

References 29

[1]	Edward L, Mui K, Cheung W H, Lee V K C, McKay G. Kinetic study on bamboo pyrolysis [J]. Ind. Eng. Chem. Res., 2008, 47 (15): 5710-5722
[2]	Jiang Z H, Liu Z J, Fei B H, Cai Z Y, Yua Y, Liu X E. The pyrolysis characteristics of moso bamboo [J]. J. Anal. Appl. Pyrolysis, 2012, 94: 48-52
[3]	Lasa H D, Salaices E, Mazumder J, Lucky R. Catalytic steam gasification of biomass: catalysts, thermodynamics and kinetics [J]. Chem. Rev., 2011, 111 (9): 5404-5433
[4]	Ranzi E, Cuoci A, Faravelli T, Frassoldati A, Migliavacca G, Pierucci S, Sommariva S. Chemical kinetics of biomass pyrolysis [J]. Energy Fuels, 2008, 22 (6): 4292-4300
[5]	Mosier N, Wyman C, Dale B, Elander R, Lee Y Y, Holtzapple M, Ladisch M. Features of promising technologies for pretreatment of lignocellulosic biomass [J]. Bioresour. Technol., 2005, 96 (6): 673-686
[6]	Swatloski R P, Spear S K, Holbery J D, Rogers R D. Dissolution of cellulose with ionic liquids [J]. J. Am. Chem. Soc., 2002, 124 (18): 4974-4975
[7]	Olivier-bourbigou H, Magna L, Morvan D. Ionic liquids and catalysis: recent progress from knowledge to applications [J]. Appl. Catal. A. Gen., 2010, 373 (1/2): 1-56
[8]	Zhao H, Holladay J E, Brown H, Zhang Z C. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural [J]. Science, 2007, 316 (5831): 1597-1600
[9]	Brandt A, Grasvik J, Hallett J P, Welton T. Deconstruction of lignocellulosic biomass with ionic liquids [J]. Green. Chem., 2013, 15: 550-583
[10]	Brandt A, Ray M J, To T Q, Leak D J, Murphy R J, Welton T. Ionic liquid pretreatment of lignocellulosic biomass with ionic liquid-water mixtures [J]. Green. Chem., 2011, 13: 2489-2499
[11]	Hou X D, Li N, Zong M H. Facile and simple pretreatment of sugar cane bagasse without size reduction using renewable ionic liquids-water mixtures [J]. Acs. Sustain. Chem. Eng., 2013, 1: 519-526
[12]	Zhang Z Y, O'Hara I M, Doherty W O S. Effects of pH on pretreatment of sugarcane bagasse using aqueous imidazolium ionic liquids [J]. Green. Chem., 2013, 15: 431-438
[13]	Zhang Z Y, O'Hara I M, Doherty W O S. Pretreatment of sugarcane bagasse by acid-catalysed process in aqueous ionic liquid solutions [J]. Bioresour. Technol., 2012, 120 (1): 149-156
[14]	López-Pastor M, Ayora-Cañada M J, Valcárcel M, Lendl B. Association of methanol and water in ionic liquids elucidated by infrared spectroscopy using two-dimensional correlation and multivariate curve resolution [J]. J. Phys. Chem. B , 2006, 110: 10896-10902
[15]	Zhang L, Xu Z, Wang Y, Li H. Prediction of the solvation and structural properties of ionic liquids in water by two-dimensional correlation spectroscopy [J]. J. Phys. Chem. B , 2008, 112: 6411-6419
[16]	Mazza M, Catana D A, Vaca-Garcia C, Cecutti C. Influence of water on the dissolution of MCC in selected ionic liquids [J]. Cellulose, 2009, 16: 207-215
[17]	Rinaldi R, Palkovits P, Schüth F. Depolymerization of cellulose using solid catalysts in ionic liquids [J]. Angew. Chem. Int. Edit., 2008, 47: 8047-8050
[18]	Kim S J, Dwiatmoko A A, Choi J W, Suh Y W, Suh D J, Oh M. Cellulose pretreatment with 1-n-butyl-3-methylimidazolium chloride for solid acid-catalyzed hydrolysis [J]. Bioresour. Technol., 2010, 101 (21): 8273-8279
[19]	Wei L G, Li K L, Ma Y C, Hou X. Dissolving lignocellulosic biomass in a 1-butyl-3-methylimidazolium chloride-water mixture [J]. Ind. Crop. Prod., 2012, 37 (1): 227-234
[20]	Fu D, Mazza G, Tamaki Y. Lignin extraction from straw by ionic liquids and enzymatic hydrolysis of the cellulosic residues [J]. J. Agric. Food. Chem., 2010, 58: 2915-2922
[21]	Çetinkol Ö P, Dibble D C, Cheng G, Kent M S, Knierim B, Auer M, Wemmer D E, Pelton J G, Melnichenko Y B, Ralph J, Simmons B A, Holmes B M. Understanding the impact of ionic liquid pretreatment on eucalyptus [J]. Biofuels, 2010, 1: 33
[22]	Cox B J, Jia S, Zhang Z C, Ekerdt J G. Catalytic degradation of lignin model compounds in acidic imidazolium based ionic liquids: Hammett acidity and anion effects [J]. Polym. Degrad. Stab., 2011, 96: 426-431
[23]	Xu Tingting (徐婷婷), Xu Junli (徐俊丽), Zhang Zhibo (张志博), Zhou Qing (周清), Xin Jiayu (辛加余), Lü Xingmei (吕兴梅), Zhang Suojiang (张锁江). Enhanced pretreatment of cornstalks by binary ionic liquids [J]. CIESC Journal (化工学报), 2013, 64 (S1): 66-72
[24]	Liu Liyang (刘黎阳), Niu Kun (牛坤), Liu Chenguang (刘晨光), Bai Fengwu (白凤武). Effect of ionic liquid pretreatment on lignocellulosic biomass from oilseeds [J]. CIESC Journal (化工学报), 2013, 64 (S1): 104-110
[25]	Cheng G, Varanasi P, Arora R, Stavila V, Simmons B A, Kent M S, Singh S. Impact of ionic liquid pretreatment conditions on cellulose crystalline structure using 1-ethyl-3-methylimidazolium acetate [J]. J. Phys. Chem. B , 2012, 116: 10049-10054
[26]	Tan H T, Lee K T, Mohamed A R. Pretreatment of lignocellulosic palm biomass using a solvent-ionic liquid [BMIM]Cl for glucose recovery: an optimisation study using response surface methodology [J]. Carbohyd. Polym., 2011, 83: 1862-1868
[27]	Kumar P, Barrett M D, Delwiche M J, Stroeve P. Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production [J]. Ind. Eng. Chem. Res., 2009, 48 (8): 3713-3729
[28]	Poletto M, Pistor V, Zeni M, Zattera A J. Crystalline properties and decomposition kinetics of MCC fibers in wood pulp obtained by two pulping processes [J]. Polym. Degrad. Stab., 2010, 96: 679-685
[29]	Yang H P, Yan R, Chen H P, Zheng C G, Lee D H, Liang D T. In-depth investigation of biomass pyrolysis based on three major components: hemicelluloses, cellulose and lignin [J]. Energy Fuels, 2006, 20 (1): 388-393