疏水性离子液体[C4mim][PF6]对木质纤维预水解液的脱毒作用

doi:10.3969/j.issn.0253-2417.2017.05.006

林产化学与工业 ›› 2017, Vol. 37 ›› Issue (5): 45-52.doi: 10.3969/j.issn.0253-2417.2017.05.006

疏水性离子液体[C₄mim][PF₆]对木质纤维预水解液的脱毒作用

程逸超^1,2, 杨金龙^1,2, 朱均均^1,2,3, 徐勇^1,2,3, 勇强^1,2, 余世袁^1,2

1. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037;
2. 南京林业大学化学工程学院, 江苏南京 210037;
3. 江苏省生物质绿色燃料与化学品重点实验室, 江苏南京 210037

收稿日期:2017-02-10 出版日期:2017-10-25 发布日期:2017-10-30
通讯作者: 朱均均,副教授,博士,研究领域为生物化工;E-mail:zhujj@njfu.edu.cn。 E-mail:zhujj@njfu.edu.cn
作者简介:程逸超(1992-),男,安徽安庆人,硕士生,研究方向为生物化工
基金资助:
“十二五”国家科技支撑计划资助（2015BAD15B09）；江苏省普通高校研究生科研创新计划资助项目（SJLX_0406）；江苏高校优势学科建设工程资助项目（无编号）

Detoxification of Lignocellulosic Prehydrolyzate by Hydrophobic Ionic Liquid[C₄mim] [PF₆]

CHENG Yichao^1,2, YANG Jinlong^1,2, ZHU Junjun^1,2,3, XU Yong^1,2,3, YONG Qiang^1,2, YU Shiyuan^1,2

1. Jiangsu Co-innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China;
2. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;
3. Jiangsu Key Lab of Biomass-based Green Fuel and Chemicals, Nanjing 210037, China

Received:2017-02-10 Online:2017-10-25 Published:2017-10-30

摘要/Abstract

摘要： 将稀酸蒸汽爆破预处理后的玉米秸秆进行预水解，以离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[C₄mim][PF₆]）萃取脱除预水解液中的抑制物，并对萃取脱毒条件进行优化，进一步分析了离子液体的脱毒效果。研究结果表明，最佳萃取条件为：水油相体积比1：2、35℃、250 r/min下萃取60 min。在此条件下，水解液中的主要抑制物甲酸、乙酸、乙酰丙酸、5-羟甲基糠醛、糠醛和总酚的去除率分别达到24.72%、21.84%、47.99%、82.76%、100%和39.70%，且可发酵性糖几乎无损失。通过对主要抑制物与离子液体脱毒性能分析可知，随着离子液体[C_nmim][PF₆]（n=4，6，8）中阳离子烷基碳链增长，离子液体对抑制物萃取能力下降；抑制物疏水性越强，与离子液体的氢键作用越强，萃取分离效果越好；pH值越低，对抑制物的去除效果越好；乙酸、5-羟甲基糠醛、4-羟基苯甲醛在[C₄mim][PF₆]中去除率基本不随抑制物初始质量浓度改变而发生变化。

关键词: 木质纤维原料, 抑制物, 离子液体, 萃取, 脱毒

Abstract: In this study, a new green detoxification technology named-ionic liquid extraction was used for detoxification of the prehydrolyzate obtained from the washed acid-catalyzed steam-exploded corn stover in order to improve the ethanol fermentability of yeast. 1-butyl-3-methyl imidazole hexafluorophosphate([C₄mim] [PF₆]) was selected as the extraction agent and its extraction conditions had been optimized. The optimal extraction conditions were as follows:the ratio of aqueous to organic phase 1:2, 35℃, 250 r/min, and 60 min. Under these conditions, the removal rate of formic acid, acetic acid, levulinic acid, 5-hydroxymethylfurfural, furfural and total phenols in the hydrolysate reached 24.72%, 21.84%, 47.99%, 82.76%, 100% and 39.7% respectively, the extraction efficiencies of the main inhibitors were high and the loss of sugars was negligible. The results of detoxification mechanism indicated that the extraction efficiency of the inhibitors decreased with the increase of alkyl chain length on the cation of ionic liquid[C_nmim] [PF₆] (n=4, 6, 8); the more hydrophobic the inhibitors were, the stronger the hydrogen bonding with ionic liquid was; the lower the pH value was, the better the extraction efficiency of inhibitors was.The removal rate of acetic acid, 5-hydroxymethylfurfural and 4-hydroxybenzaldehyde in[C₄mim] [PF₆] did not change with the initial mass concentration of inhibitors.

Key words: lignocellulose, inhibitor, ionic liquid, extraction, detoxification

中图分类号:

TQ353

程逸超, 杨金龙, 朱均均, 徐勇, 勇强, 余世袁. 疏水性离子液体[C₄mim][PF₆]对木质纤维预水解液的脱毒作用[J]. 林产化学与工业, 2017, 37(5): 45-52.

CHENG Yichao, YANG Jinlong, ZHU Junjun, XU Yong, YONG Qiang, YU Shiyuan. Detoxification of Lignocellulosic Prehydrolyzate by Hydrophobic Ionic Liquid[C₄mim] [PF₆][J]. Chemistry and Industry of Forest Products, 2017, 37(5): 45-52.

参考文献

[1] SRIVASTAVA N,RAWAT R,OBEROI H S,et al. A review on fuel ethanol production from lignocellulosic biomass[J]. International Journal of Green Energy,2015,12(9):949-960.
[2] BRETHAUERS,STUDER M H. Biochemical conversion processes of lignocellulosic biomass to fuels and chemicals:A review[J]. CHIMIA International Journal for Chemistry,2015,69(10):572-581.
[3] LIMAYEM A,RICKE S C. Lignocellulosic biomass for bioethanol production:Current perspectives,potential issues and future prospects[J]. Progress in Energy and Combustion Science,2012,38(4):449-467.
[4] SOUDHAM V P,BRANDBERG T,MIKKOLA J P,et al. Detoxification of acid pretreated spruce hydrolysates with ferrous sulfate and hydrogen peroxide improves enzymatic hydrolysis and fermentation[J]. Bioresource Technology,2014,166:559-565.
[5] JÖNSSON L J,ALRIKSSON B,NILVEBRANT N O. Bioconversion of lignocellulose:Inhibitors and detoxification[J]. Biotechnology for Biofuels,2013,6:16.
[6] PIENKOS P T,ZHANG M. Role of pretreatment and conditioning processes on toxicity of lignocellulosic biomass hydrolysates[J]. Cellulose,2009,16(4):743-762.
[7] JEONG S Y,TRINH L T P,LEE H J,et al. Improvement of the fermentability of oxalic acid hydrolysates by detoxification using electrodialysis and adsorption[J]. Bioresource Technology,2014,152:444-449.
[8] MITHRA M G,PADMAJA A G. Phenolic inhibitors of saccharification and fermentation in lignocellulo-starch prehydrolysates and comparative efficacy of detoxification treatments[J]. Journal of Biomass to Biofuel,2016,3:1-15.
[9] 申园园. 超声辅助-纳米零价铁/过氧化氢降解离子液体[D]. 洛阳:河南科技大学硕士学位论文,2013. SHEN Y Y. Detoxification of acid pretreated spruce hydrolysates with ferrous sulfate and hydrogen peroxide improves enzymatic hydrolysis and fermentation[D]. Luoyang:Master Degree Thesis of Henan University of Science and Technology,2013.
[10] OLIVEIRA F S,ARAÚJO J M M,FERREIRA R,et al. Extraction of L-lactic,L-malic,and succinic acids using phosphonium-based ionic liquids[J]. Separation and Purification Technology,2012,85(10):137-146.
[11] 赵扬,裴渊超,武坤,等. 利用咪唑类离子液体分离发酵液中的糠醛[J]. 河南师范大学学报:自然科学版,2007,35(4):212. ZHAO Y,PEI Y C,WU K,et al. Separation of furfural from fermentation broth by using imidazoles ionic liquids[J]. Journal of Henan Normal University:Natural Science,2007,35(4):212.
[12] 万辉,黄德英,蔡源,等.[omim] BF₄离子液体萃取酚类化合物的研究[J]. 高校化学工程学报,2008,22(1):162-165. WAN H,HUANG D Y,CAI Y,et al. Extraction of phenolic compounds with[omim] BF₄ ionic liquid[J]. Journal of Chemical Engineering of Chinese Universities,2008,22(1):162-165.
[13] 杨金龙,荣亚运,高露,等. 咪唑类离子液体对木质纤维预水解液的脱毒[J]. 化工学报,2015,67(4):1490-1496. YANG J L,RONG Y Y,GAO L,et al. Detoxification of lignocellulosic prehydrolyzate using imidazolium-based ionic liquid[J]. CIESC Journal,2015,67(4):1490-1496.
[14] ZHU J J,YANG J L,ZHU Y Y,et al. Cause analysis of the effects of acid-catalyzed steam-exploded corn stover prehydrolyzate on ethanol fermentation by Pichia stipitis CBS 5776[J]. Bioprocess and Biosystems Engineering,2014,37(11):2215-2222.
[15] 江智婧,朱均均,李鑫,等. 反相高效液相色谱法定量分析木质素的主要降解产物[J]. 色谱,2011,29(1):59-62. JIANG Z J,ZHU J J,LI X,et al. Determination of main degradation products of lignin using reversed-phase high performance liquid chromatography[J]. Chinese Journal of Chromatography,2011,29(1):59-62.
[16] LI J B,HENRIKSSON G,GELLERSTEDT G. Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion[J]. Bioresource Technology,2007,98(16):3061-3068.
[17] JÖNSSON L J,MARTíN C. Pretreatment of lignocellulose:Formation of inhibitory by-products and strategies for minimizing their effects[J]. Bioresource Technology,2016,199:103-112.
[18] LAI C H,LI X,ZHU J J,et al. Detoxification of steam-exploded corn stover prehydrolyzate with organobentonite enhances ethanol fermentation by Pichia stipitis[J]. Bioresources,2016,11(1):1905-1918.
[19] 宋旭东,李肖华,姬登祥,等. 咪唑类疏水性离子液体用于萃取苯酚的研究[J]. 浙江工业大学学报,2009,37(3):251-254. SONG X D,LI X H,JI D X,et al. Research on extraction of phenol with imidazole-based hydrophobic ionic liquids[J]. Journal of Zhejiang University of Technology,2009,37(3):251-254.
[20] HOU Y C,REN Y H,PENG W,et al. Separation of phenols from oil using imidazolium-based ionic liquids[J]. Industrial and Engineering Chemistry Research,2013,52(50):18071-18075.
[21] 吕廷婷,季金苟,夏之宁,等. 离子液体萃取有机物的研究进展[J]. 化工进展,2010,29(5):801-806. LV T T,JI J G,XIA Z N,et al. Progress in room temperature ionic liquids for extraction of organic compounds[J]. Chemical Industry and Engineering Progress,2010,29(5):801-806.
[22] 毛世越,刘汉兰. 疏水性离子液体萃取氯酚类物质[J]. 化工学报,2015,66(S1):260-264. MAO S Y,LIU H L. Extraction of chlorophenols with imidazole-based hydrophobic ionic liquids[J]. CIESC Journal,2015,66(S1):260-264.
[23] YANG Q W,XING H B,SU B G,et al. The essential role of hydrogen-bonding interaction in the extractive separation of phenolic compounds by ionic liquid[J]. AIChE Journal,2013,59(5):1657-1667.
[24] 张香平,白银鸽,闫瑞一,等. 离子液体萃取分离有机物研究进展[J]. 化工进展,2016,35(6):1587-1605. ZHANG X P,BAI Y G,YAN R Y,et al. Progress in ionic liquids for extraction of organic compounds[J]. Chemical Industry and Engineering Progress,2016,35(6):1587-1605.
[25] CHEN D X,OUYANG X K,WANG Y G,et al. Liquid-liquid extraction of caprolactam from water using room temperature ionic liquids[J]. Separation and Purification Technology,2013,104:263-267.
[26] REICHARDT C,WELTON T. Solvents and Solvent Effects in Organic Chemistry[M]. New York:John Wiley & Sons,2011.
[27] 李闲,张锁江,张建敏,等. 疏水性离子液体用于萃取酚类物质[J]. 过程工程学报,2005,5(2):148-151. LI X,ZHANG S J,ZHANG J M,et al. Extraction of phenols with hydrophobic ionic liquids[J]. The Chinese Journal of Process Engineering,2005,5(2):148-151.
[28] WANG J J,PEI Y C,ZHAO Y,et al. Recovery of amino acids by imidazolium based ionic liquids from aqueous media[J]. Green Chemistry,2005,7(4):196-202.

疏水性离子液体[C₄mim][PF₆]对木质纤维预水解液的脱毒作用

Detoxification of Lignocellulosic Prehydrolyzate by Hydrophobic Ionic Liquid[C₄mim] [PF₆]

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