低共熔溶剂和次氯酸钠组合预处理秸秆及在丁醇发酵中的应用

doi:10.16085/j.issn.1000-6613.2020-0281

摘要/Abstract

摘要：

随着传统化石能源日趋枯竭，木质纤维素生物质等可再生资源的综合利用得到越来越多的关注。为了更好地利用木质纤维素生物质，采用物理、化学或生物方法降低其结构顽抗性是必不可少的步骤。在前期研究中，本文作者所在实验室发现了一种乙胺盐酸盐为氢键受体、乳酸为氢键供体的新型低共熔溶剂（EaCl∶LAC），其对玉米芯有很好的去除半纤维素的作用。本文将EaCl∶LAC用于预处理水稻秸秆，并结合碱性氧化剂NaClO，进一步提高了木质素的去除率。在最优条件下，经EaCl∶LAC/NaClO预处理后水稻秸秆的半纤维素和木质素的去除率分别为94.9％和80.2％。将预处理后水稻稻秆经纤维素酶解可得到总还原糖浓度为60.46g/L的秸秆水解液。采用梭菌Clostridium saccharobutylicum DSM13864利用稻秆水解液进行丁醇发酵，72h后丁醇浓度为10.16g/L，丁醇的糖醇产率为0.22g/g_{total sugar}。本文提供了一种提高木质纤维素生物质酶解效率和水解液还原糖浓度的方法，无需外源添加葡萄糖和脱毒处理，可直接用于发酵合成生物丁醇。

关键词: 木质纤维素生物质, 低共熔溶剂, 丁醇发酵, 组合预处理

Abstract:

With depletion of traditional fossil energies, comprehensive utilization of renewable resources such as lignocellulosic biomass has received increasing attention. For efficient utilization of lignocellulosic biomass, reducing structural recalcitrance of lignocellulosic biomass by physical, chemical or biological methods is a prerequisite. In our previous study, a new deep eutectic solvent (EaCl∶LAC) was developed with ethylamine hydrochloride as hydrogen bond acceptor and lactic acid as hydrogen bond donor. EaCl∶LAC is efficient in removing the hemicellulose from corncob. In this study, EaCl∶LAC was combined with a basic oxidant NaClO for the pretreatment of rice straw, resulting elevated hemicellulose and lignin removal percentages. After optimization, total reducing sugars in rice straw hydrolysate pretreated by EaCl∶LAC/NaClO was increased to 60.46g/L, with hemicellulose removal of 94.9% and delignification of 80.2%. Furthermore, rice straw hydrolysate was utilized for biobutanol fermentation by Clostridium saccharobutylicum DSM13864, achieving butanol titer of 10.16g/L^{and productivity of 0.22g/g_{total sugar} after 72 hours. This study provides a promising and effective method for pretreatment of lignocellulosic biomass, which can be facilely used in biofuel fermentation without external sugar and detoxification.}

Key words: lignocellulosic biomass, deep eutectic solvent, butanol fermentation, combinatorial pretreatment

中图分类号:

Q815

李浩, 邢婉茹, 许国超, 倪晔. 低共熔溶剂和次氯酸钠组合预处理秸秆及在丁醇发酵中的应用[J]. 化工进展, 2020, 39(12): 5211-5218.

Hao LI, Wanru XING, Guochao XU, Ye NI. Combinatorial pretreatment of straw with DES and sodium hypochlorite and its application in butanol fermentation[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5211-5218.

参考文献

1	ANWAR Z, GULFRAZ M, IRSHAD M. Agro-industrial lignocellulosic biomass a key to unlock the future bio-energy: a brief review [J]. Journal of Radiation Research & Applied Sciences, 2014, 7(2): 163-173.
2	DONG L, CAO G, LEI Z. Alkali/urea pretreatment of rice straw at low temperature for enhanced biological hydrogen production [J]. Bioresource Technology, 2018, 267(21): 71-76.
3	LIM J S, MANAN Z A, ALWI S R W, et al. A review on utilisation of biomass from rice industry as a source of renewable energy [J]. Renewable & Sustainable Energy Reviews, 2012, 16(5): 3084-3094.
4	BINOD P, SINDHU R, SINGHANIA R R, et al. Bioethanol production from rice straw: an overview [J].Bioresource Technology, 2010, 101(13): 4767-4774.
5	马欢, 刘伟伟, 刘萍, 等. 微波预处理对水稻秸秆糖化率与成分和结构的影响[J]. 农业机械学报, 2014, 45(10): 180-186.
5	MA H, LIU W W, LIU P, et al. Effects of microwave pretreatment on enzymatic saccharification and lignocellulosic structure of rice straw [J]. Transactions of the Chinese Society for Agricultural Machinery, 2014, 45(10): 180-186.
6	KADAM K L, FORREST L H, JACOBSON W A. Rice straw as a lignocellulosic resource: collection, processing, transportation, and environmental aspects [J]. Biomass & Bioenergy, 2000, 18(5): 369-389.
7	陈亮, 苏小军, 熊兴耀, 等. 辐照预处理水稻秸秆酶解糖化与发酵产乙醇工艺[J]. 核农学报, 2015, 29(4): 704-709.
7	CHEN L, SU X J, XIONG X Y, et al. Enzymatic saccharification and fermentation of irradiation-pretreated rice straw for ethanol [J]. Journal of Nuclear Agricultural Sciences, 2015, 29(4): 704-709.
8	YANG H H, TSAI C H, CHAO M R, et al. Source identification and size distribution of atmospheric polycyclic aromatic hydrocarbons during rice straw burning period [J]. Atmospheric Environment, 2006, 40(7): 1266-1274.
9	GADDE B, BONNET S, MENKE C, et al. Air pollutant emissions from rice straw open field burning in India, Thailand and the Philippines [J]. Environmental Pollution, 2009, 157(5): 1554-1558.
10	KORENAGA T, LIU X, HUANG Z. The influence of moisture content on polycyclic aromatic hydrocarbons emission during rice straw burning [J]. Chemosphere-Global Change Science, 2001, 3(1): 117-122.
11	JACOBS J, KREUTZER R, SMITH D. Rice burning and asthma hospitalizations, Butte County, California, 1983—1992 [J]. Environmental Health Perspectives, 1997, 105(9): 980-985.
12	HIMMEL M E, DING S Y, JOHNSON D K, et al. Biomass recalcitrance: engineering plants and enzymes for biofuels production [J]. Science, 2007, 315(5813): 804-807.
13	CHIARAMONTI D, PRUSSI M, FERRERO S, et al. Review of pretreatment processes for lignocellulosic ethanol production, and development of an innovative method [J]. Biomass & Bioenergy, 2012, 46(11): 25-35.
14	张振, 臧中盛, 刘苹, 等. 木质纤维素预处理方法的研究进展[J]. 湖北农业科学, 2012, 51(7): 1306-1309.
14	ZHANG Z, ZANG Z S, LIU P, et al. Research advances of pretreatment technology of lignocellulose [J]. Hubei Agricultural Sciences, 2012, 51(7): 1306-1309.
15	HSU T C, GUO G L, CHEN W H, et al. Effect of dilute acid pretreatment of rice straw on structural properties and enzymatic hydrolysis [J]. Bioresource Technology, 2010, 101(13): 4907-4913.
16	陈尚钘, 勇强, 徐勇, 等. 稀酸预处理对玉米秸秆纤维组分及结构的影响[J]. 中国粮油学报, 2011, 26(6): 13-19.
16	CHENG S Y, YONG Q, XU Y, et al. Effect of dilute acid pretreatment on fibre components and structure of corn stover [J]. Journal of the Chinese Cereals and Oils Association, 2011, 26(6): 13-19.
17	易守连. 农作物秸秆木质纤维素组分分离及高效糖化工艺研究[D]. 合肥: 合肥工业大学, 2010.
17	YI S L. Separation and efficient saccharification of lignocellulose from crop straw[D]. Hefei: Hefei University of Technology, 2010.
18	ELGHARBAWY A A, ALAM M Z, MONIRUZZAMAN M, et al. Ionic liquid pretreatment as emerging approaches for enhanced enzymatic hydrolysis of lignocellulosic biomass [J]. Biochemical Engineering Journal, 2016, 109(1): 252-267.
19	SMITH E L, ABBOTT A P, RYDER K S. Deep eutectic solvents (DESs) and their applications [J]. Chemical Reviews, 2014, 114(21): 11060-11082.
20	邢婉茹. 水稻秸秆的低共熔溶剂预处理及其高值化利用的研究[D]. 无锡: 江南大学, 2018.
20	XING W R. Pretreatment of rice straw by deep eutectic solvents and its high-value utilization [D]. Wuxi: Jiangnan University, 2018.
21	GUNNY A A N, ARBAIN D, NASHEF E M, et al. Applicability evaluation of deep eutectic solvents-cellulase system for lignocellulose hydrolysis [J]. Bioresource Technology, 2015, 181(7): 297-302.
22	XU G C, DING J C, HAN R Z, et al. Enhancing cellulose accessibility of corn stover by deep eutectic solvent pretreatment for butanol fermentation [J]. Bioresour Technology, 2016, 203(5): 364-369.
23	XING W R, XU G C, DONG J J, et al. Novel dihydrogen-bonding deep eutectic solvents: pretreatment of rice straw for butanol fermentation featuring enzyme recycling and high solvent yield [J]. Chemical Engineering Journal, 2018, 333(3): 712-720.
24	DING J C, XU G C, HAN R Z, et al. Biobutanol production from corn stover hydrolysate pretreated with recycled ionic liquid by Clostridium saccharobutylicum DSM 13864 [J]. Bioresource Technology, 2015, 199(1): 228-234.
25	HE Y C, DING Y, XUE Y F, et al. Enhancement of enzymatic saccharification of corn stover with sequential Fenton pretreatment and dilute NaOH extraction [J]. Bioresour Technology, 2015, 193(19):324-330.
26	REDDY N, YANG Y. Properties and potential applications of natural cellulose fibers from the bark of cotton stalks [J]. Bioresour Technology, 2009, 100(14): 3563-3569.
27	CAI D, LI P, LUO Z, et al. Effect of dilute alkaline pretreatment on the conversion of different parts of corn stalk to fermentable sugars and its application in acetone-butanol-ethanol fermentation [J]. Bioresour Technology, 2016, 211(13): 117-124.

[1]	马伊, 曹世伟, 王家骏, 林立群, 邢延, 曹腾良, 卢峰, 赵振伦, 张志军. 低共熔溶剂回收废旧锂离子电池正极材料的研究进展[J]. 化工进展, 2023, 42(S1): 219-232.
[2]	杨许召, 李庆, 袁康康, 张盈盈, 韩敬莉, 吴诗德. 含Gemini离子液体低共熔溶剂热力学性质[J]. 化工进展, 2023, 42(6): 3123-3129.
[3]	叶玉玺, 丁晓茜, 池华睿, 朱楷伦, 刘杨, 王凌云, 郭庆杰. 疏水性低共熔溶剂氢键交互作用调控及萃取铜性能[J]. 化工进展, 2022, 41(S1): 397-406.
[4]	何晨露, 邱晨茜, 方娟, 杨旋, 赖建军, 郑新宇, 吕建华, 陈燕丹, 黄彪. 基于低共熔溶剂体系的氮掺杂超级电容炭[J]. 化工进展, 2022, 41(9): 4946-4953.
[5]	程明强, 汝娟坚, 华一新, 王丁, 耿笑, 张文文, 黄皓铭, 王道祥. 低共熔溶剂在废旧锂离子电池正极材料回收中的研究进展[J]. 化工进展, 2022, 41(6): 3293-3305.
[6]	解先利, 刘云云, 余强, 张宇, 张荣清, 邱雨心. 低共熔溶剂预处理提高甘草渣酶解效果优化[J]. 化工进展, 2022, 41(3): 1349-1356.
[7]	阮佳纬, 叶香珠, 陈立芳, 漆志文. 离子液体和低共熔溶剂催化二氧化碳合成有机碳酸酯的研究进展[J]. 化工进展, 2022, 41(3): 1176-1186.
[8]	刘乾静, 陈晓淼, 王芷, 史吉平, 李保国, 刘莉. 低共熔溶剂预处理杨木水解渣拆解木质素[J]. 化工进展, 2022, 41(10): 5612-5618.
[9]	董艳梅, 安艳霞, 马阳阳, 张剑, 李梦琴. 深度共熔溶剂预处理木质纤维素生物质研究进展[J]. 化工进展, 2021, 40(3): 1594-1603.
[10]	易兰, 李文英, 冯杰. 离子液体/低共熔溶剂在煤基液体分离中的应用[J]. 化工进展, 2020, 39(6): 2066-2078.
[11]	刘昊然, 王韵淇, 李秀萍, 赵荣祥. C₆H₁₁NO/nCF₃SO₃H型低共熔溶剂氧化脱除模拟油中的二苯并噻吩[J]. 化工进展, 2020, 39(5): 1632-1640.
[12]	窦金孝,赵永奇,段晓谞,柴红宁,余江龙. 络合亚铁乙二醇-四丁基溴化铵低共熔溶剂协同吸收SO₂和NO[J]. 化工进展, 2020, 39(2): 453-460.
[13]	成洪业, 漆志文. 低共熔溶剂用于萃取分离的研究进展[J]. 化工进展, 2020, 39(12): 4896-4907.
[14]	唐晓东, 张晓普, 李晶晶, 王治宇, 杨柳, 王春. 低共熔溶剂在车用燃料脱硫中的研究进展[J]. 化工进展, 2018, 37(11): 4197-4204.
[15]	王伟, 闫秀懿, 张磊, 周菁辉. 木质纤维素生物质水热液化的研究进展[J]. 化工进展, 2016, 35(02): 453-462.