玉米芯残渣的碱性亚硫酸盐预处理及其反应动力学模型

楼宏铭¹ 林美露¹ 邱珂贤¹ 蔡诚¹ 庞煜霞¹ 杨东杰¹ 邱学青¹

(1.华南理工大学化学与化工学院, 广东广州 510641)

【摘要】玉米芯提取木糖后残留了大量富含纤维素和木质素的废弃物。针对玉米芯残渣 (corncob residues, CCR) 中木质素含量高和半纤维素含量很低的特点, 采用碱性亚硫酸盐法进行预处理。研究了预处理p H、液固比、温度、亚硫酸盐用量等条件对纤维素保留率、木质素去除率、底物酶解效率以及预处理液中木质素磺酸钠含量的影响规律。结果表明, 当亚硫酸钠用量为10% (质量) 、氢氧化钠为5% (质量) 、液固比为6:1、160℃预处理1 h时, 可去除86.1%的木质素、保留82.4%的纤维素, 底物的72 h酶解率达85.1%[酶载量为5 FPU· (g葡聚糖) ^-1], 预处理液中木质素磺酸钠的收率为31.5 g· (100 g CCR) ^-1。为了指导放大试验和工程应用, 提出了一个能准确预测底物木质素含量的参数——木质素因子 (lignin factor, LF) , 在此基础上成功建立了脱木质素反应动力学经验公式以及底物酶解效率的预测方程, 预测值与实测值误差在10%之内。

【关键词】 生物质; 碱性亚硫酸盐预处理; 数学模拟; 预测; 反应动力学;

【DOI】

【基金资助】 国家自然科学基金项目 (21676109, 21376100) supported by the National Natural Science Foundation of China (21676109, 21376100) 广州市科技计划项目 (201707020025) Science and Technology Program of Guangzhou, China (201707020025) 广东省特支计划 (2016TX03Z298) Special Support Plan for Cultivating High-level Talents of Guangdong, China (2016TX03Z298) 广东省国际合作项目 (2013B051000011) International Cooperation Program of Guangdong, China (2013B051000011)

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References

[1]SOMERVILLE C, YOUNGS H, TAYLOR C, et al.Feedstocks for lignocellulosic biofuels[J].Science, 2010, 329:790-792.

[2]LI H, DENG A, REN J, et al.Catalytic hydrothermal pretreatment of corncob into xylose and furfural via solid acid catalyst[J].Bioresource Technology, 2014, 158:313-320.

[3]OH S J, JUNG S H, KIM J S.Co-production of furfural and acetic acid from corncob using Zn Cl2 through fast pyrolysis in a fluidized bed reactor[J].Bioresource Technology, 2013, 144:172-178.

[4]ZHANG L, YU H, WANG P, et al.Production of furfural from xylose, xylan and corncob in gamma-valerolactone using FeC l3·6H2O as catalyst[J].Bioresource Technology, 2014, 151:355-360.

[5]TANG Y, ZHAO D, CRISTHIAN C, et al.Simultaneous saccharification and cofermentation of lignocellulosic residues from commercial furfural production and corn kernels using different nutrient media[J].Biotechnology for Biofuels, 2011, 4 (1) :1.

[6]XING Y, BU L, SUN D, et al.High glucose recovery from direct enzymatic hydrolysis of bisulfite-pretreatment on non-detoxified furfural residues[J].Bioresource Technology, 2015, 193:401-407.

[7]YU H, XING Y, LEI F, et al.Improvement of the enzymatic hydrolysis of furfural residues by pretreatment with combined green liquor and ethanol organosolv[J].Bioresource Technology, 2014, 167:46-52.

[8]BU L, XING Y, YU H, et al.Comparative study of sulfite pretreatments for robust enzymatic saccharification of corn cob residue[J].Biotechnol Biofuels, 2012, 5 (12) :87-91.

[9]WANG G S, PAN X J, ZHU J Y, et al.Sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL) for robust enzymatic saccharification of hardwoods[J].Biotechnology Progress, 2009, 25 (4) :1086-1093.

[10]ZHU J Y, PAN X J, WANG G S, et al.Sulfite pretreatment (SPORL) for robust enzymatic saccharification of spruce and red pine[J].Bioresource Technology, 2009, 100:2411-2418.

[11]ZHU J Y, ZHU W Y, OBRYAN P, et al.Ethanol production from SPORL-pretreated lodgepole pine:preliminary evaluation of mass balance and process energy efficiency[J].Appl.Microbiol.Biotechnol., 2010 86:1355-1365.

[12]ZHANG D S, YANG Q, ZHU J Y, et al.Sulfite (SPORL) pretreatment of switchgrass for enzymatic saccharification[J].Bioresource Technology, 2013, 129:127-134.

[13]LIU Q, LOU H M, YANG D J, et al.Research on compatibility of graft-sulfonated lignin as superplasticizers[J].Fine Chemicals, 2008, 25 (10) :1016-1020.

[14]WINOWISKI T, BRZEZINSKI J, LEBO S.Improved efficacy of lignosulfonate dispersants through a novel combination[C]//DOWNER R A, MUENINGHOFF J C, VOLGAS G C.Pesticide Formulations and Delivery Systems:Meeting the Challenges of the Current Crop Protection Industry.ASTM International, 2003.

[15]QIN Y L, YANG D J, QIU X Q.Hydroxypropyl sulfonated lignin as dye dispersant:effect of average molecular weight[J].ACSSustainable Chemistry&Engineering, 2015, 3 (12) :3239-3244.

[16]WU Y X, ZHOU J H, YE C C, et al.Optimized synthesis of lignosulphonate-gpoly (acrylic acid-co-acrylamide) superabsorbent hydrogel based on the Taguchi method[J].Iran.Polym.J., 2010, 19 (7) :511-520.

[17]SLUITER A, HAMES B, RUIZ R, et al.Determination of structural carbohydrates and lignin in biomass.LAP-002 NREL Analytical Procedure[R].National Renewable Energy Laboratory Golden, Co, 2008.

[18]PANG Y X, YANG D J, QIU X Q, et al.An improvement on the measuring method of the sulphonation degree of lignosulfonate[J].Paper Industry, 2006, 27 (11) :38-40.

[19]LIU L, SUN J, CAI C, et al.Corn stover pretreatment by inorganic salts and its effects on hemicellulose and cellulose degradation[J].Bioresource Technology, 2009, 100 (23) :5865-5871.

[20]LIU Z P.Improvement of high temperature sulfonation of wheat straw alkali lignin and its precipitation mechanism on fiber surface[D].Guangzhou:South China University of Technology, 2012.

[21]LINDGREN C, LINDSTRÖM M E.The kinetics of residual delignification and factors affecting the amount of residual lignin during kraft pulping[J].Journal of Pulp and Paper Science (JPPS) , 1996, 22 (8) :290-295.

[22]SANTOS A, RODRÍGUEZ F, GILARRANZ M A, et al.Kinetic modeling of kraft delignification of Eucalyptus globulus[J].Industrial&Engineering Chemistry Research, 1997, 36 (10) :4114-4125.

[23]DOLK M, YAN J F, MCCARTHY J L.Lignin 25.Kinetics of delignification of western Hemlock in flow-through reactors under alkaline conditions[J].Holzforschung-International Journal of the Biology, Chemistry, Physics and Technology of Wood, 1989, 43 (2) :91-98.

[24]KIM S, HOLTZAPPLE M T.Delignification kinetics of corn stover in lime pretreatment[J].Bioresource Technology, 2006, 97 (5) :778-785.

[25]ZHAN H Y.Pulping Principle and Engineering[M].3rd ed.Beijing:China Light Industry Press, 2014:26-106.

[26]SONG L L.Mechanism study on improvement of enzymatic hydrolysis of corn stover by efficient lignin modification with white-rot fungus[D].Wuhan:Huazhong University of Science and Technology, 2013.

[27]PAN X.Role of functional groups in lignin inhibition of enzymatic hydrolysis of cellulose to glucose[J].Journal of Biobased Materials and Bioenergy, 2008, 2:25-32.

[28]CUI M, HUANG R L, SU R X, et al.Au overview on lignocellulose pretreatment and recalcitrant characteristics[J].CIESC Journal, 2012, 63 (3) :677-687.

[29]LOU H, ZHU J Y, LAN T Q, et al.p H-Induced lignin surface modification to reduce nonspecific cellulase binding and enhance enzymatic saccharification of lignocelluloses[J].ChemS us Chem, 2013, 6:919-927.

[30]LOU H, WANG M, LAI H, et al.Reducing non-productive adsorption of cellulase and enhancing enzymatic hydrolysis of lignocelluloses by noncovalent modification of lignin with lignosulfonate[J].Bioresource Technology, 2013, 146:478-484.

[31]WANG Z, ZHU J Y, FU Y, et al.Lignosulfonate-mediated cellulase adsorption:enhanced enzymatic saccharification of lignocellulose through weakening nonproductive binding to lignin[J].Biotechnology for Biofuels, 2013, 6:156.

[32]ZHANG C, HOUTMAN C J, ZHU J Y.Using low temperature to balance enzymatic saccharification and furan formation during SPORL pretreatment of Douglas-fir[J].Process Biochemistry, 2014, 49:466-473.

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