Alkaline sulfite pretreatment of corncob residue and its reaction kinetic model

LOU Hongming1 LIN Meilu1 QIU Kexian1 CAI Cheng1 PANG Yuxia1 YANG Dongjie1 QIU Xueqing1

(1.School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong, China 510641)

【Abstract】Corncob residues (CCR) were obtained from corncobs by using acid hydrolysis for extraction of xylose. Due to the high content of lignin and low content of hemicellulose in corncob residues, the alkaline sulfite pretreatment was used to treat the corncob residue. The effects of pH, liquid/solid ratio, temperature and the dosage of sodium sulfite on the cellulose retained, delignification, substrate enzymatic digestibility (SED) and yield of lignosulfonate in pretreatment spent liquor were investigated. The results showed that with 10% (mass) sodium sulfite (Na2SO3) and 5% (mass) sodium hydroxide (NaOH) on CCR and 1 h pretreatment at 160 °C, the alkaline sulfite pretreatment could make 86.1% of lignin removed and 82.4% of cellulose recovered in pretreatment liquid/solid ratio of 6/1. The SED of CCR increased from 46.4% to 85.1% after 72 h hydrolysis [cellulase loading of 5 FPU·(g glucan)−1], and the yield of lignosulfonate in pretreatment spent liquor was 31.5g·(100 g CCR)−1 under the same pretreatment condition. Lignin factor (LF) was proposed to predict the lignin content of the pretreated CCR to guide the scale up test and engineering application. The delignification kinetics and prediction equation for SED of CCR were established based on the experimental data. The error of SED predicted and SED measured was within 10%.

【Keywords】 biomass; alkaline sulfite pretreatment; mathematical modeling; prediction; reaction kinetics;


【Funds】 National Natural Science Foundation of China (21676109, 21376100) Science and Technology Program of Guangzhou, China (201707020025) Special Support Plan for Cultivating High-level Talents of Guangdong, China (2016TX03Z298) International Cooperation Program of Guangdong Province, China (2013B051000011)

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    [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 ZnCl2 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 FeCl3·6H2O 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 (in Chinese).

    [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]. ACS Sustainable 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 (in Chinese).

    [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 (in Chinese).

    [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 (in Chinese).

    [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 (in Chinese).

    [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 (in Chinese).

    [29] LOU H, ZHU J Y, LAN T Q, et al. pH-induced lignin surface modification to reduce nonspecific cellulase binding and enhance enzymatic saccharification of lignocelluloses [J]. ChemSusChem, 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.

This Article


CN: 11-1946/TQ

Vol 69, No. 01, Pages 507-514

January 2018


Article Outline


  • Introduction
  • 1 Experimental materials and test method
  • 2 Results and discussion
  • 3 Conclusions
  • Symbol description
  • References