Characterization of Lignins Isolated from Alkali Treated Prehydrolysate of Corn Stover

doi:10.1016/S1004-9541(13)60468-1

Abstract

Abstract: Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure. Thermogravimetric analysis was applied to follow the thermal degradation, and wet chemical method was used to determine the sugar content. The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl, guaiacyl and p-hydroxyphenyl units, containing associated polysaccharides, lipids, and melted salts. Some of the crude lignin was chemically linked to hemicelluloses (mainly xylan). The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains, fatty acids, triterpenols, waxes, and derivatives of aromatic. The sugar content of purified lignin was less than 2.11%, mainly composed of guaiacyl units. DTG_max of purified lignin was 359℃. The majority of the hydroxyl groups were phenolic hydroxyl groups. The main type of linkages in purified lignin was β-O-4. Other types of linkages included β-5, β-β and α-O-4.

Key words: lignin structure, cellulose ethanol, alkaline pretreatment, corn stover, purification

LEI Mingliu, ZHANG Hongman, ZHENG Hongbo, LI Yuanyuan, HUANG He, XU Rong . Characterization of Lignins Isolated from Alkali Treated Prehydrolysate of Corn Stover[J]. Chin.J.Chem.Eng., 2013, 21(4): 427-433.

References

1 Zakzeski, J., Bruijnincx, P.C.A., Jongerius, A.L., Weckhuysen, B.M., “The catalytic valorization of lignin for the production of renewable chemicals”, Chem. Rev., 110 (6), 3552-3599 (2010).

2 Himmel, M.E., Ding, S.Y., Johnson, D.K., Adney, W.S., Nimlos, M.R., Brady, J.W., Foust, T.D., “Biomass recalcitrance: engineering plants and enzymes for biofuels production”, Science, 315 (5813), 804 (2007).

3 Chandra, R., Bura, R., Mabee, W., Berlin, A., Pan, X., Saddler, J., “Substrate pretreatment: The key to effective enzymatic hydrolysis of lignocellulosics?”, Adv. Biochem. Eng. Biotechnol., 108, 67-93 (2007).

4 Alvira, P., Tomas-Pejo, E., Ballesteros, M., Negro, M.J., “Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review”, Bioresour. Technol, 101 (13), 4851-4861 (2010).

5 Zheng, Y., Pan, Z., Zhang, R., “Overview of biomass pretreatment for cellulosic ethanol production”, Int. J. Agr. Biol. Eng., 2 (3), 51 (2009).

6 Kumar, P., Barrett, D.M., Delwiche, M.J., Stroeve, P., “Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production”, Ind. Eng. Chem. Res., 48 (8), 3713-3729 (2009).

7 Yang, B., Wyman, C.E., “Pretreatment: the key to unlocking low-cost cellulosic ethanol”, Biofuels Bioprod. Bior., 2 (1), 26-40 (2008).

8 Sun, X., Xu, F., Sun, R., Wang, Y., Fowler, P., Baird, M., “Characteristics of degraded lignins obtained from steam exploded wheat straw”, Polym. Degrad. Stabili., 86 (2), 245-256 (2004).

9 Ruiz-Rosas, R., Bedia, J., Lallave, M., Loscertales, I., Barrero, A., Rodriguez-Mirasol, J., Cordero, T., “The production of submicron diameter carbon fibers by the electrospinning of lignin”, Carbon, 48 (3), 696-705 (2010).

10 Chujo, Y., Kajiwara, Y., “Microwave-enhanced hybridizations of biopolymers with silica: effective method for rapid preparation and homogeneous dispersion”, Polym. Bull., 66 (8), 1039-1050 (2011).

11 El-Mekkawi, S.A., Ismail, I.M., El-Attar, M.M., Fahmy, A.A., Mohammed, S.S., “Utilization of black liquor as concrete admixture and set retarder aid”, J. Adv. Res., 2 (2), 163-169 (2011).

12 Rodrigues Pinto, P.C., Borges da Silva, E.A., Rodrigues, A.r.E.d., “Insights into oxidative conversion of lignin to high-added-value phenolic aldehydes”, Ind. Eng. Chem. Res., 50 (2), 741-748 (2010).

13 Gosselink, R., De Jong, E., Guran, B., Abacherli, A., “Co-ordination network for lignin-standardisation, production and applications adapted to market requirements (EUROLIGNIN)”, Ind. Crop. Prod., 20 (2), 121-129 (2004).

14 Nadji, H., Diouf, P., Benaboura, A., Bedard, Y., Riedl, B., Stevanovic, T., “Comparative study of lignins isolated from Alfa grass (Stipa tenacissima L.)”, Bioresour. Technol., 100 (14), 3585-3592 (2009).

15 Guerra, A., Lucia, L.A., Argyropoulos, D.S., “Isolation and characterization of lignins from Eucalyptus grandis Hill ex Maiden and Eucalyptus globulus Labill. by enzymatic mild acidolysis (EMAL)”, Holzforschung, 62 (1), 24-30 (2008).

16 Wu, S., Argyropoulos, D., “An improved method for isolating lignin in high yield and purity”, J. Pulp. Pap. Sci., 29 (7), 235-240 (2003).

17 Evtuguin, D., Neto, C., Silva, A., Domingues, P., Amado, F., Robert, D., Faixs, O., “Comprehensive study on the chemical structure of dioxane lignin from plantation Eucalyptus globulus wood”, J. Agric. Food Chem., 49 (9), 4252-4261 (2001).

18 Sun, R., Xiao, B., Lawther, J., “Fractional and structural characterization of ball-milled and enzyme lignins from wheat straw”, J. Appl. Polym. Sci., 68 (10), 1633-1641 (1998).

19 Toledano, A., Serrano, L., Labidi, J., “Enhancement of lignin production from olive tree pruning integrated in a green biorefinery”, Ind. Eng. Chem. Res., 50 (11), 6573-6579 (2011).

20 Wörmeyer, K., Ingram, T., Saake, B., Brunner, G., Smirnova, I., “Comparison of different pretreatment methods for lignocellulosic materials. Part II: Influence of pretreatment on the properties of rye straw lignin”, Bioresour. Technol., 102 (5), 4157-4164 (2011).

21 Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., Crocker, D., “Determination of structural carbohydrates and lignin in biomass”, NREL, Golden, CO, (2004).

22 Lin, Z., “Study on the corn stover efficiency of pretreatment and enzymatic hydrolysis”, Ph. D. Thesis, Nanjing Univ. Technol., Nanjing (2010). (in Chinese)

23 Sun, X.F., Jing, Z., Fowler, P., Wu, Y., Rajaratnam, M., “Structural characterization and isolation of lignin and hemicelluloses from barley straw”, Ind. Crop. Prod., 33 (3), 588-598 (2011).

24 Lundquist, K., Chang, H., Lin, S., “Isolation and purification”, In: Methods of lignin chemistry; Springer-Verlag, Berlin, Germany (1992).

25 Baptista, C., Robert, D., Duarte, A., “Relationship between lignin structure and delignification degree in Pinus pinaster kraft pulps”, Bioresour. Technol., 99 (7), 2349-2356 (2008).

26 Marques, A., Pereira, H., Rodrigues, J., Meier, D., Faix, O., “Isolation and comparative characterization of a Bj rkman lignin from the saponified cork of Douglas-fir bark”, J. Anal. Appl. Pyrol., 77 (2), 169-176 (2006).

27 Pan, X.J., Sano, Y., “Comparison of acetic acid lignin with milled wood and alkaline lignins from wheat straw”, Holzforschung, 54 (1), 61-65 (2000).

28 El Mansouri, N.E., Mancera, C., Ferrando, F., Salvado, J., “Kraft lignin behavior during reaction in an alkaline medium”, Biomass Bioenerg., 35 (5), 2072-2079 (2011).

29 Fu, P., Hu, S., Xiang, J., Sun, L., Yang, T., Zhang, A., Zhang, J., “Mechanism study of rice straw pyrolysis by Fourier transform infrared technique”, Chin. J. Chem. Eng., 17 (3), 522-529 (2009).

30 Yuan, T.Q., He, J., Xu, F., Sun, R.C., “Fractionation and physico-chemical analysis of degraded lignins from the black liquor of Eucalyptus pellita KP-AQ pulping”, Polym. Degrad. Stabili., 94 (7), 1142-1150 (2009).

31 Yang, H., Yan, R., Chen, H., Lee, D.H., Zheng, C., “Characteristics of hemicellulose, cellulose and lignin pyrolysis”, Fuel, 86 (12-13), 1781-1788 (2007).

32 Wu., S.B., Tan, Y., Guo, Y.L., Liu, J.Y., “Thermogravimetric properties of black liquor and corresponding kinetic analysis”, J. S. CHN Univ. Technol., 6, 59-63 (2007).

33 Kondo, T., Ohshita, T., Kyuma, T., “Comparison of characteristics of soluble lignins from untreated and ammonia-treated wheat straw”, Anim. Feed Sci. Tech., 39 (3-4), 253-263 (1992).

34 Sun, R., Lawther, J.M., Banks, W.B., “Effects of extraction time and different alkalis on the composition of alkali-soluble wheat straw lignins”, J. Agr. Food Chem., 44 (12), 3965-3970 (1996).

35 Faix, O., “Fourier transform infrared spectroscopy”, In: Methods of Lignin Chemistry, Springer-Verlag, Berlin, Germany (1992).

36 Popescu, C., Popescu, M., Singurel, G., Vasile, C., Argyropoulos, D., Willfor, S., “Spectral characterization of eucalyptus wood”, Appl. Spectrosc., 61 (11), 1168-1177 (2007).

37 Sun, X.F., Fowler, P., Baird, M.S., “Extraction and characterization of original lignin and hemicelluloses from wheat straw”, J. Agr. Food Chem., 53 (4), 860-870 (2005).

38 Seca, A.M.L., Cavaleiro, J.a.S., Domingues, F.M.J., Silvestre, A.J.D., Evtuguin, D., “Structural characterization of the bark and core lignins from Kenaf (Hibiscus cannabinus)”, J. Agr. Food Chem., 46 (8), 3100-3108 (1998).

39 Jiang, X., Ellis, N., Zhong, Z., “Characterization of pyrolytic lignin extracted from bio-oil”, Chin. J. Chem. Eng., 18 (6), 1018-1022 (2010).

40 Marques, G., Gutiérrez, A., del Río, J.C., “Chemical characterization of lignin and lipophilic fractions from leaf fibers of curaua (Ananas erectifolius)”, J. Agr. Food Chem., 55 (4), 1327-1336 (2007).

41 Oliveira, L., Evtuguin, D.V., Cordeiro, N., Silvestre, A.J.D., Silva, A.M.S., Torres, I.C., “Structural characterization of lignin from leaf sheaths of ‘Dwarf Cavendish’ banana plant”, J. Agr. Food Chem., 54 (7), 2598-2605 (2006).

42 Lundquist, K.,“Proton (¹H) NMR spectroscopy”, In: Methods of Lignin Chemistry, Springer-Verlag, Berlin, Germany (1992).

[1]	Piqiang Tan, Xiaoyu Li, Shiyan Wang, Zhiyuan Hu, Diming Lou. Selective catalytic reduction failure of low NH₃-NO_x ratio [J]. Chinese Journal of Chemical Engineering, 2021, 32(4): 231-240.
[2]	Kai Zhu, Chaoqun Yao, Yanyan Liu, Guangwen Chen. Using expansion units to improve CO₂ absorption for natural gas purification-A study on the hydrodynamics and mass transfer [J]. Chinese Journal of Chemical Engineering, 2021, 29(1): 35-46.
[3]	Xue Gao, Sisi Wen, Bingling Yang, Jian Xue, Haihui Wang. Enhanced air filtration performance under high-humidity condition through electrospun membranes with optimized structure [J]. Chinese Journal of Chemical Engineering, 2020, 28(7): 1788-1795.
[4]	Xinping Li, Yaowei Wang, Tangyin Wu, Shichao Song, Bin Wang, Shenglai Zhong, Rongfei Zhou. High-performance SSZ-13 membranes prepared using ball-milled nanosized seeds for carbon dioxide and nitrogen separations from methane [J]. Chinese Journal of Chemical Engineering, 2020, 28(5): 1285-1292.
[5]	Jing Guo, Weizhou Jiao, Guisheng Qi, Zhiguo Yuan, Youzhi Liu. Applications of high-gravity technologies in gas purifications: A review [J]. Chinese Journal of Chemical Engineering, 2019, 27(6): 1361-1373.
[6]	Jia Ju, Feixue Liang, Xiaoxin Zhang, Ran Sun, Xiaoguang Pan, Xiaoyun Guan, Guanning Cui, Xuan He, Mengyan Li. Advancement in separation materials for blood purification therapy [J]. Chinese Journal of Chemical Engineering, 2019, 27(6): 1383-1390.
[7]	Xinke Leng, Yanjun Zhong, Dehua Xu, Xinlong Wang, Lin Yang. Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin [J]. Chinese Journal of Chemical Engineering, 2019, 27(5): 1050-1057.
[8]	Hairong Yuan, Yanyan Lan, Jialin Zhu, Akiber Chufo Wachemo, Xiujin Li, Liang Yu. Effect on anaerobic digestion performance of corn stover by freezing-thawing with ammonia pretreatment [J]. Chin.J.Chem.Eng., 2019, 27(1): 200-207.
[9]	Zhengshu Dai, Meng Yu, Daozhe Rui, Xuejun Zhang, Yang Zhao. Investigation on a vertical radial flow adsorber designed by a novel parallel connection method [J]. Chin.J.Chem.Eng., 2018, 26(3): 484-493.
[10]	Huisheng Lü, Xingfang Shi, Yonghui Li, Fanmei Meng, Shuangyan Liu, Li Yan. Multi-objective regulation in autohydrolysis process of corn stover by liquid hot water pretreatment [J]. , 2017, 25(4): 499-506.
[11]	Chunli Liu, Weihui Bi, Dongliang Chen, Suobo Zhang, Hongchao Mao. Positively charged nanofiltration membrane fabricated by poly(acid-base) complexing effect induced phase inversion method forheavy metal removal [J]. Chin.J.Chem.Eng., 2017, 25(11): 1685-1694.
[12]	Minbo Yang, Xiao Feng, Guilian Liu. A unified graphical method for integration of hydrogen networks with purification reuse [J]. , 2016, 24(7): 891-896.
[13]	Emad. M. Elsehly, N. G. Chechenin, A. V. Makunin, H. A. Motaweh, E. A. Vorobyeva, K. A. Bukunov, E. G. Leksina, A. B. Priselkova. Characterization of functionalized multiwalled carbon nanotubes and application as an effective filter for heavy metal removal from aqueous solutions [J]. , 2016, 24(12): 1695-1702.
[14]	Zhiqiang Zhang, Shanying Hu, Dingjiang Chen, Bing Zhu. An analysis of an ethanol-based, whole-crop refinery system in China [J]. Chin.J.Chem.Eng., 2016, 24(11): 1609-1618.
[15]	Xianli Shi, Li Deng, Fangfang Sun, Jieyu Liang, Xu Deng. Key factors governing alkaline pretreatment of waste activated sludge [J]. Chin.J.Chem.Eng., 2015, 23(5): 842-846.