有机酸溶木质素氢解制备单酚化合物的研究

迂文兵; 沈德魁

doi:10.19912/j.0254-0096.tynxb.2021-1391

PDF(1943 KB)

太阳能学报 ›› 2023, Vol. 44 ›› Issue (4) : 225-230. DOI: 10.19912/j.0254-0096.tynxb.2021-1391

有机酸溶木质素氢解制备单酚化合物的研究

迂文兵, 沈德魁

作者信息 +

STUDY ON HYDROGENOLYSIS OF ORGANIC ACID SOLUBLE LIGNIN INTO MONOPHENOL COMPOUND

Yu Wenbing, Shen Dekui

Author information +

文章历史 +

摘要

首先利用木本类（硬木和软木）和禾本类不同生物质原料制备有机酸溶木质素,发现木本木质素的碳、氢元素含量和高位热值高于禾本木质素,软木木质素中β-O-4、β-β和β-5键含量高于硬木和禾本木质素。然后,通过不同种类木质素在乙醇/异丙醇中氢解实验发现,木本木质素氢解得到产物产率高于禾本木质素,其中杉木木质素的单酚产率最高,约为8.07%（质量分数）。此外,木本木质素解聚产生的单酚化合物以无侧链和三元碳侧链为主,而禾本木质素以二元碳侧链化合物为主。

Abstract

Different biomass feedstocks of woody （hardwood and softwood） and gramineous species were first used to prepare organic acid soluble lignin. It is found that the contents of carbon and hydrogen element and high heating value of woody lignin are higher than those of gramineous lignins, and the contents of β-O-4, β-β and β-5 bond of softwood lignin are higher than those of hardwood and graminous lignin. Then, the hydrogenolysis reactions of different lignins in ethanol/isopropanol show that the monophenol yield of woody lignin are higher than those of gramineous lignin, and the highest monophenol yield of Chinese fir lignin is about 8.07%. In addition, the monophenols from woody lignin are predominantly no side-chain or ternary carbon side chain compounds, whereas grass lignin are depolymerized into predominantly binary carbon side chain compounds.

导出引用

迂文兵, 沈德魁. 有机酸溶木质素氢解制备单酚化合物的研究[J]. 太阳能学报. 2023, 44(4): 225-230 https://doi.org/10.19912/j.0254-0096.tynxb.2021-1391

Yu Wenbing, Shen Dekui. STUDY ON HYDROGENOLYSIS OF ORGANIC ACID SOLUBLE LIGNIN INTO MONOPHENOL COMPOUND[J]. Acta Energiae Solaris Sinica. 2023, 44(4): 225-230 https://doi.org/10.19912/j.0254-0096.tynxb.2021-1391

中图分类号： KT6

参考文献

[1] DAS L, LI M, STEVENS J, et al.Characterization and catalytic transfer hydrogenolysis of deep eutectic solvent extracted sorghum lignin to phenolic compounds[J]. ACS sustainable chemistry & engineering, 2018, 6(8): 10408-10420.
[2] ZHOU M H, SHARMA B K, LIU P, et al.Catalytic in situ hydrogenolysis of lignin in supercritical ethanol: effect of phenol, catalysts, and reaction temperature[J]. ACS sustainable chemistry & engineering, 2018, 6(5): 6867-6875.
[3] JIA L, FENG X, DENG J, et al.Extraction and characterization of lignin from corncob by organic acid aqueous solutions[J]. Fine chemicals, 2013, 30(6): 628-633.
[4] ZHANG J H, DENG H B, LIN L, et al.Isolation and characterization of wheat straw lignin with a formic acid process[J]. Bioresource technology, 2010, 101(7): 2311-2316.
[5] XU F, SUN J X, SUN R C, et al.Comparative study of organosolv lignins from wheat straw[J]. Industrial crops & products, 2006, 23(2): 180-193.
[6] XU F, ZHAO H, ZHAO G J, et al.Chemical characteristic of organosolv lignins from wheat straw[J]. Transactions of China pulp and paper, 2007, 22(4): 23-27.
[7] ZHAO W W, SIMMONS B, SINGH S, et al.From lignin association to nano-/micro-particle preparation: extracting higher value of lignin[J]. Green chemistry, 2016, 18(21): 5693-5700.
[8] WANG H L, BEN H X, RUAN H, et al.Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals[J]. ACS sustainable chemistry & engineering, 2017, 5(2): 1824-30.
[9] TOTONG S, DAORATTANACHAI P, LAOSIRIPOJANA N, et al.Catalytic depolymerization of alkaline lignin to value-added phenolic-based compounds over Ni/CeO₂-ZrO₂ catalyst synthesized with a one-step chemical reduction of Ni species using NaBH₄ as the reducing agent[J]. Fuel processing technology, 2020, 198(10): 106248.
[10] GAO X Q, ZHU S H, LI Y W.Selective hydrogenolysis of lignin and model compounds to monophenols over AuPd/CeO₂[J]. Molecular catalysis, 2019, 462(10): 69-76.
[11] ERICKSON M, LARSSON S, MIKSCHE G E, et al.Gaschromatographische analyse von ligninoxydationsprodukten. VII. ein verbessertes verfahren zur charakterisierung von ligninen durch methylierung und oxydativen abbau[J]. Acta chemica scandinavica, 1973, 27(1): 127-40.
[12] NIMZ H.Beech lignin-proposal of a constitutional scheme[J]. Angewandte chemie international edition in English, 1974, 13(5): 313-21.
[13] CAO Y, ZHANG C, TSANG D C W, et al. Hydrothermal liquefaction of lignin to aromatic chemicals: impact of lignin structure[J]. Industrial & engineering chemistry research, 2020, 59(39): 16957-69.
[14] DEUSS P J, SCOTT M, TRAN F, et al.Aromatic monomers by in situ conversion of reactive intermediates in the acid-catalyzed depolymerization of lignin[J]. Journal of the American Chemical Society, 2015, 137(23): 7456-7467.
[15] LIMARTA S O, HA J M, PARK Y K, et al.Efficient depolymerization of lignin in supercritical ethanol by a combination of metal and base catalysts[J]. Journal of industrial and engineering chemistry, 2018, 57(4): 45-54.
[16] MAI F H, WEN Z, BAI Y F, et al.Selective conversion of enzymatic hydrolysis lignin into Alkylphenols in supercritical ethanol over a WO₃/γ-Al₂O₃ catalyst[J]. Industrial & engineering chemistry research, 2019, 58(24): 10255-10363.
[17] TALEBI A M, BERTELLA S, QUESTELL-SANTIAGO Y M, et al. Establishing lignin structure-upgradeability relationships using quantitative 1H-13C heteronuclear single quantum coherence nuclear magnetic resonance (HSQC-NMR) spectroscopy[J]. Chemical science, 2019, 10(35): 8135-42.
[18] ZHAO L P, ZHANG B, WANG X, et al.Study on gasification performance of different kinds of biomass with microwave heating[J]. Acta energiae solaris sinica, 2021, 42(9): 394-399.
[19] JIANG T D.Lignin[M]. Beijing: Chemical Industy Press, 2009, 20-21.
[20] TAI D S, PAN X Q.Chemical properties of grass lignin[J]. China pulp & paper, 1989, 8(1): 11-16.
[21] ZHANG B, QI Z J, LI X X, et al.ReO_x/AC catalyzed cleavage of C-O bonds in lignin model compounds and alkaline lignins[J]. ACS sustainable chemistry & engineering, 2019, 7(1): 208-215.
[22] FALEVA A V, KOZHEVNIKOV A Y, POKRYSHKIN S A, et al.Structural characteristics of different softwood lignins according to 1D and 2D NMR spectroscopy[J]. Journal of wood chemistry and technology, 2020, 40(3): 178-189.
[23] JIANG Z C, HE T, LI J M, et al.Selective conversion of lignin in corncob residue to monophenols with high yield and selectivity[J]. Green chem, 2014, 16(9): 4257-4265.
[24] PIN T C, NASCIMENTO V M, COSTA A C, et al.Structural characterization of sugarcane lignins extracted from different protic ionic liquid pretreatments[J]. Renewable energy, 2020, 161(7): 579-592.
[25] SETTE M, WECHSELBERGER R, CRESTINI C.Elucidation of lignin structure by quantitative 2D NMR[J]. Chemistry - a European journal, 2011, 17(34): 9529-9535.
[26] BANKS WB, SUN R, LAWTHER J M.A tentative chemical structure of wheat straw lignin[J]. Industrial crops and products, 1997, 6(1): 1-8.
[27] LI H W, ZHENG X L, ZHANG H M, et al.Selective cleavage of ester linkages in lignin catalyzed by La-Doped Ni/MgO[J]. ACS sustainable chemistry & engineering, 2020, 8(41): 15685-15695.