木质素是自然界中除纤维素外第二大生物质资源,由于其高分子结构中含有丰富的芳环结构及活性含氧基团(如酚羟基等),因此通过解聚生产化工原料和化学品可以部分替代化石能源,有利于缓解能源危机。由于木质素总体利用率较低,如何通过化学方法将其转化为高附加值的化学品是实现木质素高价值化和资源化利用的重要途径之一。综述了木质素解聚转化方法,阐述了催化剂设计,归纳了木质素制备高分子材料的应用优势,提出了木质素磺酸盐通过水滑石催化解聚制取小分子化合物,并以其为原料制备绿色粘合剂的新工艺,并对木质素解聚转化利用的发展方向进行了展望,为木质素高值化和资源化利用提供了理论基础。
Other than cellulose,lignin was the second largest biomass resource in nature.Due to the abundant aromatic units and active group (such as phenolic hydroxyl,etc.) in its' polymer structure,the depolymerization of lignin can partially substituted the fossil resources,which is beneficial to alleviate the energy crisis.At present,the overall utilization of lignin is still low.It was one of the important ways to achieve the high value and resource utilization of lignin by converting it into high value-added chemicals via chemical methods.The utilization of lignin through depolymerization was reviewed,the catalyst design was discussed.Moreover,the advantages of preparation of macromolecule materials by lignin were summarized.On the basis of characteristics of lignin conversion,a new process was proposed for the preparation of green binder by using small molecular compounds prepared from lignin sulfonate by depolymerization using hydrotalcite as catalyst via hydrolysis method.The development direction of depolymerization-conversion utilization technology was forecasted,which would provide a theoretical basis for the high value and the utilization of lignin resources.
[1] Yan K,Liu Y Q,Lu Y R,et al.Catalytic application of layered double hydroxide-derived catalysts for the conversion of biomass-derived molecules[J].Catalysis Science & Technology,2017,7(8):1622-1645.
[2] 路瑶,魏贤勇,宗志敏,等.木质素的结构研究与应用[J].化学进展,2013,25(5):838-858.
[3] Zakzeski J,Bruijnincx P C A,Jongerius A L,et al.The catalytic valorization of lignin for the production of renewable chemicals[J].Chemical Reviews,2010,110(6):3552-3599.
[4] Yaghoubi K,Pazouki M,Shojaosadati S A.Variable optimization for biopulping of agricultural residues by ceriporiopsis subvermispora[J].Bioresource Technology,2008,99(10):4321-4328.
[5] Ma Z Q,Troussard E,Bokhoven J A V.Controlling the selectivity to chemicals from lignin via catalytic fast pyrolysis[J].Applied Catalysis A (General),2012,423-424(18):130-136.
[6] 陈彦广,张雷,韩洪晶,等.钙钛矿型混合离子电子导体在能源转化中应用的研究进展[J].化学通报,2015(7):601-612.
[7] 陈彦广.核壳催化剂催化氧化木质素制取芳香基含氧化合物的方法:中国,ZL201610043490.2[P].2018-03-06.
[8] Wild P D,Laan R V D,Kloekhorst A,et al.Lignin valorisation for chemicals and (transportation) fuels via (catalytic) pyrolysis and hydrodeoxygenation[J].Environmental Progress & Sustainable Energy,2009,28(3):461-469.
[9] Zakzeski J,Jongerius A L,Bruijnincx P C,et al.Catalytic lignin valorization process for the production of aromatic chemicals and hydrogen[J].Chemsuschem,2012,5(8):1602-1609.
[10] Huang X M,Korányi T I,Boot M D,et al.Catalytic depolymerization of lignin in supercritical ethanol[J].Chemsuschem,2014,7(8):2276-2288.
[11] Liguori L,Barth T.Palladium-nafion SAC-13 catalysed depolymerisation of lignin to phenols in formic acid and water[J].Journal of Analytical & Applied Pyrolysis,2011,92(2):477-484.
[12] Singh S K,Ekhe J D.Towards effective lignin conversion:HZSM-5 catalyzed one-pot solvolytic depolymerisation/hydrodeoxygenation of lignin into value added compounds[J].Rsc Advances,2014,4(53):27971-27978.
[13] Thring R W.Alkaline degradation of ALCELL® lignin[J].Biomass & Bioenergy,1994,7(1/6):125-130.
[14] Long J X,Zhang Q,Wang T J,et al.An efficient and economical process for lignin depolymerization in biomass-derived solvent tetrahydrofuran[J].Bioresource Technology,2014,154(1):10-17.
[15] 王冠华,陈洪章.秸秆汽爆炼制木质素制备酚醛泡沫材料[J].生物工程学报,2014,30(6):901-910.
[16] Li B,Wang Y Y,Mahmood N,et al.Preparation of bio-based phenol formaldehyde foams using depolymerized hydrolysis lignin[J].Industrial Crops & Products,2017,97:409-416.
[17] Xue B L,Wen J L,Sun R C.Lignin-based rigid polyurethane foam reinforced with pulp fiber:synthesis and characterization[J].Acs Sustainable Chemistry & Engineering,2014,2(6):1474-1480.
[18] Zhuang X W,Li S H,Ma Y F,et al.Preparation and characterization of lignin-phenolic foam[J].Advanced Materials Research,2011,236:1014-1018.
[19] Wang G H,Chen H Z.Carbohydrate elimination of alkaline-extracted lignin liquor by steam explosion and its methylolation for substitution of phenolic adhesive[J].Industrial Crops & Products,2014,53(1):93-101.
[20] Cheng S,Yuan Z,Leitch M,et al.Highly efficient de-polymerization of organosolv lignin using a catalytic hydrothermal process and production of phenolic resins/adhesives with the depolymerized lignin as a substitute for phenol at a high substitution ratio[J].Industrial Crops & Products,2013,44(44):315-322.
[21] Xue B L,Wen J L,Zhu M Q,et al.Lignin-based polyurethane film reinforced with cellulose nanocrystals[J].Rsc Advances,2014,4(68):36089-36096.
[22] 黄萍,方向晨,白富栋,等.无规聚醚多元醇化学改性木质素薄膜的制备与表征[J].功能高分子学报,2015,28(3):259-264.
[23] Parajuli D,Inoue K,Ohto K,et al.Adsorption of heavy metals on crosslinked lignocatechol:a modified lignin gel[J].Reactive & Functional Polymers,2005,62(2):129-139.
[24] Pucciariello R,Villani V,Bonini C,et al.Physical properties of straw lignin-based polymer blends[J].Polymer,2004,45(12):4159-4169.
[25] Kadla J F,Kubo S,Venditti R A,et al.Lignin-based carbon fibers for composite fiber applications[J].Carbon,2002,40(15):2913-2920.
基金资助
国家自然科学基金(51674089);黑龙江省杰出青年科学基金项目(JC2018002);黑龙江省博士后科研启动基金(LBH-Q16037);东北石油大学研究生创新项目(YJSCX2017-014NEPU)
PDF
(1131KB)
