为了应对工业废水带来的环境污染以及解决高值化利用木质素资源的问题, 综述了近年来国内外以木质素为原料制备水凝胶的研究进展, 介绍了木质素基水凝胶的制备方法, 以及木质素水凝胶在废水处理中的研究进展。木质素基水凝胶的制备方法主要包括:互穿或半互穿网络聚合法、交联共聚法、木质素与单体接枝聚合法及原子转移自由基聚合(ATRP)和逆加成断裂转移(RAFT)聚合法, 其中化学交联共聚法是目前制备木质素基水凝胶流程最简便、最环保的方法。木质素基水凝胶对废水中的有机污染物和重金属有很高效的吸附去除效果, 其对亚甲基蓝的吸附效率高达9646.92mg/g, 此外, 还可通过解吸实现重金属等的回收, 且吸附-解吸循环10次仍可达到100%的有效率。同时, 还发现木质素基水凝胶是良好的载体, 可负载纳米金属、荧光碳点等功能性材料, 实现催化降解、高效检测等多种功能。建议今后对木质素基水凝胶制备方法工业化及对实际废水中污染物的选择性及竞争性吸附等方面展开研究, 以实现木质素废料的高效资源化利用。
In order to cope with the environmental pollution caused by industrial wastewater and to solve the problem of high-value utilization of lignin, this paper reviewed the research progress of lignin-based hydrogels prepared from lignin at home and abroad in recent years, and introduced the preparation methods of lignin-based hydrogels and the research progress of lignin hydrogels in wastewater treatment.The results of literature research showed that the preparation methods of lignin-based hydrogels mainly included:interpenetrating or semi-interpenetrating network polymerization, cross-link copolymerization, lignin-monomer graft polymerization, and ATRR and RAFT polymerization.Among them, the chemical cross-linking copolymerization method was the simplest and most environmentally friendly method for the preparation of lignin-based hydrogels process.In addition, lignin-based hydrogels could not only efficiently adsorb and remove organic pollutants and heavy metals from water, in which the adsorption efficiency of the hybrid hydrogel of modified lignin and montmorillonite for methylene blue was as high as 9646.92mg/g, but also could achieve the recovery of heavy metals and other wastes through desorption, and the adsorption-desorption cycle of 10 times could still reach 100% efficiency.Meanwhile, the lignin-based hydrogel could be used as a good carrier to load functional materials such as nanometals and fluorescent carbon dots to achieve various functions such as catalytic degradation and efficient detection.Future research on the industrialization of lignin-based hydrogel preparation methods and selective and competitive adsorption of pollutants in actual wastewater was recommended to achieve efficient resource utilization of lignin waste.
[1] Datta R,Kelkar A,Baraniya D,et al.Enzymatic degradation of lignin in soil:a review[J].Sustainability,2017,9(7):1163.
[2] 鲁秀国,陈晶.化学改性木质素吸附水中重金属的研究进展[J].化工新型材料,2021,49(11):279-282.
[3] 贾转,万广聪,李明富,等.化学改性在木素基酚醛树脂胶黏剂制备中的研究进展[J].中国造纸,2018,37(3):72-79.
[4] 陈彦广,薛峰,韩洪晶,等.木质素解聚转化及其在高分子材料中的应用[J].化工新型材料,2019,47(5):19-22.
[5] You X,Wang X,Zhang H J,et al.Supertough lignin hydrogels with multienergy dissipative structures and ultrahigh antioxidative activities[J].ACS Applied Materials & Interfaces,2020,12(35):39892-39901.
[6] 运晓静,迟明超,郭晨艳,等.木质素基水凝胶的研究进展[J].中国造纸,2019,38(10):62-67.
[7] Song B,Liang H,Sun R,et al.Hydrogel synthesis based on lignin/sodium alginate and application in agriculture[J].International Journal of Biological Macromolecules,2020,144:219-230.
[8] Wang Q,Guo J,Lu X,et al.Wearable lignin-based hydrogel electronics:a mini-review[J].International Journal of Biological Macromolecules,2021,181:45-50.
[9] Farhat W,Venditti R,Mignard N,et al.Polysaccharides and lignin based hydrogels with potential pharmaceutical use as a drug delivery system produced by a reactive extrusion process[J].International Journal of Biological Macromolecules,2017,104:564-575.
[10] Thakur S,Govender P P,Mamo M A,et al.Progress in lignin hydrogels and nanocomposites for water purification:future perspectives[J].Vacuum,2017,146:342-355.
[11] 冯清华,谌凡更.含木质素水凝胶的研究进展[J].纤维素科学与技术,2011,19(4):67-73.
[12] 易锦馨,霍志鹏,Asiri Abdullah M,等.农林废弃生物质吸附材料在水污染治理中的应用[J].化学进展,2019,31(5):760-772.
[13] Meng Y,Lu J,Cheng Y,et al.Lignin-based hydrogels:a review of preparation,properties,and application[J].International Journal of Biological Macromolecules,2019,135:1006-1019.
[14] Zhao J,Zheng K,Nan J,et al.Synthesis and characterization of lignosulfonate-graft-poly (acrylic acid)/hydroxyethyl cellulose semi-interpenetrating hydrogels[J].Reactive and Functional Polymers,2017,115:28-35.
[15] Jesús E,Sabino M A.Effect of the presence of lignin or peat in IPN hydrogels on the sorption of heavy metals[J].Polymer Bulletin,2010,65(5):495-508.
[16] Ravishankar K,Venkatesan M,Desingh R P,et al.Biocompatible hydrogels of chitosan-alkali lignin for potential wound healing applications[J].Materials Science and Engineering:C,2019,102:447-457.
[17] Li F,Wang X,Yuan T,et al.A lignosulfonate-modified graphene hydrogel with ultrahigh adsorption capacity for Pb(Ⅱ) removal[J].Journal of Materials Chemistry A,2016,4(30):11888-11896.
[18] Teng X,Xu H,Song W,et al.Preparation and properties of hydrogels based on PEGylated lignosulfonate amine[J].ACS Omega,2017,2(1):251-259.
[19] 冯清华.含木质素水凝胶的合成及其性能研究[D].广州:华南理工大学,2012.
[20] Liu H,Chung H.Lignin-based polymers via graft copolymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2017,55(21):3515-3528.
[21] Matyjaszewski K.Atom transfer radical polymerization (ATRP):current status and future perspectives[J].Macromolecules,2012,45(10):4015-4039.
[22] Xu Y,Yuan L,Wang Z,et al.Lignin and soy oil-derived polymeric biocomposites by ‘grafting from’ RAFT polymerization[J].Green Chemistry,2016,18(18):4974-4981.
[23] 陈佼,刘欢,刘浩霖,等.生物炭对阳离子染料的吸附性能研究进展[J].工业水处理,2022,42(8):27-33.
[24] 徐继红,穆新科,洪思明,等.木质素基水凝胶对亚甲基蓝染料的吸附性能[J].环境工程学报,2015,9(10):4877-4882.
[25] Wang Y,Xiong Y,Wang J,et al.Ultrasonic-assisted fabrication of montmorillonite-lignin hybrid hydrogel:highly efficient swelling behaviors and super-sorbent for dye removal from wastewater[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,520:903-913.
[26] Wei S,Chen W,Tong Z,et al.Synthesis of a functional biomass lignin-based hydrogel with high swelling and adsorption capability towards Acid Red 73[J].Environmental Science and Pollution Research,2021,28:51306-51320.
[27] 李萌.阳离子型木质素基水凝胶的制备及其在废水处理中的应用[D].济南:齐鲁工业大学,2016.
[28] Li X,Fan H,Fan X.Effect of chemical structure of organics on pore wetting[J].Chemical Engineering Science,2015,137:458-465.
[29] Li X,Zhang L,Yang Z,et al.Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process:a review[J].Separation and Purification Technology,2020,235:116213.
[30] Tahari N,De Hoyos-Martinez P L,Abderrabba M,et al.Lignin-montmorillonite hydrogels as toluene adsorbent[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2020,602:125108.
[31] Liu Y,Chen H,Mo Q,et al.Removal of cadmium and tetracycline by lignin hydrogels loaded with nano-FeS:nanoparticle size control and content calculation[J].Journal of Hazardous Materials,2021,416:126262.
[32] Mitran E,Dellinger B,Mccarley R L.Highly size-controlled,low-size-dispersity nickel nanoparticles from poly(propylene imine) dendrimer-Ni(Ⅱ) complexes[J].Chemistry of Materials,2010,22(24):6555-6563.
[33] Liu Y,Huang Y,Zhang C,et al.Nano-FeS incorporated into stable lignin hydrogel:a novel strategy for cadmium removal from soil[J].Environmental Pollution,2020,264:114739.
[34] 黎新明,尹国强,崔英德.基于半纤维素和木质素的水凝胶研究进展[J].化工新型材料,2011,39(9):21-25.
[35] 王莹,王星敏,熊杰,等.接枝插层合成木质素基水凝胶的制备因素解析[J].环境化学,2020,39(8):2217-2226.
[36] Sun Y,Ma Y,Fang G,et al.Synthesis of acid hydrolysis lignin-g-poly-(acrylic acid) hydrogel superabsorbent composites and adsorption of lead ions[J].BioResources,2016,11(3):5731-5742.
[37] Rico-García D,Ruiz-Rubio L,Pérez-Alvarez L,et al.Lignin-based hydrogels:synthesis and applications[J].Polymers,2020,12(1):81.
[38] Parajuli D,Inoue K,Ohto K,et al.Adsorption of heavy metals on crosslinked lignocatechol:a modified lignin gel[J].Reactive and Functional Polymers,2005,62(2):129-139.
[39] Parajuli D,Adhikari C R,Kuriyama M,et al.Selective recovery of gold by novel lignin-based adsorption gels[J].Industrial & Engineering Chemistry Research,2006,45(1):8-14.
[40] Jiao G,Ma J,Li Y,et al.Removed heavy metal ions from wastewater reuse for chemiluminescence:successive application of lignin-based composite hydrogels[J].Journal of Hazardous Materials,2021,421:126722.
[41] Gao C,Wang X,Zhai S,et al.Enhanced catalytic activity of nanosilver with lignin/polyacrylamide hydrogel for reducing p-nitrophenol[J].International Journal of Biological Macromolecules,2019,134:202-209.
[42] Gao C,Wang X,Wang H,et al.Highly efficient and stable catalysis of p-nitrophenol via silver/lignin/polyacrylic acid hydrogel[J].International Journal of Biological Macromolecules,2020,144:947-953.
[43] Zhang L,Lu H,Chu J,et al.Lignin-directed control of silver nanoparticles with tunable size in porous lignocellulose hydrogels and their application in catalytic reduction[J].ACS Sustainable Chemistry & Engineering,2020,8(33):12655-12663.
[44] Yuan H,Peng J,Ren T,et al.Novel fluorescent lignin-based hydrogel with cellulose nanofibers and carbon dots for highly efficient adsorption and detection of Cr(Ⅵ)[J].Science of the Total Environment,2021,760:143395.
基金资助
国家重大科技专项课题(2016ZX05040003)
PDF
