木质纤维素生物质水热液化的研究进展

doi:10.16085/j.issn.1000-6613.2016.02.017

摘要/Abstract

摘要： 对木质纤维素生物质的模型化合物(纤维素、半纤维素和木质素)的水热液化机理进行了剖析。纤维素和半纤维素降解路径主要是水解成单糖并进一步生成酸类、醛类、酮类等。木质素结构较复杂,液化产物中含有大量苯系化合物,具体木质纤维素生物质的水热液化反应更为复杂,不同的木质纤维素生物质原料水热液化产生的生物油含量不同;分析了原料种类、催化剂、反应温度、反应压力、对水热液化过程以及产品组成和收率的影响;对生物质水热液化制备生物油的研究进行了展望,认为发展木质纤维素生物质水热条件下降解的数学模型,开发新型反应器、研制催化剂,是今后生物质水热液化工程实验的发展方向。

关键词: 木质纤维素生物质, 水热液化, 模型化合物, 降解路径, 生物油

Abstract: This paper summarizes the degradation mechanisms and hydrolysis products of cellulose,hemicellulose and lignocellulosic biomass materials under hydrothermal liquefaction conditions. Cellulose and hemicellulose degrade to monosaccharides,and then to acids,aldehydes and ketones. The hydrothermal liquefaction products of lignin contain a lot of phenolic compounds. Hydrothermal liquefaction of specific lignocellulosic biomass is more complex,and different lignocellulosic biomass feedstocks lead to different bio-oil yield by hydrothermal liquefaction. Key factors determining the hydrolysis behavior in hydrothermal liquefaction are also discussed,including biomass type,catalyst,temperature,pressure,and reaction time on the yield and the distribution of products. Future research prospects to further improve the technology are discussed. It is pointed out that developing mathematical model of the hydrothermal decomposition,designing the suitable reactor,and selecting appropriate catalysts will be the directions of engineering experiments in the future.

Key words: lignocellulosic biomass, hydrothermal liquefaction, model compounds, degradation pathway, bio-oil

中图分类号:

王伟, 闫秀懿, 张磊, 周菁辉. 木质纤维素生物质水热液化的研究进展[J]. 化工进展, 2016, 35(02): 453-462.

WANG Wei, YAN Xiuyi, ZHANGLei, ZHOU Jinghui . Research progress of hydrothermal liquefaction of lignocellulosic biomass[J]. Chemical Industry and Engineering Progree, 2016, 35(02): 453-462.

参考文献

[1] 刘刚,沈镭. 中国生物质能源的定量评价及其地理分布[J]. 自然资源学报,2007(1):9-19.
[2] 陆强,朱锡锋,李全新,等. 生物质快速热解制备液体燃料[J]. 化学进展,2007(s2):1064-1071.
[3] HUBER G W,IBORRA S,CORMA A. Synthesis of transportation fuels from biomass:chemistry,catalysts,and engineering[J]. Chemical Revews,2006,106(9):4044-4098.
[4] International Energy Outlook. World petroleum and other liquid fuels[R]. Washington:Energy Information Administration,2013.
[5] AKHTAR J,AMIN N A S. A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass [J]. Renewable and Sustainable Energy Reviews,2011,15(3):1615-1624.
[6] KRUSE A,DINJUS E. Hot compressed water as reaction medium and reactant:properties and synthesis reactions [J]. The Journal of Supercritical Fluids,2007,39(3):362-380.
[7] YU Y,LOU X,WU H. Some recent advances in hydrolysis of biomass in hot-compressed water and its comparisons with other hydrolysis methods[J]. Energy & Fuels,2008,22(1):46-60.
[8] TOOR S S,ROSENDAHL L,RUDOLF A. Hydrothermal liquefaction of biomass:a review of subcritical water technologies[J]. Energy,2011,36(5):2328-2342.
[9] CANTERO D A,BERMEJO M D,COCERO M J. Kinetic analysis of cellulose depolymerization reactions in near critical water [J]. The Journal of Supercritical Fluids,2013:48-57.
[10] SASAKI M,ADSCHIRI T,ARAI K. Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water[J]. AIChE Journal,2004,50(1):192-202.
[11] SASAKI M,FANG Z,FUKUSHIMA Y,et al. Dissolution and hydrolysis of cellulose in subcritical and supercritical water[J]. Industrial & Engineering Chemistry Research,2000,39(8):2883-2890.
[12] SASAKI M,KABYEMELA B,MALALUAN R,et al. Cellulose hydrolysis in subcritical and supercritical water [J]. The Journal of Supercritical Fluids,1998,13(1/2/3):261-268.
[13] MATSUMURA Y,SASAKI M,OKUDA K,et al. Supercritical water treatment of biomass for energy and material recovery[J]. Combustion Science and Technology,2006,178(1):509-536.
[14] YIN S,TAN Z. Hydrothermal liquefaction of cellulose to bio-oil under acidic,neutral and alkaline conditions [J]. Applied Energy,2012,92:234-239.
[15] KRUSE A,GAWLIK A. Biomass conversion in water at 330-410℃ and 30—50MPa. Identification of key compounds for indicating different chemical reaction pathways[J]. Industrial & Engineering Chemistry Research,2003,42(2):267-279.
[16] YU-WU Q M,WEISS-HORTALA E,BARNA R. Hydrothermal conversion of glucose in multiscale batch processes:analysis of the gas,liquid and solid residues [J]. The Journal of Supercritical Fluids,2013,79:76-83.
[17] BARBIER J,CHARON N,DUPASSIEUX N,et al. Hydrothermal conversion of glucose in a batch reactor. A detailed study of an experimental key-parameter:the heating time[J]. The Journal of Supercritical Fluids,2011,58(1):114-120.
[18] CATALLO W J,SHUPE T F,COMEAUX J L,et al. Transformation of glucose to volatile and semi-volatile products in hydrothermal (HT) systems [J]. Biomass and Bioenergy,2010,34(1):1-13.
[19] SINAG A,KRUSE A,SCHWARZKOPF V. Formation and degradation pathways of intermediate products formed during the hydropyrolysis of glucose as a model substance for wet biomass in a tubular reactor[J]. Engineering in Life Sciences,2003,3(12):469-473.
[20] BOBLETER O. Hydrothermal degradation of polymers derived from plants[J]. Progress in Polymer Science,1994,19(5):797-841.
[21] MOK W S L,ANTAL M J. Uncatalyzed solvolysis of whole biomass hemicellulose by hot compressed liquid water[J]. Industrial & Engineering Chemistry Research,1992,31(4):1157-1161.
[22] AIDA T M,SHIRAISHI N,KUBO M,et al. Reaction kinetics of d-xylose in sub- and supercritical water [J]. The Journal of Supercritical Fluids,2010,55(1):208-216.
[23] SROKOL Z,BOUCHE A G,VAN ESTRIK A,et al. Hydrothermal upgrading of biomass to biofuel,studies on some monosaccharide model compounds[J]. Carbohydrate Research,2004,339(10):1717-1726.
[24] JING Q,LÜ X. Kinetics of non-catalyzed decomposition of d-xylose in high temperature liquid water[J]. Chinese Journal of Chemical Engineering,2007,15(5):666-669.
[25] 陆强. 生物质选择性热解液化的研究[D]. 合肥:中国科学技术大学,2010.
[26] 于光. 木化生物质的加氢液化[D]. 青岛:青岛科技大学,2010.
[27] 隋鑫金. 工业木质素催化液化制备酚类化学品的研究[D]. 广州:华南理工大学,2011.
[28] BARBIER J,CHARON N,DUPASSIEUX N,et al. Hydrothermal conversion of lignin compounds:a detailed study of fragmentation and condensation reaction pathways [J]. Biomass and Bioenergy,2012,46:479-491.
[29] KANETAKE W T,SASAKI M,GOTO M. Decomposition of a lignin model compound under hydrothermal conditions[J]. Chemical Engineering & Technology,2007,30(8):1113-1122.
[30] LIU A,PARK Y,HUANG Z,et al. Product identification and distribution from hydrothermal conversion of walnut shells[J]. Energy & Fuels,2006,20(2):446-454.
[31] ZHANG B,VON KEITZ M,VALENTAS K. Thermal effects on hydrothermal biomass liquefaction[J]. Applied Biochemistry and Biotechnology,2008,147(1-3):143-150.
[32] ZHANG B,VON KEITZ M,VALENTAS K. Thermochemical liquefaction of high-diversity grassland perennials [J]. Journal of Analytical and Applied Pyrolysis,2009,84(1):18-24.
[33] KARAGÖZ S,BHASKAR T,MUTO A,et al. Comparative studies of oil compositions produced from sawdust,rice husk,lignin and cellulose by hydrothermal treatment[J]. Fuel,2005,84(7/8):875-884.
[34] BHASKAR T,SERA A,MUTO A,et al. Hydrothermal upgrading of wood biomass:influence of the addition of K₂CO₃ and cellulose/lignin ratio [J]. Fuel,2008,87(10/11):2236-2242.
[35] ZHONG C,WEI X. A comparative experimental study on the liquefaction of wood [J]. Energy,2004,29(11):1731-1741.
[36] QU Y,WEI X,ZHONG C. Experimental study on the direct liquefaction of Cunninghamia lanceolata in water [J]. Energy,2003,28(7):597-606.
[37] SHUI H,JIANG Q,CAI Z,et al. Co-liquefaction of rice straw and coal using different catalysts[J]. Fuel,2013,109:9-13.
[38] LI L,YOU Q,WU S,et al. Co-liquefaction behavior of corn straw and Shengli lignite[J]. Journal of the Energy Institute,2015. DOI:10.1016/j.joei1025.03.006.
[39] GAI C,LI Y,PENG N,et al. Co-liquefaction of microalgae and lignocellulosic biomass in subcritical water[J]. Bioresource Technology,2015,185:240-245.
[40] YAKABOYLU O,HARINCK J,SMIT K G,et al. Testing the constrained equilibrium method for the modeling of supercritical water gasification of biomass[J]. Fuel Processing Technology,2015,138:74-85.
[41] MOSTEIRO-ROMERO M,VOGEL F,WOKAUN A. Liquefaction of wood in hot compressed water Part 2—modeling of particle dissolution[J]. Chemical Engineering Science,2014,109:220-235.
[42] ZHANG Z. Computational fluid dynamics modeling of a continuous tubular hydrothermal liquefaction reactor[D]. Urbana: University of Illinois at Urbana-Champaign,2013.
[43] SHARMA B,INGALLS R G,JONES C L,et al. Biomass supply chain design and analysis:basis,overview,modeling,challenges,and future[J]. Renewable and Sustainable Energy Reviews,2013,24:608-627.
[44] SINGH R,PRAKASH A,BALAGURUMURTHY B,et al. Chapter 10—hydrothermal liquefaction of biomass[M]// Recent Advances in Thermo-Chemical Conversion of Biomass,Sukumaran A P B S. Boston:Elsevier,2015,269-291.
[45] ELLIOTT D C,BILLER P,ROSS A B,et al. Hydrothermal liquefaction of biomass:developments from batch to continuous process[J]. Bioresource Technology,2015,178:147-156.
[46] BENSAID S,CONTI R,FINO D. Direct liquefaction of ligno-cellulosic residues for liquid fuel production[J]. Fuel,2012,94:324-332.
[47] SINGH R,BHASKAR T,BALAGURUMURTHY B. Chapter 11— hydrothermal upgradation of algae into value-added hydrocarbons[M]//Biofuels from Algae,Soccol A P L C. Amsterdam:Elsevier,2014:235-260.
[48] CANTERO D A,DOLORES BERMEJO M,José Cocero M. Reaction engineering for process intensification of supercritical water biomass refining[J]. The Journal of Supercritical Fluids,2015,96(1):21-35.
[49] WAHYUDIONO,SASAKI M,GOTO M. Conversion of biomass model compound under hydrothermal conditions using batch reactor[J]. Fuel,2009,88(9):1656-1664.
[50] TANG X,WANG S,QIAN L,et al. Corrosion behavior of nickel base alloys,stainless steel and titanium alloy in supercritical water containing chloride,phosphate and oxygen[J]. Chemical Engineering Research and Design,2015,100:530-541.
[51] KARIMI K,KHERADMANDINIA S,TAHERZADEH M J. Conversion of rice straw to sugars by dilute-acid hydrolysis[J]. Biomass and Bioenergy,2006,30(3):247-253.
[52] SINGH R,BALAGURUMURTHY B,PRAKASH A,et al. Catalytic hydrothermal liquefaction of water hyacinth[J]. Bioresource Technology,2015,178:157-165.
[53] KUMAR S,GUPTA R B. Biocrude production from switchgrass using subcritical water[J]. Energy & Fuels,2009,23(10):5151-5159.
[54] ZHANG Z,ZHAO Z K. Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid[J]. Bioresource Technology,2010,101(3):1111-1114.
[55] LI C,ZHANG Z,ZHAO Z K. Direct conversion of glucose and cellulose to 5-hydroxymethylfurfural in ionic liquid under microwave irradiation[J]. Tetrahedron Letters,2009,50(38):5403-5405.
[56] TUNGAL R,SHENDE R. Subcritical aqueous phase reforming of wastepaper for biocrude and H[J]. Energy & Fuels,2013,27(6):3194-3203.
[57] TUNGAL R,SHENDE R V. Hydrothermal liquefaction of pinewood (Pinus ponderosa) for H₂,biocrude and bio-oil generation[J]. Applied Energy,2014,134:401-412.
[58] ZHANG S,JIN F,HU J,et al. Improvement of lactic acid production from cellulose with the addition of Zn/Ni/C under alkaline hydrothermal conditions[J]. Bioresource Technology,2011,102(2):1998-2003.
[59] SUN P,HENG M,SUN S,et al. Direct liquefaction of paulownia in hot compressed water:influence of catalysts[J]. Energy,2010,35(12):5421-5429.
[60] TEKIN K,KARAGÖZ S,BEKTAŞ S. Hydrothermal liquefaction of beech wood using a natural calcium borate mineral[J]. The Journal of Supercritical Fluids,2012,72:134-139.
[61] 王立华,袁兴中,曾光明,等. 生物质水热法催化液化的实验研究[J]. 太阳能学报,2009,30(8):1134-1138.
[62] CHEN Y,WANG F,YANG Z. Preparation and upgrading of hydrocarbon oil from deoxy-liquefaction of oil crop[J]. Bioresource Technology,2013,146:472-477.
[63] PEREGO C,BIANCHI D. Biomass upgrading through acid-base catalysis[J]. Chemical Engineering Journal,2010,161(3):314-322.
[64] MASTRAL J F,BERRUECO C,GEA M,et al. Catalytic degradation of high density polyethylene over nanocrystalline HZSM-5 zeolite [J]. Polymer Degradation And Stability,2006,91(12):3330-3338.
[65] XU J,JIANG J,DAI W,et al. Liquefaction of sawdust in hot compressed ethanol for the production of bio-oils[J]. Process Safety and Environmental Protection,2012,90(4):333-338.
[66] MURANAKA Y,IWAI A,HASEGAWA I,et al. Selective production of valuable chemicals from biomass by two-step conversion combining pre-oxidation and hydrothermal degradation [J]. Chemical Engineering Journal,2013,234:189-194.
[67] ROMAN-LESHKOV Y,CHHEDA J N,DUMESIC J A. Phase modifiers promote efficient production of hydroxymethylfurfural from fructose[J]. Science,2006,312(5782):1933-1937.