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磷酸活化法活性炭孔隙结构的调控机制

左宋林

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文章导航 > 新型炭材料  > 2018 >  33(4): 289-302
左宋林. 磷酸活化法活性炭孔隙结构的调控机制. 新型炭材料, 2018, 33(4): 289-302.
引用本文: 左宋林. 磷酸活化法活性炭孔隙结构的调控机制. 新型炭材料, 2018, 33(4): 289-302.
shu
ZUO Song-lin. A review of the control of pore texture of phosphoric acid-activated carbons. New Carbon Mater., 2018, 33(4): 289-302.
Citation: ZUO Song-lin. A review of the control of pore texture of phosphoric acid-activated carbons. New Carbon Mater., 2018, 33(4): 289-302.
shu

磷酸活化法活性炭孔隙结构的调控机制

  • 南京林业大学 化学工程学院, 江苏省农林生物质资源国家重点实验室培育建设点, 江苏 南京 210037

基金项目: 国家自然科学基金（3127062，31470600）.
详细信息
    通讯作者:

    左宋林,教授,博士.E-mail:zslnl@njfu.com.cn

  • 中图分类号: TQ127.1+1

A review of the control of pore texture of phosphoric acid-activated carbons

  • College of Chemical Engineering, Nanjing Forestry University, State Key Laboratory of Chemistry and Utilization of Agriculture and Forestry Biomass in Jiangsu Province, Nanjing 210037, China

Funds: National Natural Science Foundation of China(3127062, 31470600).

    摘要
  • 摘要: 磷酸活化法是植物纤维原料制备活性炭的主要化学活化方法。笔者系统综述了磷酸活化过程中活性炭孔隙结构的调控机制。从化学的观点，笔者提出植物纤维原料的磷酸活化在本质上是磷酸-生物高分子复合体的形成与热处理两个过程。基于这一概念，分析了植物纤维原料的组成与结构、浸渍条件等因素对磷酸-生物高分子复合体的组成与结构的影响，全面总结了植物纤维原料种类与预处理、植物细胞壁结构和结晶度、浸渍比、浸渍方式、温度和时间等组成、结构与条件对磷酸法活性炭孔隙结构的形成与发展的影响规律。在磷酸-生物高分子热处理过程中，系统总结了炭化温度、升温速率与中间停留温度等加热历程、惰性气体、氧化性气体和水蒸气等气氛对磷酸活化法活性炭孔隙结构的影响规律。最后概述了氧化性气氛和氧化试剂对磷酸活化过程的影响机理，以及磷酸活化过程中固相炭化和气相炭化对活性炭孔隙结构发展的贡献。
    Abstract: Phosphoric acid activation is a chemical activation process that has been widely used to produce activated carbons from lignocellulose. The author systemically reviews the process from the role of the acid, and the pore structure, chemical properties and uses of these activated carbons. This review provides comprehensive information on the control of the pore structure and proposes that the interaction of the phosphoric acid and the lignocellulose results in the formation of phosphoric acid/biopolymer composites so that the activation can be simply regarded as two successive steps, which are formation and thermal decomposition of such composites. Based on this idea, the paper comprehensively analyzes the effect of many factors including the composition and texture of the raw materials and the impregnation parameters on the constituents and structures of the H3PO4/biopolymer composite and thus on the pore structure of the activated carbon. These complex factors include (1) the composition of the lignocellulose and pretreatment of the raw materials, (2) cellular structure and crystallinity, (3) impregnation parameters such as impregnation ratio, method, temperature and time. During the subsequent heat treatment of the H3PO4/biopolymer composite, the significant effect of the heating program on the formation and development of pore structure, including such parameters as temperature, heating rate and any intermediate isothermal treatment, and carbonization atmosphere including inert gases, oxidative gases and steam are reviewed. Finally, the roles of the oxidative atmosphere and other oxidants during activation are outlined, and two types of carbonization and their effect on pore development are also proposed and discussed.
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    • 参考文献(86)
  • 张成旺, 左宋林, 胡贺. 废弃粉状活性炭制备糖液脱色用成型活性炭[J]. 林业工程学报, 2016, 1(4):69-73. (ZHANG Cheng-wang, ZUO Song-lin, HU He. Preparation of formed activated carbon for decolorizing sugar solution from waste powered activated carbon[J]. Journal of Forestry Engineering, 2016, 1(4):69-73.)
    左宋林. 磷酸活化法制备活性炭综述(一)磷酸的作用机理[J]. 林产化学与工业, 2017, 37(3):1-9. (Zuo Song-lin. Review on phosphoric acid activation for preparation of activated carbon(Ⅰ):roles of phosphoric acid[J]. Chemistry and Industry of Forest Products, 2017, 37(3):1-9.)
    Zuo S L, Liu J L, Yang J X, et al. Effects of the crystallinity of lignocellulosic material on the porosity of phosphoric acid activated carbon[J]. Carbon, 2009, 47(15):3578-3580.
    Guo Y, Rockstraw D A. Physical and chemical properties of carbons synthesized from xylan, cellulose, and Kraft lignin by H3PO4activation[J]. Carbon, 2006, 44(8):1464-1475.
    Hayashi J, Kazehaya A, Katsuhiko M, et al. Preparation of activated carbon from lignin by chemical activation[J]. Carbon, 2000, 38(13):1873-1878.
    Fierro V, Torné-Fernádez V, Celzard A, et al. Influence of the demineralization on the chemical activation of Kraft lignin with orthophosphoric acid[J]. Journal of Hazardous Materials, 2007, 149:126-133.
    Olivares-Marín M M, Fernández G C, Macías G A, et al. Thermal behavior of lignocellulosic material in the presence of phosphoric acid. Influence of the acid content in the initial solution[J]. Carbon, 2006, 44(11):2347-50.
    Jagtoyen M, Derbyshire F. Activated carbons from yellow poplar and white oak by H3PO4 activation[J]. Carbon, 1998, 36(7-8):1085-1097.
    Torrellas S Á,Lovera R G, Escalona N, et al. Chemical-activated carbons from peach stones for the adsorption of emerging contaminants in aqueous solutions[J]. Chemical Engineering Journal, 2015, 279:788-798.
    Baquero M C, Giraldo L, Morenoet J C. Activated carbons by pyrolysis of coffee bean husks in presence of phosphoric acid[J]. Journal of Analytical and Applied Pyrolysis. 2003, 70(2):779-784.
    Diao Y L, Walwender W P, Fan L T. Activated carbons prepared from phosphoric acid activation of grain sorghum[J]. Bioresource Technology, 2002, 81:45-52
    Diaz-Diez M A, Gomez-Serrano V, Fernandez Gonzalez C,et al. Porous texture of activated carbon prepared by phosphoric acid activation of woods[J]. Applied Surface Science, 2004, 238:309-313.
    Sun Y Y, Li H, Li G C, et al. Characterization and ciprofloxacin adsorption properties of activated carbons prepared from biomass wastes by H3PO4 activation[J]. Bioresource technology, 2016, 217:239-244.
    Williams PT, Reed AR. High grade activated carbon matting derived from the chemical activation and pyrolysis of natural fibre textile waste[J]. Journal of Analytical and Applied Pyrolysis, 2004, 71(2):971-986.
    El-Hendawy ANA, Samra SE, Dirgis BS. Adsorption characteristics of activated carbons obtained from corncobs[J]. Colloid and Surface A-Physicochemical and Engineering Aspects, 2001, 180(3):209-221.
    Vernersson T, Bonelli PR, Cerrella EG,et al. Arundodonax cane as a precursor for activated carbons preparation by phosphoric acid activation[J]. Bioresource Technology, 2002, 83(2):95-104.
    Suárez-García F, Martínez-Alonso A, Tascón JMD. Pore texture of activated carbons prepared from phosphoric acid of apple pulp[J]. Carbon, 2001, 39(7):1111-1115.
    Suárez-García F, Martínez-Alonso A, Tascón J M D.A comparative study of the thermal decomposition of apple pulp in the absence and presence of phosphoric acid[J].Polymer Degradation and Stability, 2002, 75(2):375-383.
    Guo YP, Rockstraw DA. Activated carbons prepared from rice hull by one-step phosphoric acid activation[J]. Microporous and Mesoporous Materials, 2007, 100(1-3):12-19.
    Li Y, Zhang X, Yang R, et al. The role of H3PO4 in the preparation of activated carbon from NaOH-treated rice husk residue[J]. RSC Advances, 2015, 5(41):32626-32636
    Fierro V, Muñiz G, Basta A H, et al. Rice straw as precursor of activated carbons:Activation with ortho-phosphoric acid[J]. Journal of Hazardous Materials, 2010, 181(1-3):27-34.
    El-Hendawy ANA, Alexander A J, Andrews R J, et al. Effects of activation schemes on porous, surface and thermal properties of activated carbons prepared from cotton stalks[J]. Journal of Analytical and Applied Pyrolysis, 2008, 82(2):272-278.
    Rosas JM, Bedia J, Rodríguez-Mirasol J, et al. HEMP-derived activated carbon fibers by chemical activation with phosphoric acid[J]. Fuel, 2009, 88(1):19-26.
    Njoku V O, Islam M A, Asif M, et al. Adsorption of 2, 4-dichlorophenoxyacetic acid by mesoporous activated carbon prepared from H3PO4-activated langsat empty fruit bunch[J]. Journal of Environmental Management, 2015, 154:138-144.
    Prahas D, Kartika Y, Indraswati N, et al. Activated carbon from jackfruit peel waste by H3PO4 chemical activation:Pore structure and surface chemistry characterization[J]. Chemical Engineering Journal, 2008, 140:32-42.
    Hadoun H, Sadaoui Z, Souami N, et al. Characterization of mesoporous carbon prepared from date stems by H3PO4 chemical activation[J]. Applied Surface Science, 2013, 280:1-7.
    Heidari A, Younesi H, Rashidi A, et al. Adsorptive removal of CO2 on highly microporous activated carbons prepared from Eucalyptus camaldulensis wood:effect of chemical activation[J]. Journal of the Taiwan Institute of Chemical Engineers,2014, 45(2):579-588.
    Carrott PJM, Ribeiro MML, Mourão PAM. Pore size control in activated carbons obtained by pyrolysis under different conditions of chemically impregnated cork[J]. Journal of Analytical and Applied Pyrolysis, 2006, 75(2):120-127.
    Girgis BS, EI-Hendawy ANA. Porosity development in activated carbons obtained from date pits under chemical activation with phosphoric acid[J]. Microporous and Mesoporous Materials, 2002, 52(2):105-117.
    Jaine J, Calafat A, Labady M. Preparation and characterization of activated carbons from coconut shell impregnated with phosphoric acid[J]. Carbon, 1989, 27(2):191-195.
    Youssef AM, Radwan NRE, Abdel-Gawad I, et al. Textural properties of activated carbons from apricot stones[J]. Colloid and Surface A-Physicochemical and Engineering Aspects, 2005, 252(2-3):43-51.
    Jagtoyen M, Thwaites M, Stencel J, et al. Adsorbent carbon synthesis from coals by phosphoric acid activation[J]. Carbon, 1992, 30(7):1089-1096.
    Teng H, Yen TS, Hsu LY. Preparation of activated carbon from bituminous coal with phosphoric acid activation[J]. Carbon, 1998, 36(9):1387-95.
    Suhas PJM, Carrott MML,Carrott R. Lignin-from natural adsorbent to activated carbon:a review[J]. Bioresource Technology, 2007, 98:2301-2312.
    Rabinovich ML, Fedoryak O, Dobele G, et al. Carbon adsorbents from industrial hydrolysis lignin:The USSR/Eastern European experience and its importance for modern biorefineries[J]. Renewable and Sustainable Energy Reviews, 2016, 57:1008-1024.
    Fierro V, Torné-Fernández V, Montané D,et al. Study of the decomposition of kraft lignin impregnated with orthophosphoric acid[J]. Thermochimica Acta, 2005, 433(1-2):142-148.
    Hayashi J, Muroyama K, Gomes VG, et al. Fractal dimensions of activated carbons prepared from lignin by chemical activation[J]. Carbon, 2002, 40:617-636.
    Myglovets M, Poddubnaya O I, Sevastyanova O, et al. Preparation of carbon adsorbents from lignosulfonate by phosphoric acid activation for the adsorption of metal ions[J].Carbon, 2014, 80:771-783.
    Castro-Muñiz A,Suárez-García F, Martínez-Alonso A, et al. Activated carbon fibers with a high content of surface functional groups by phosphoric acid activation of PPTA[J]. Journal of Colloid and Interface Science, 2011, 361:307-315.
    Jagtoyen M, Groppo J, Derbyshire F. Activated carbons from bituminous coals by reactionwith H3PO4:The influence of coal cleaning[J]. Fuel Processing Technology, 1993, 34:85-96.
    Puziy AM, Poddubnaya OI, Martínez-Alonso A, et al. Synthetic carbons activated with phosphoric acid:Ⅱ. Porous structure[J].Carbon, 2002, 40(19):1507-1519.
    Puziy AM, Puddubana O I, Martinez-Alonso A, et al. Synthetic carbons activated with phosphoric acid. Carbons prepared in air[J]. Carbon, 2003, 41(6):1181-1191.
    符若文, 刘玲, 陆耘, 等. 活性碳纤维吸附的研究Ⅱ-磷酸活化活性碳纤维的制备工艺与吸附性能关系[J]. 新型炭材料, 1997, 12(4):39-44. (FU Ruo-wen, LIU Ling, LU Yun, et al. Studies on the adsorption of activated carbon fibers Ⅱ-Relation between the adsorption capacity and preparation technology of activated carbon fibers by phosphoric acid activation. New Carbon Materials, 1997, 12(4):39-44.)
    Fabián SG, Amelia MA, Juan TMD. Activated carbon fibers from Nomex by chemical activation with phosphoric acid[J]. Carbon, 2004, 42(8-9):1419-1426.
    Rosas JM, Bedia J, Rodríguez-Mirasol J, et al. HEMP-derived activated carbon fibers by chemical activation with phosphoric acid[J]. Fuel, 2009, 88(1):19-26.
    Vázquez-Santos MB, Suárez-García F, Martínez-Alonso A, et al. Activated carbon fibers with a high heteroatom content by chemical activation of PBO with phosphoric acid[J]. Langmuir, 2012, 28(13):5850-5860.
    Liu H, Zhang J, Ngo HH, et al. Carbohydrate-based activated carbon with high surface acidity and basicity for nickel removal from synthetic wastewater[J]. RSC Advances, 2015, 5(64):52048-52056.
    Rabemanolontsoa H, Saka S. Various pretreatments of lignocellulosics[J]. Bioresource Technology, 2016, 199:83-91.
    Mosier N, Wyman C, Dale B, et al. Features of promising technologies for pretreatment of lignocellulosicbiomass[J]. Bioresource Technology, 2005, 96(6):673-686.
    Heidari A, Younesi H, Rashidi A, et al. Adsorptive removal of CO2 on highly microporous activated carbons prepared from Eucalyptuscamaldulensis wood:effect of chemical activation[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(2):579-588.
    Zhu G, Deng X, Hou M, et al. Comparative study on characterization and adsorption properties of activated carbons by phosphoric acid activation from corncob and its acid and alkaline hydrolysis residues[J]. Fuel Processing Technology, 2016, 144:255-261.
    Tehrani N F, Javier SA, Kiros Y. Coffee extract residue for production of ethanol and activated carbons[J]. Journal of Cleaner Production,2015, 91:64-70.
    Sun Y,Yang G,Zhang JP, et al.Activated carbon preparation from lignin by H3PO4 activation and its application to gas separation[J].Chemical Engineering Technology, 2012, 35(2):309-316.
    Kennedy LJ, Vijaya JJ, Sekaran G. Effect of two-stage process on the preparation and characterization of porous carbon composite from rice husk by phosphoric acid activation[J]. Industrial & Engineering Chemistry Research, 2004, 43:1832-1838.
    Yorgun S, Derya Y. Preparation and characterization of activated carbons from Paulownia wood by chemical activation with H3PO4[J]. Journal of the Taiwan Institute of Chemical Engineers, 2015, 53:122-131.
    Reddy KSK, Shoaibi AAl, Srinivasakannan C. Preparation of porous carbon from date palm seeds and process optimization[J]. International Journal of Environmental Science and Technology, 2015, 12(3):959-966.
    Altenor S, Carene B, Emmanuel E, et al. Adsorption studies of methylene blue and phenol onto vetiver roots activated carbon prepared by chemical activation[J]. Journal of Hazardous Materials, 2009, 165(1-3):1029-1039.
    Yavuz R, Akyildiz H, Karatepe N, et al. Influence of preparation conditions on porous structures of olive stone activated by H3PO4[J].Fuel Processing Technology, 2010, 91(1):80-87.
    Zuo SL, Yang JX, Liu JL, et al. Effect of the heating history of impregnated lignocellulosic material on Pore development during phosphoric acid activation[J]. Carbon, 2010, 48(11):3293-3295.
    Wang YF, Zuo SL, Zhu Y, et al. Role of oxidant during phosphoric acid activation of lignocellulosic material[J]. Carbon, 2014, 66:734-737.
    Ma XD, Feng OY. Adsorption properties of biomass-based activated carbon prepared with spent coffee grounds and pomelo skin by phosphoric acid activation[J]. Applied Surface Science, 2013, 268:566-570.
    Lim WC, Srinivasakannan C, Balasubramanian N. Activation of palm shells by phosphoric acid impregnation for high yielding activated carbon[J]. Journal of Analytical and Applied Pyrolysis, 2010, 88(2):181-186.
    Lin G F, Jiang J C,Wu K J, et al. Effects of heat pretreatment during impregnation on the preparation of activated carbon from Chinese fir wood by phosphoric acid activation[J]. Bioenergy Research, 2013, 6(4):1237-1242.
    Romero-Anaya A J, Lillo-Ródenas M A,Lecea CSM, et al. Hydrothermal and conventional H3PO4 activation of two natural bio-fibers[J]. Carbon, 2012, 50(9):3158-3169
    González-Domínguez JM, Fernández-González C, Alexandre-Franco M, et al.The influence of the impregnation method on yield of activated carbon produced by H3PO4 activation[J]. Materials Letters, 2011, 65(9):1423-1426
    Jagtoyen M, Derbyshire F. Some consideration of the origins of porosity in carbons from chemically activated wood[J]. Carbon, 1993, 31(7):1185-1192.
    Molina-Sabio M, Rodríguez-Reinoso F, Caturla F, et al. Porosity in granular carbons activated with phosphoric acid[J]. Carbon, 1995, 33(8):105-113.
    Liou TH. Development of mesoporous structure and high adsorption capacity of biomass-based activated carbon by phosphoric acid and zinc chloride activation[J]. Chemical Engineering Journal, 2010, 158(2):129-142.
    Nahil M A, Williams PT. Pore characteristics of activated carbons from the phosphoric acid chemical activation of cotton stalks[J]. Biomass and Bioenergy, 2012, 37:142-149.
    Puziy AM, Puddubana OI, Martinez-Alonso A, et al. Synthetic carbons activated with phosphoric acid I. Surface chemistry and ion binding properties[J]. Carbon, 2002, 40(9):1493-505.
    左宋林, 森田光博. 空气-磷酸活化木炭制备酸性颗粒活性炭的研究[J]. 林产化学与工业, 2010, 30(6):13-16. (ZUO Song-lin, MORITA Mitsuhiro. Study on preparation of acidic activated carbon by air-phosphoric acid activation of charcoal[J]. Chemistry and Industry of Forest Products, 2010, 30(6):13-16.)
    王永芳, 左宋林. 含磷活性炭作为双电层电容器电极材料的电化学性能[J]. 物理化学学报, 2016, 32(2):481-492. (WANG Yong-Fang, ZUO Song-Lin. Electrochemical properties of phosphorus-containing activated carbon electrodes on electrical double-layer capacitors[J]. Acta Phys. Chim. Sin., 2016, 32(2):481-492.)
    Kyzas G Z, Deliyanni E A, Matis K A. Activated carbons produced by pyrolysis of waste potato peels:cobalt ions removal by adsorption[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2016, 490:74-83.
    Reddy KSK, Shoaibi A A, Srinivasakannan C. Preparation of porous carbon from date palm seeds and process optimization[J]. International Journal of Environmental Science and Technology, 2015, 12:959-966.
    Yu LW, Tatsumi DK, Zuo SL,et al. Promotion of crystal growth on biomass-based carbon using phosphoric acid treatments[J]. BioResources, 2015, 10(2):2406-2417.
    Chen MD, Kang XY, Wumaier TD, et al. Preparation of activated carbon from cotton stalk and its application in supercapacitor[J]. Journal of Solid State Electrochemistry, 2013, 17:1005-1012.
    Caturla F, Molina-Sabio M, Rodriguez-Reinoso F. Preparation of activated carbon by chemical activation with ZnCl2[J]. Carbon, 1991, 29(7):999-1007.
    Molina-Sabio M, Caturla F, Rodríguez-Reinoso F. Influence of the atmosphere used in the carbonization of phosphoric acid impregnated peach stones[J]. Carbon 1995; 33(8):1180-1182.
    Benaddi H, Legras D, Rouzaud JN, et al. Influence of the atmosphere in the chemical activation of wood by phosphoric acid[J]. Carbon, 1998, 36(3):306-309.
    Benaddi1 H, Bandosz T J, Jagiellob J, et al. Surface functionality and porosity of activated carbons obtained from chemical activation of wood[J]. Carbon, 2000, 38:669-674.
    Budinova T, Ekinci E, Yardim F, et al. Characterization and application of activated carbon produced by H3PO4 and water vapor activation[J]. Fuel Process Technology, 2006, 87(10):899-905.
    Klijanienko A, Lorenc-Grabowska E, Gryglewicz G. Development of mesoporosity during phosphoric acid activation of wood in steam atmosphere[J]. Bioresource Technology, 2008, 99(15):7208-7214.
    Iwona L, Yperman J, Carleer R, et al. Tailoring of porous texture of hemp stem-based activated carbon produced by phosphoric acid activation in steam atmosphere[J]. Journal of Porous Materials, 2015, 22(1):283-289.
    Zuo SL, Yang JX, Liu JL, et al. Significance of the carbonization of volatile pyrolytic products on the properties of activated carbon by phosphoric acid activation[J]. Fuel Processing Technology, 2009, 90(7-8):994-1001.
    Zuo SL, Xiao ZL, Yang JX. Evolution of gaseous products from biomass pyrolysis in the presence of phosphoric acid[J]. Journal of Analytical and Applied Pyrolysis, 2012, 95:236-240.
    Yuso AM, Rubio B, Izquierdo MT. Influence of activation atmosphere used in the chemical activation of almond shell on the characteristics and adsorption performance of activated carbons[J]. Fuel Processing Technology, 2014, 119:74-80.
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  • 收稿日期:  2018-02-27
  • 录用日期:  2018-08-30
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