热解自活化法制备生物质基微孔型活性炭

孙康; 冷昌宇; 蒋剑春; 卜权; 林冠峰; 卢辛成; 朱光真

doi:10.1016/S1872-5805(17)60134-3

热解自活化法制备生物质基微孔型活性炭

doi: 10.1016/S1872-5805(17)60134-3

孙康^1,2,
冷昌宇¹,
蒋剑春^1,2,,
卜权³,
林冠峰⁴,
卢辛成¹,
朱光真¹

1.
中国林业科学研究院林产化学工业研究所, 江苏南京 210042;
2.
中国林业科学研究院林业新技术研究所, 北京 100091;
3.
江苏大学农业装备工程学院, 江苏大学, 江苏镇江 212013;
4.
福建农林大学金山学院, 福建福州 350002

基金项目: 林业公益性行业专项（201404610）；国家自然基金（31400510）.

详细信息

作者简介:
孙康,博士,副研究员.E-mail:sunkang0226@163.com

通讯作者:
蒋剑春,研究员.E-mail:bio-energy@163.com

中图分类号: TQ127.1⁺1
计量
- 文章访问数: 597
- HTML全文浏览量: 132
- PDF下载量: 344
- 被引次数: 0
出版历程
- 收稿日期: 2017-04-06
- 录用日期: 2017-11-13
- 修回日期: 2017-08-09
- 刊出日期: 2017-10-28

Microporous activated carbons from coconut shells produced by self-activation using the pyrolysis gases produced from them, that have an excellent electric double layer performance

1.
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China;
2.
Research Institute of Forestry New Technology of Forestry, Chinese Academy of Forestry, Beijing 100091, China;
3.
School of Agricultural Equipment Engineering, Jiangsu University, Zhenjiang 212013, China;
4.
Jinshan College of Fujian Agriculture and Forestry University, Fuzhou 350002, China

Funds: State Forestry Public Benefit Research Sector (201404610); Natural Science Foundation of China (31400510).

摘要

摘要: 提出热解自活化制备生物质基活性炭的新方法，制备过程不添加任何活化剂。将生物质原料置于可密闭反应器，在高温高压条件下进行热解自活化反应。结果表明，椰子壳是热解自活化制备微孔型活性炭的最佳原料，选择活化温度900℃并保持6 h，制备出了具有网络状发达微孔结构的活性炭，微孔率高达87.8%，比表面积1 194.4 m²/g，总孔容积0.528 cm³/g，碘吸附值1 280 mg/g，亚甲基蓝吸附值315 mg/g。同时，作为电化学储能电极材料，比电容可达258 F/g，而且阻抗小，3 000次充电循环后比电容仍能保持97.2%。热解自活化机理研究表明，生物质热解过程中产生的水蒸气、二氧化碳和反应器内的空气形成了良好的活化气氛，密闭反应器内形成的自生压力促进了水蒸气/二氧化碳与固体炭的活化反应速度，明显提高了微孔率。为了验证热解自活化法对其他生物质原料的适用性，还选择了杏核、核桃壳和松木屑作为原料进行热解自活化实验，并制得了高吸附力的活性炭样品。因此，热解自活化是一种无污染、清洁方便、产品得率高的新型活化方法，可产生良好的经济和环境效益。
- 生物质 /
- 微孔活性炭 /
- 热解自活化 /
- 电极材料 /
- 机理分析
Abstract: Coconut shell-based activated carbons were prepared by self-activation using the pyrolysis gases generated from them. The process was carried out at high temperatures in a closed reactor filled with coconut shell under a high pressure that was generated by pyrolysis gases. Results indicate that the activated carbon prepared at 900℃ for 6 h has a specific surface area, total pore volume, micropore percentage, iodine adsorption capacity and methylene blue adsorption capacity of 1 194.4 m²/g, 0.528 cm³/g, 87.8%, 1 280 mg/g and 315 mg/g, respectively. When used as the electrode material of electrochemical capacitors this activated carbon exhibits a specific capacitance of 258 F/g, a high capacitance retention rate of 97.2% after 3 000 charge/discharge cycles and a small impedance. The water vapor and carbon dioxide generated by the pyrolysis of the coconut shell in the closed reactor act as activating agents and also increase the pressure of the reaction system. This is favorable for the activation of the formed char. This self-activation method was also used to prepare activated carbons with high adsorption capacities for iodine and methylene blue from almond stones, pecan shells and slash pine sawdust, indicating that it is a very simple, efficient, environmentally friendly and economical method for the preparation of biomass-based activated carbons for supercapacitor electrode materials and adsorption.
- Biomass /
- Microspores activated carbon /
- Self-activation pyrolysis /
- Electrode material /
- Mechanism analysis

HTML全文

下载: 全尺寸图片幻灯片

参考文献(30)

Qiang L, Yin W, Jian Y, et al. Preparation and characterization of activated carbons from spirit lees by physical activation[J]. Carbon, 2012, 55(1):376.

Jagtoyen M, Derbyshire F. Activated carbons from yellow and white oak by H₃PO₄ activation[J]. Carbon, 1998, 36(7-8):1085-1097.

Caturla F, Molina-Sabio M, Rodríguez-Reinoso F. Preparation of activated carbon by chemical activation with ZnCl₂[J]. Carbon, 1991, 29(7):999-1007.

Elmouwahidi A, Zapata-Benabithe Z, Carrasco-Marín F, et al. Activated carbons from KOH-activation of argan (Argania spinosa) seed shells as supercapacitor electrodes[J]. Bioresource Technology, 2012, 111(1):185-190.

Pol S V,Pol V G,Gedanken A.Reactions under autogenerated pressure at elevated temperature (RAPET) of various alkoxides:formation of metals/metal oxides-carbon core-hell structures[J]. Chemistry, 2004, 10(18):4467-473.

Gershi H, Gedanken A, Keppner H, et al. One-step synthesis of prolate spheroidal-shaped carbon produced by the thermolysis of octene under its autogenerated pressure[J]. Carbon, 2011,49(4):1067-1074.

Man S T, Antal M J. Preparation of activated carbons from macadamia nut shell and coconut shell by air activation[J]. Industrial & Engineering Chemistry Research, 1999, 38(11):4268-4276.

Qu W H, Xu Y Y, Lu A H. Converting biowaste corncob residue into high value added porous carbon for supercapacitor electrodes[J]. Bioresource Technology, 2015, 189:285-291.

Doyle M D, Loushine RJ, Agee K A, et al. Preparation of highly porous binderless activated carbon electrodes from fibres of oil palm empty fruit bunches for application in supercapacitors.[J]. Journal of Endodontics, 2013, 132(3):254-261.

Nishihara H, Itoi H, Kogure T, et al. Investigation of the ion storage/transfer behavior in an electrical double-layer capacitor by using ordered microporous carbons as model materials[J]. Chemistry, 2009, 15(15):5355-5363.

Ma G, Qian Y, Sun K. Nitrogen-doped porous carbon derived from biomass waste for high-performance supercapacitor[J]. Bioresource Technology, 2015, 197:137-142.

Kötz R, Carlen M. Principles and applications of electrochemical capacitors[J]. Electrochimica Acta, 2000, 45(s 15-16):2483-2498.

Fang B, Binder L. A modified activated carbon aerogel for high-energy storage in electric double layer capacitors[J]. Journal of Power Sources, 2006, 163(1):616-622.

Zhu Y, Murali S, Cai W, S et al. Graphene and graphene oxide:synthesis, properties, and applications[J]. Advanced Materials, 2010, 22(35):3906-3924.

Jiang W, Zhai S, Wei L. Nickel hydroxide-carbon nanotube nanocomposites as supercapacitor electrodes:crystallinity dependent performances[J]. Nanotechnology, 2015, 26(31).

Yu H R, Cho S, Jung M J. Electrochemical and structural characteristics of activated carbon-based electrodes modified via phosphoric acid[J]. Microporous & Mesoporous Materials, 2013, 172(172):131-135.

Redondo E, Carretero-González J, Goikolea E. Effect of pore texture on performance of activated carbon supercapacitor electrodes derived from olive pits[J]. Electrochimica Acta, 2015, 160:178-184.

Qu D. Studies of the activated carbons used in double-layer supercapacitors[J]. Journal of Power Sources, 2002, 109(2):403-411.

Chang J, Gao Z, Wang X. Activated porous carbon prepared from paulownia flower for high performance supercapacitor electrodes[J]. Electrochimica Acta, 2015, 157:290-298.

Oh I, Kim M, Kim J. Deposition of Fe₃O₄ on oxidized activated carbon by hydrazine reducing method for high performance supercapacitor[J]. Microelectronics Reliability, 2015, 55(1):114-122.

Sundaram E G, Natarajanb E. Department. Pyrolysis of coconut shell:an experimental investigation[J]. 2009, 6(2):33-39.

Rodríguez-Reinoso F, Molina-Sabio M, González M T. The use of steam and CO₂ as activating agents in the preparation of activated carbons[J]. Carbon, 1995, 33(1):15-23.

Xing J, Xia S, Dong K. Preparation and characterization of activated carbon from acorn shell by physical activation with H₂O-CO₂ in two-step pretreatment[J]. Bioresource Technology, 2013, 136(4):163-168.

Shim T, Yoo J, Ryu C. Effect of steam activation of biochar produced from a giant Miscanthus on copper sorption and toxicity[J]. Bioresource Technology, 2015, 197:85-90.

RodríGuez-Valero M A, MartíNez-Escandell M, Molina-Sabio M. CO₂ activation of olive stones carbonized under pressure[J]. Carbon, 2001, 39(2):320-323.

Lahijani P, Zainal Z A, Mohamed A R. Microwave-enhanced CO₂ gasification of oil palm shell char[J]. Bioresource Technology, 2014, 158(2):193-200.

Roberts D G, Harris D J. Char gasification with O₂, CO₂, and H₂O:Effects of pressure on intrinsic reaction kinetics[J]. Energy Fuels, 2000, 14(2):483-489.

Seebauer V, Petek J, Staudinger G. Effects of particle size, heating rate and pressure on measurement of pyrolysis kinetics by thermogravimetric analysis[J]. Fuel, 1997, 76(13):1277-1282.

Jiang L, Yan J, Hao L, et al. High rate performance activated carbons prepared from ginkgo shells for electrochemical supercapacitors[J]. Carbon, 2013, 56(56):146-154.

Sánchez-González J, Stoeckli F, Centeno T A. The role of the electric conductivity of carbons in the electrochemical capacitor performance[J]. Journal of Electroanalytical Chemistry, 2011, 657(657):176-180.

施引文献

资源附件(0)

访问统计