碳纳米管-石墨烯气凝胶制备及其对水中乳化油的吸附特性

doi:10.11949/j.issn.0438-1157.20170895

化工学报 ›› 2018, Vol. 69 ›› Issue (4): 1508-1517.DOI: 10.11949/j.issn.0438-1157.20170895

碳纳米管-石墨烯气凝胶制备及其对水中乳化油的吸附特性

马雁冰, 刘会娥, 陈爽, 丁传芹

中国石油大学(华东)化学工程学院, 山东青岛 266580

收稿日期:2017-07-12 修回日期:2017-11-14 出版日期:2018-04-05 发布日期:2018-04-05
通讯作者: 刘会娥
基金资助:
山东省自然科学基金项目（ZR2017MB015）；重质油国家重点实验室资助项目（SLKZZ-2017002）；中国石油科技创新基金项目（2017D-5007-0601）。

Facile synthesis of carbon nanotubes-graphene aerogels and its adsorption property for emulsified oil in water

MA Yanbing, LIU Hui'e, CHEN Shuang, DING Chuanqin

College of Chemical Engineering, China University of Petroleum, Qingdao 266580, Shandong, China

Received:2017-07-12 Revised:2017-11-14 Online:2018-04-05 Published:2018-04-05
Supported by:
supported by the Natural Science Foundation of Shandong Province (ZR2017MB015), the Projects of State Key Laboratory of Heavy Oil Processing (SLKZZ-2017002) and the PetroChina Innovation Foundation (2017D-5007-0601).

摘要/Abstract

摘要：

以改进的Hummers-Offeman法制备出的氧化石墨（GO）与羧基化多壁碳纳米管（CNTs—COOH）为原料，聚乙烯吡咯烷酮（PVP）为交联剂，乙二胺（EDA）为还原剂，水热还原法制得羧基碳纳米管-石墨烯复合气凝胶（CGA）。调整GO与CNTs—COOH的质量比获得密度在8.40～14.42 mg·cm^-3之间的气凝胶，并确定在GO：CNTs—COOH=3：1（质量）时得到的气凝胶的机械强度最优。通过扫描电子显微镜（SEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）对所制备的CGA进行表征，得知GO与CNTs—COOH已成功还原组装成多孔状三维气凝胶结构。以水中乳化柴油作为研究对象，考察CGA样品在不同温度下对乳化柴油的吸附特性。结果表明，CGA的吸附量在前6 min迅速上升，在30 min左右达到吸附平衡，且平衡吸附量随温度升高而增加。吸附过程遵循准二级动力学模型，体系表观活化能为7.10 kJ·mol^-1。利用颗粒内扩散模型分析得出，CGA对乳化油的吸附分为外表面吸附过程和内部孔道吸附过程（内部大孔道吸附、中孔道和微孔道内扩散3个阶段）。

关键词: 羧基碳纳米管, 石墨烯, 气凝胶, 复合材料, 吸附, 动力学

Abstract:

Graphene oxide (GO) was prepared by an improved Hummers-Offeman's method. The GO and carboxylated multi-walled carbon nanotubes (CNTs-COOH) was used as raw materials, polyvinyl pyrrolidone (PVP) as crosslinking agent and ethylenediamine (EDA) as the reducing agent. Hydro-thermal method was adopted in the preparation of carbon nanotubes-graphene aerogel (CGA). The density was between 8.40 mg·cm^-3 and 14.42 mg·cm^-3 for CGAs under different mass ratios of GO to CNTs-COOH. The mechanical strength of the composite aerogel under the mass ratio of GO:CNTs-COOH=3:1 is optimal. The characterized results by scanning electron microscopy (SEM), X ray diffraction (XRD), X ray photoelectron spectroscopy (XPS) showed that GO and CNTs-COOH have been successfully assembled into reducing porous aerogel structure. The study on CGA sample adsorption characteristics of emulsified diesel oil in water at different temperatures showed that the adsorption capacity of CGA increased rapidly in the first 6 min. The adsorption equilibrium was achieved in about 30 min. With the increase of temperature, the equilibrium adsorption capacity increased gradually. The adsorption process follows pseudo-second order kinetics model. The apparent activation energy is 7.10 kJ·mol^-1. Through the particle diffusion model analysis, it is found that the adsorption process of CGA is divided into an outer surface adsorption and pore adsorption processes, which include large inner pore adsorption, mesopore adsorption and small-size pore adsorption.

Key words: carboxylated carbon nanotubes, graphene, aerogels, composites, adsorption, kinetics

中图分类号:

TQ013.2

马雁冰, 刘会娥, 陈爽, 丁传芹. 碳纳米管-石墨烯气凝胶制备及其对水中乳化油的吸附特性[J]. 化工学报, 2018, 69(4): 1508-1517.

MA Yanbing, LIU Hui'e, CHEN Shuang, DING Chuanqin. Facile synthesis of carbon nanotubes-graphene aerogels and its adsorption property for emulsified oil in water[J]. CIESC Journal, 2018, 69(4): 1508-1517.

参考文献 30

[1]	ORGE C A, SOUSA J P S, GONÇALVES F, et al. Development of novel mesoporous carbon materials for the catalytic ozonation of organic pollutants[J]. Catalysis Letters, 2009, 132(1/2):1-9.
[2]	WANG X, KALALI E N, WAN J T, et al. Carbon-family materials for flame retardant polymeric materials[J]. Progress in Polymer Science, 2017, 69(1):22-46.
[3]	LIN C G, HU J, SONG Y F. Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage, and sensor systems[J]. Advances in Inorganic Chemistry, 2017, 8(3):776-789.
[4]	ⅡJIMA S. Helical microtubules of graphitic carbon[J]. Nature, 1991, 354(6348):56-58.
[5]	RAFIEE M A. Graphene[J]. Dissertations & Theses-Gradworks, 2011, 442(7100):282-286.
[6]	HU H, ZHAO Z, WAN W, et al. Ultralight and highly compressible graphene aerogels[J]. Advanced Materials, 2013, 25(15):2219-2223.
[7]	WU Y, YI N, HUANG L, et al. Three-dimensionally bonded spongy graphene material with super compressive elasticity and near-zero Poisson's ratio[J]. Nature Communications, 2015, 6(6141):1-10.
[8]	REN H, SHI X, ZHU J, et al. Facile synthesis of N-doped graphene aerogel and its application for organic solvent adsorption[J]. Journal of Materials Science, 2016, 51(13):6419-6427.
[9]	SUN H, XU Z, GAO C. Aerogels:multifunctional, ultra-flyweight, synergistically assembled carbon aerogels[J]. Advanced Materials, 2013, 25(18):2632-2632.
[10]	LV P, YU K, TAN X, et al. Super-elastic graphene/carbon nanotube aerogels and their application as a strain-gauge sensor[J]. RSC Advances, 2016, 6(14):11256-11261.
[11]	WAN W, ZHANG R, LI W, et al. Graphene-carbon nanotube aerogel as an ultra-light, compressible and recyclable highly efficient absorbent for oil and dyes[J]. Environmental Science Nano, 2016, 3(1):107-113.
[12]	朱慧, 刘会娥, 黄剑坤, 等. 多壁碳纳米管吸附处理柴油废水的动力学特性[J]. 化工学报, 2015, 66(12):4865-4873. ZHU H, LIU H E, HUANG J K, et al. Kinetics for adsorption treatment of diesel oil waste water by multi-walled carbon nanotubes[J]. CIESC Journal, 2015, 66(12):4865-4873.
[13]	COTE L J, KIM F, HUANG J. Langmuir-blodgett assembly of graphite oxide single layers[J]. Journal of the American Chemical Society, 2009, 131(3):1043-1051.
[14]	黄剑坤, 刘会娥, 黄扬帆, 等. 石墨烯气凝胶的制备及其对水中油分的吸附特性[J]. 化工学报, 2016, 67(12):5048-5056. HUANG J K, LIU H E, HUANG Y F, et al. Facile synthesis of MWCNT/SiO2 nano-composites as high-performance adsorbents for diesel removal from oily water[J]. CIESC Journal, 2016, 67(10):4485-4492.
[15]	HUANG J, LIU H, CHEN S, et al. Hierarchical porous MWCNTs-silica aerogel synthesis for high-efficiency oily water treatment[J]. Journal of Environmental Chemical Engineering, 2016, 4(3):3274-3282.
[16]	SUI Z, MENG Q, ZHANG X, et al. Green synthesis of carbon nanotube-graphene hybrid aerogels and their use as versatile agents for water purification[J]. Journal of Materials Chemistry, 2012, 22(18):8767-8771.
[17]	LIN Y, EHLERT G J, BUKOWSKY C, et al. Superhydrophobic functionalized graphene aerogels[J]. ACS Applied Materials & Interfaces, 2011, 3(7):2200-2203.
[18]	HO Y S, MCKAY G. Pseudo-second order model for sorption processes[J]. Process Biochemistry, 1999, 34(5):451-465.
[19]	WU C H. Adsorption of reactive dye onto carbon nanotubes:equilibrium, kinetics and thermodynamics[J]. Journal of Hazardous Materials, 2007, 144(1):93-100.
[20]	NOLLET H, ROELS M, LUTGEN P, et al. Removal of PCBs from wastewater using fly ash[J]. Chemosphere, 2003, 53(6):655-665.
[21]	KAVITHA D, NAMASIVAYAM C. Experimental and kinetic studies on methylene blue adsorption by coir pith carbon[J]. Bioresource Technology, 2007, 98(1):14-21.
[22]	MALL I D, SRIVASTAVA V C, AGARWAL N K, et al. Removal of Congo red from aqueous solution by bagasse fly ash and activated carbon:kinetic study and equilibrium isotherm analyses[J]. Chemosphere, 2005, 61(4):492-501.
[23]	WU F C, TSENG R L, JUANG R S. Initial behavior of intraparticle diffusion model used in the description of adsorption kinetics[J]. Chemical Engineering Journal, 2009, 153(1):1-8.
[24]	ZHANG S, SHAO T, KOSE H S, et al. Adsorption kinetics of aromatic compounds on carbon nanotubes and activated carbons[J]. Environmental Toxicology and Chemistry, 2012, 31(1):79-85.
[25]	刘俊涛. 三维复合型石墨烯气凝胶的合成及其对重金属的去除研究[D]. 北京:中国科学院大学, 2016. LIU J T. Synthesis of three dimensional composite graphene aerogels and their removal of heavy metals[D]. Beijing:University of Chinese Academy of Sciences, 2016.
[26]	HAN Q, YANG L, LIANG Q, et al. Three-dimensional hierarchical porous graphene aerogel for efficient adsorption and preconcentration of chemical warfare agents[J]. Carbon, 2017, 122(201):556-563.
[27]	FIGARO S, AVRIL J P, BROUERS F, et al. Adsorption studies of molasse's wastewaters on activated carbon:modelling with a new fractal kinetic equation and evaluation of kinetic models[J]. Journal of Hazardous Materials, 2009, 161(2/3):649-656.
[28]	WU F C, TSENG R L, JUANG R S. Initial behavior of intraparticle diffusion model used in the description of adsorption kinetics[J]. Chemical Engineering Journal, 2009, 153(1):1-8.
[29]	CHEUNG W, SZETO Y, MCKAY G. Intraparticle diffusion processes during acid dye adsorption onto chitosan[J]. Bioresource Technology, 2007, 98(15):2897-2904.
[30]	LIU C, LIU H, XU A, et al. In situ reduced and assembled three-dimensional graphene aerogel for efficient dye removal[J]. Journal of Alloys & Compounds, 2017, 714(245):522-529.

碳纳米管-石墨烯气凝胶制备及其对水中乳化油的吸附特性

Facile synthesis of carbon nanotubes-graphene aerogels and its adsorption property for emulsified oil in water

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[2]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[3]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[4]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[5]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[6]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[7]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[8]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[9]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[10]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[11]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[12]	徐文杰, 贾献峰, 王际童, 乔文明, 凌立成, 王任平, 余子舰, 张寅旭. 有机硅/酚醛杂化气凝胶的制备和性能研究[J]. 化工学报, 2023, 74(8): 3572-3583.
[13]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[14]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[15]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.