四乙烯五胺修饰介孔硅胶吸附CO<sub>2</sub>性能的研究

陈琳琳; 王霞; 郭庆杰

四乙烯五胺修饰介孔硅胶吸附CO₂性能的研究

青岛科技大学化工学院, 清洁化工过程山东省高校重点实验室, 山东青岛 266042

基金项目: 国家自然科学基金(21276129); 山东省自然科学杰出青年基金(JQ 200904).

详细信息

通讯作者:
郭庆杰,男,教授,Tel:0532-84022757,Fax:0532-84022757,E-mail:qj_guo@yahoo.com.

中图分类号: TQ028
计量
- 文章访问数: 518
- HTML全文浏览量: 26
- PDF下载量: 732
- 被引次数: 0
出版历程
- 收稿日期: 2014-07-31
- 修回日期: 2014-09-29
- 刊出日期: 2015-01-30

Study on CO₂ adsorption properties of tetraethylenepentamine modified mesoporous silica gel

Key Laboratory of Clean Chemical Processing of Shandong Province, Qingdao University of Science & Technology, Qingdao 266042, China

摘要

摘要: 采用浸渍法将四乙烯五胺(TEPA)负载到介孔硅胶(SG)上,制备了一系列胺功能化的CO₂吸附材料(TEPA-SG).利用傅里叶变换红外光谱(FT-IR)、热重分析(TGA)和N₂吸脱附等分析方法对样品进行了表征,并在固定床反应器中考察了TEPA负载量、吸附温度对CO₂吸附性能的影响,同时通过添加不同质量分数的聚乙二醇(PEG)考察了羟基对吸附性能及再生性能的促进作用.结果表明,当TEPA负载量为40%(质量分数)、吸附温度为70 ℃时,TEPA-SG的吸附量高达2.21 mmol/g;PEG的加入改变了氨基与CO₂的相互作用机理,当TEPA与PEG的质量比为3:1,总负载量为40%时,CO₂的吸附量为2.70 mmol/g,且经过10次吸脱附循环实验后,CO₂吸附量仍保持在2.66 mmol/g,表现出较好的循环稳定性.Clausius-Clapeyron方程计算得该过程的等量吸附热为30~40 kJ/mol,且随吸附量的增大等量吸附热逐渐减小,表明TEPA30/PEG10-SG吸附剂表面存在能量不均匀性.
- 介孔硅胶 /
- 四乙烯五胺 /
- 聚乙二醇 /
- CO₂吸附
Abstract: A novel tetraethylenepentamine (TEPA) modified mesoporous silica gel (SG) sorbent (TEPA-SG) for CO₂ capture was prepared by the wet impregnation method. The prepared samples were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analyzer (TGA), and N₂ adsorption-desorption technologies. Meanwhile, the effects of TEPA loadings and adsorption temperatures on the adsorption capacity were investigated in a self-assembled fixed bed reactor. Different weight percentages of polyethylene glycol (PEG) were added to TEPA-SG to study the promoting effect of hydroxyl groups on the adsorption capacity and regenerability. The results show that the SG modified by 40% TEPA has a maximum adsorption capacity of 2.21 mmol/g at 70 ℃ and atmospheric pressure. Moreover, the adsorption capacity increases to 2.70 mmol/g by adding a desirable amount of PEG, and after ten cyclic adsorption-desorption tests, the adsorption capacity is maintained at 2.66 mmol/g, demonstrating that as-prepared TEPA and PEG modified sorbent displays an excellent regenerability. In addition, the isosteric heat of adsorption based on the Clasius-Clapeyron equation approaches 30~40 kJ/mol, and decreases gradually with increasing the adsorption capacity, indicating that the surface of TEPA30/PEG10-SG sorbent shows an energetic heterogeneity.
- mesoporous silica gel /
- tetraethylenepentamine /
- polyethylene glycol /
- CO₂ adsorption

HTML全文

参考文献(26)

费维扬, 艾宁, 陈健. 温室气体CO₂的捕集和分离—分离技术面临的挑战与机遇[J]. 化工进展, 2005, 24(1): 1-4.(FEI Wei-yang, AI Ning, CHEN Jian. Capture and separation of greenhouse gases CO₂-The challenge and opportunity for separation technology[J]. Chem Ind Eng Prog, 2005, 24(1): 1-4.)

LI P Z, ZHAO Y L. Nitrogen-rich porous adsorbents for CO₂ capture and storage[J]. Chem Asian J, 2013, 8(8): 1680-1691.

LIU Y M, YE Q, SHEN M, CHEN J, PAN H, SHI Y. Carbon dioxide capture by functionalized solid amine sorbents with simulated flue gas conditions[J]. Environ Sci Technol, 2011, 45(13): 5710-5716.

刘之琳, 滕阳, 张锴, 曹晏, 潘伟平. 不同有机胺修饰MCM-41的CO₂吸附性能和热稳定性[J]. 燃料化学学报, 2013, 41(4): 469-476.(LIU Zhi-lin, TENG Yang, ZHANG Kai, CAO Yan, PAN Wei-ping. CO₂ adsorption properties and thermal stability of different amine-impregnated MCM-41 materials[J]. J Fuel Chem and Technol, 2013, 41(4): 469-476.)

MA X L, WANG X X, SONG C S. "Molecular basket" sorbent for separation of CO₂ and H₂S from various gas streams[J]. J Am Chem Soc, 2009, 131(16): 5777-5783.

李勇, 李磊, 闻霞, 王峰, 赵宁, 肖福魁, 魏伟, 孙予罕. 二次嫁接法制备氨基修饰的硅基二氧化碳吸附剂[J]. 燃料化学学报, 2013, 41(9): 1122-1128.(LI Yong, LI Lei, WEN Xia, WANG Feng, ZHAO Ning, XIAO Fu-kui, WEI Wei, SUN Yu-han. Synthesis of amine modified silica for the capture of carbon dioxide by a twice grafting method[J]. J Fuel Chem Technol, 2013, 41(9): 1122-1128.)

SON W J, CHOI J S, AHN W S. Adsorptive removal of carbon dioxide using polyethyleneimine-loaded mesoporous silica materials[J]. Microporous Mesoporous Mater, 2008, 113(1/3): 31-40.

PLAZA M G, PEVIDA C, ARENILLAS A, RUBIERA F, PIS J J. CO₂ capture by adsorption with nitrogen enriched carbons[J]. Fuel, 2007, 86(14): 2204-2212.

徐康文, 冯丽娟, 王景刚, 李宇慧, 李春虎. 介孔硅胶在柴油氧化-吸附组合脱硫中的应用研究[J]. 燃料化学学报, 2012, 40(8): 1009-1013.(XU Kang-wen, FENG Li-juan, WANG Jing-gang, LI Yu-hui, LI Chun-hu. Application of mesoporous silica gel in desulfurization of diesel oil via oxidation-adsorption process[J]. J Fuel Chem Technol, 2012, 40(8): 1009-1013.)

WANG K, SHANG H Y, LI L, YAN X L, YAN Z F, LIU C G, ZHA Q F. Efficient CO₂ capture on low-cost silica gel modified by polyethylenimine[J]. J Nat Gas Chem, 2012, 21(3): 319-323.

ROUQUEROL J, AVNIR D, FAIRBRIDGE C W, EVERETT D H, HAYNES J H, PERNICONE N, RAMSAY J D F, SING K S W, UNGER K K. Recommendations for the characterization of porous solids (Technical Report)[J]. Pure Appl Chem, 1994, 66(8): 1739-1758.

DIDAS S A, KULKARNI A R, SHOLL D S, JONES C W. Role of amine structure on carbon dioxide adsorption from ultradilute gas streams such as ambient air[J]. ChemSusChem, 2012, 5(10): 2058-2064.

SATYAPAL S, FILBURN T, TRELA J, STRANGE J. Performance and properties of a solid amine sorbent for carbon dioxide removal in space life support applications[J]. Energy Fuels, 2001, 15(2): 250-255.

YUE M B, SUN L B, CAO Y, WANG Z J, WANG Y, YU Q, ZHU J H. Promoting the CO₂ adsorption in the amine-containing SBA-15 by hydroxyl group[J]. Microporous Mesoporous Mater, 2008, 114(1): 74-81.

YAN W, TANG J, BIAN Z J, HU J, LIU H L. Carbon dioxide capture by amine-impregnated mesocellular-foam-containing template[J]. Ind Eng Chem Res, 2012, 51(9): 3653-3662.

史晶金, 刘亚敏, 陈杰, 张瑜, 施耀. 氨基功能化SBA-16对CO₂的动态吸附特性[J]. 物理化学学报, 2010, 26(11): 3023-3029.(SHI Jing-jin, LIU Ya-min, CHEN Jie, ZHANG Yu, SHI Yao. Dynamic performance of CO₂ dsorption with amine-modified SBA-16[J]. Acta Phys-Chim Sin, 2010, 26(11): 3023-3029.)

YAN X L, ZHANG Y, QIAO K, LI X, ZHANG Z Q, YAN Z F, KOMARNENI S. Clover leaf-shaped Al₂O₃ extrudate as a support for high-capacity and cost-effective CO₂ sorbent[J]. J Hazard Mater, 2011, 192(3): 1505-1508.

KHALIL S H, AROUA M H, DAUD W M A W. Study on the improvement of the capacity of amine-impregnated commercial activated carbon beds for CO₂ adsorbing[J]. Chem Eng J, 2012, 183: 15-20.

王春蓉. 改性硅胶吸附分离N₂/CO₂的研究[J]. 化学与粘合, 2009, 31(6): 76-78.(WANG Chun-rong. Study on modified silica gel for adsorptive separation of N₂/CO₂[J]. Chem Adhesion, 2009, 31(6): 76-78.)

ZHU T, YANG S, CHOI D K, ROW K H. Adsorption of carbon dioxide using polythyleneimine modified silica gel[J]. Korean J Chem Eng, 2010, 27(6): 1910-1915.

ZHANG Z H, MA X L, WANG D X, SONG C S, WANG Y G. Development of silica-supported polyethylenimine sorbents for CO₂ capture from flue gas[J]. AIChE J, 2012, 58(8): 2495-2502.

GUERRERO R S, BELMABKHOUT Y, SAYARI A. Modeling CO₂ adsorption on amine-functionalized mesoporous silica: 1. A semi-empirical equilibrium model[J]. Chem Eng J, 2010, 161(1/2): 173-181.

高帅, 郑青榕. 甲烷在活性炭上吸附平衡模型的研究[J]. 燃料化学学报, 2013, 41(3): 380-384.(GAO Shuai, ZHENG Qing-rong. Comparisons of adsorption models for methane adsorption equilibrium on activated carbon[J]. J Fuel Chem Technol, 2013, 41(3): 380-384.)

KERAMATI M, GHOREYSHI A A. Improving CO₂ adsorption onto activated carbon through functionalization by chitosan and triethylenetetramine[J]. Physica E, 2014, 57: 161-168.

AHN H, MOON J H, HYUN S H, LEE C H. Diffusion mechanism of carbon dioxide in zeolite 4A and CaX pellets[J]. Adsorption, 2004, 10(2): 111-128.

KUMAR K V, DE CASTRO M M, MARTINEZ-ESCANDELL M, MOLINA-SABIO M, RODRIGUEZ-REINOSO F. A site energy distribution function from Toth isotherm for adsorption of gases on heterogeneous surfaces[J]. Phys Chem Chem Phys, 2011, 13(13): 5753-5759.

施引文献

资源附件(0)

访问统计