CO_2在三聚氰胺酚醛纤维上的吸附分离
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摘要
以三聚氰胺、间苯三酚和甲醛为原料,通过水热缩聚反应合成了三聚氰胺酚醛纤维(PMF),考察了温度对PMF合成的影响。以扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N_2吸脱附和傅里叶变换红外(FT-IR)光谱等表征了PMF的形貌和结构,并采用体积法测定不同温度下CO_2和N_2在PMF上的单组分吸附平衡等温线。结果表明,在393 K下合成的PMF具有较大的比表面积(64 m2/g)和较高的CO_2吸附量(1.83 mmol/g,298 K、118 k Pa)。穿透柱实验表明,在298 K、200-600 k Pa,CO_2-N_2混合气在PMF上均可实现有效分离。将PMF在873 K下,N_2、H2及水蒸气等多种气氛中进行后处理,其比表面积和微孔孔容均显著增加,其中,在15%H_2O气氛中处理后,样品CO_2吸附量提高至2.83 mmol/g(298 K、118 k Pa)。
Phloroglucinol-melamine-formaldehyde polymeric nanofibers( PMF) were hydrothermally synthesized by a polycondensation method using melamine, phloroglucinol and formaldehyde as starting materials. The effect of temperature on the PMF synthesis was investigated. The morphology and structure of the as-synthesized PMF were characterized by the scanning electron microscope( SEM),transmission electron microscope( TEM),N_2adsorption-desorption and Fourier-transform infrared spectrometer( FT-IR) etc. Pure gas adsorption equilibrium isotherms of CO_2 and N_2were determined by the volumetric method. The PMF sample synthesized at 393 K presented a higher specific surface area( 64 m2/g) and a higher adsorption capacity of CO_2( 1.83 mmol/g @ 118 kPa,298 K). Breakthrough column experiments indicated that efficient separation of CO_2-N_2 mixtures could be achieved on the PMF at 298 K and various pressures ranging from 200 to 600 kPa. After the PMF was thermally treated at 873 K in various atmospheres such as N_2,H2,water vapor,etc.,it was found that the specific surface area and micropore volume were greatly increased. Among the posttreated PMF samples,the one treated in 15% H2 O stream showed an improved CO_2 adsorption amount up to 2.83 mmol/g at 298 K and118 kPa.
Phloroglucinol-melamine-formaldehyde polymeric nanofibers( PMF) were hydrothermally synthesized by a polycondensation method using melamine, phloroglucinol and formaldehyde as starting materials. The effect of temperature on the PMF synthesis was investigated. The morphology and structure of the as-synthesized PMF were characterized by the scanning electron microscope( SEM),transmission electron microscope( TEM),N_2adsorption-desorption and Fourier-transform infrared spectrometer( FT-IR) etc. Pure gas adsorption equilibrium isotherms of CO_2 and N_2were determined by the volumetric method. The PMF sample synthesized at 393 K presented a higher specific surface area( 64 m2/g) and a higher adsorption capacity of CO_2( 1.83 mmol/g @ 118 kPa,298 K). Breakthrough column experiments indicated that efficient separation of CO_2-N_2 mixtures could be achieved on the PMF at 298 K and various pressures ranging from 200 to 600 kPa. After the PMF was thermally treated at 873 K in various atmospheres such as N_2,H2,water vapor,etc.,it was found that the specific surface area and micropore volume were greatly increased. Among the posttreated PMF samples,the one treated in 15% H2 O stream showed an improved CO_2 adsorption amount up to 2.83 mmol/g at 298 K and118 kPa.
引文
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[11]郝仕油,肖强,钟依均,朱伟东,杨辉.氨基功能化SBA-15的直接合成及其对CO2的吸附性能研究[J].无机化学学报,2010,26(6):982-988.(HAO Shi-you,XIAO Qiang,ZHONG Yi-jun,ZHU Wei-dong,YANG Hui. One-pot synthesis of amino-functionalized SBA-15 and their CO2adsorption properties[J]. Chin J Inorg Chem,2010,26(6):982-988.)
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[18] PEI C Y,BEN T,GUO H,XU J,DENG F,XIANG Z H,CAO D P,QIU S L. Targeted synthesis of electroactive porous organic framew orks containing triphenyl phosphine moieties[J]. Phil Trans R Soc A,2013,371(2000):1-15.
[19] LIU L,LI P Z,ZHU L L,ZOU R Q,ZHAO Y L. Microporous polymelamine network for highly selective CO2adsorption[J]. Polymer,2013,54(2):596-600.
[20] XU C,HEDIN N. Synthesis of microporous organic polymers with high CO2-over-N2selectivity and CO2adsorption[J]. J M ater Chem A,2013,1(10):3406-3414.
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[24] ZHOU H H,XU S,SU H P,WANG M,QIAO W M,LING L C,LONG D H. Facile preparation and ultra-microporous structure of melamine-resorcinol-formaldehyde polymeric microspheres[J]. Chem Commun,2013,49(36):3763-3765.
[25] WANG M,WANG J,QIAO W M,LING L C,LONG D H. Scalable preparation of nitrogen-enriched carbon microspheres for efficient CO2capture[J]. RSC Adv,2014,4(106):61456-61464.
[26] XIAO Q,WEN J J,GUO Y N,HU J X,WANG J G,ZHANG F M,TU G M,ZHONG Y J,ZHU W D. Synthesis,carbonization,and CO2adsorption properties of phloroglucinol-melamine-formaldehyde polymeric nanofibers[J]. Ind Eng Chem Res,2016,55(49):12667-12674.
[27] PERALTA D,CHAPLAIS G,SIMON-MASSERON A,BARTHELET K,CHIZALLET C,QUOINEAUD A A,PIRNGRUBER G D.Comparison of the behavior of metal-organic framew orks and zeolites for hydrocarbon separations[J]. J Am Chem Soc,2012,134(19):8115-8126.
[28] STRELKO V V,KUTS V S,THROWER P A. On the mechanism of possible influence of heteroatoms of nitrogen,boron and phosphorus in a carbon matrix on the catalytic activity of carbons in electron transfer reactions[J]. Carbon,2000,38(10):1499-1503.
[29] LIU L,DENG Q F,HOU X X,YUAN Z Y. User-friendly synthesis of nitrogen-containing polymer and microporous carbon spheres for efficient CO2capture[J]. J M ater Chem,2012,22(31):15540-15548.
[2]黄雪芹,肖强,钟依均,朱伟东.湿磨法制备纳米Li4SiO4材料用于高温捕集CO2[J].燃料化学学报,2016,44(9):1119-1124.(HUANG Xue-qin,XIAO Qiang,ZHONG Yi-jun,ZHU Wei-dong. A wet ball-milling method to nanocrystalline Li4SiO4materials for CO2capture at high temperatures[J]. J Fuel Chem Technol,2016,44(9):1119-1124.)
[3]高峰,李存梅,王媛,孙国华,李开喜.树脂基球状活性炭的制备及对二氧化碳吸附性能的研究[J].燃料化学学报,2014,42(1):116-120.(GAO Feng,LI Cun-mei,WANG Yuan,SUN Guo-hua,LI Kai-xi. Preparation of resin-base spherical activated carbon and study on adsorption properties tow ards CO2[J]. J Fuel Chem Technol,2014,42(1):116-120.)
[4] MA T Y,LIU L,YUAN Z Y. Direct synthesis of ordered mesoporous carbons[J]. Chem Soc Rev,2013,42(9):3977-4003.
[5] BAE Y S,SNURR R Q. Development and evaluation of porous materials for carbon dioxide separation and capture[J]. Angew Chem Int Ed,2011,50(49):11586-11596.
[6] HARLICK P J E,TEZEL F H. An experimental adsorbent screening study for CO2removal from N2[J]. Microporous Mesoporous Mater,2004,76(1/3):71-79.
[7] HE Y F,SEATON N A. Heats of adsorption and adsorption heterogeneity for methane,ethane,and carbon dioxide in MCM-41[J]. Langmuir,2006,22(3):1150-1155.
[8]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[J].燃料化学学报,2015,43(1):108-115.(CHEN Lin-lin,WANG Xia,GUO Qing-jie. Study on CO2adsorption properties of tetraethylenepentamine modified mesoporous silica gel[J].J Fuel Chem Technol,2015,43(1):108-115.)
[9] WANG D,MA X,SENTORUNSHALABY C,SONG C S. Development of carbon-based“molecular basket”sorbent for CO2capture[J]. Ind Eng Chem Res,2012,51(7):3048-3057.
[10]赵会玲,胡军,汪建军,周丽绘,刘洪来.介孔材料氨基表面修饰及其对CO2的吸附性能[J].物理化学学报,2007,23(6):801-806.(ZHAO Hui-ling,HU Jun,WANG Jian-jun,ZHOU Li-hui,LIU Hong-lai. CO2capture by the amine-modified mesoporous materials[J].Acta Phys-Chim Sin,2007,23(6):801-806.)
[11]郝仕油,肖强,钟依均,朱伟东,杨辉.氨基功能化SBA-15的直接合成及其对CO2的吸附性能研究[J].无机化学学报,2010,26(6):982-988.(HAO Shi-you,XIAO Qiang,ZHONG Yi-jun,ZHU Wei-dong,YANG Hui. One-pot synthesis of amino-functionalized SBA-15 and their CO2adsorption properties[J]. Chin J Inorg Chem,2010,26(6):982-988.)
[12] HERM Z R,SWISHER J A,SMIT B,KRISHNA R,LONG J R. Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture[J]. J Am Chem Soc,2011,133(15):5664-5667.
[13] LI J R,KUPPLER R J,ZHOU H C. Selective gas adsorption and separation in metal-organic frameworks[J]. Chem Soc Rev,2009,38(5):1477-1504.
[14] MILLWARD A R,YAGHI O M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature[J]. J Am Chem Soc,2005,127(51):17998-17999.
[15] DING S Y,WANG W. Covalent organic frameworks(COFs):from design to applications[J]. Chem Soc Rev,2013,42(2):548-568.
[16] XIANG Z H,CAO D P. Porous covalent-organic materials:Synthesis,clean energy application and design[J]. J Mater Chem A,2013,1(8):2691-2718.
[17] BEN T,PEI C Y,ZHANG D L,XU J,DENG F,JING X F,QIU S L. Gas storage in porous aromatic frameworks(PAFs)[J]. Energy Environ Sci,2011,4(10):3991-3999.
[18] PEI C Y,BEN T,GUO H,XU J,DENG F,XIANG Z H,CAO D P,QIU S L. Targeted synthesis of electroactive porous organic framew orks containing triphenyl phosphine moieties[J]. Phil Trans R Soc A,2013,371(2000):1-15.
[19] LIU L,LI P Z,ZHU L L,ZOU R Q,ZHAO Y L. Microporous polymelamine network for highly selective CO2adsorption[J]. Polymer,2013,54(2):596-600.
[20] XU C,HEDIN N. Synthesis of microporous organic polymers with high CO2-over-N2selectivity and CO2adsorption[J]. J M ater Chem A,2013,1(10):3406-3414.
[21] SCHWAB M G,FASSBENDER B,SPIESS H W,THOMAS A,FENG X,MULLEN K. Catalyst-free preparation of melamine-based microporous polymer netw orks through schiff base chemistry[J]. J Am Chem Soc,2009,131(21):7216-7217.
[22] HU J X,SHANG H,WANG J G,LUO L,XIAO Q,ZHONG Y J,ZHU W D. Highly enhanced selectivity and easy regeneration for the separation of CO2over N2on melamine-based microporous organic polymers[J]. Ind Eng Chem Res,2014,53(29):11828-11837.
[23]胡敬秀,张静,邹建锋,肖强,钟依均,朱伟东.源自密胺基多孔聚合物的富氮微孔炭及选择性吸附CO2[J].物理化学学报,2014,30(6):1169-1174.(HU Jing-xiu,ZHANG Jing,ZOU Jian-feng,XIAO Qiang,ZHONG Yi-jun,ZHU Wei-dong. Nitrogen-rich microporous carbon derived from melamine-based porous polymer for selective CO2adsorption[J]. Acta Phys-Chim Sin,2014,30(6):1169-1174.)
[24] ZHOU H H,XU S,SU H P,WANG M,QIAO W M,LING L C,LONG D H. Facile preparation and ultra-microporous structure of melamine-resorcinol-formaldehyde polymeric microspheres[J]. Chem Commun,2013,49(36):3763-3765.
[25] WANG M,WANG J,QIAO W M,LING L C,LONG D H. Scalable preparation of nitrogen-enriched carbon microspheres for efficient CO2capture[J]. RSC Adv,2014,4(106):61456-61464.
[26] XIAO Q,WEN J J,GUO Y N,HU J X,WANG J G,ZHANG F M,TU G M,ZHONG Y J,ZHU W D. Synthesis,carbonization,and CO2adsorption properties of phloroglucinol-melamine-formaldehyde polymeric nanofibers[J]. Ind Eng Chem Res,2016,55(49):12667-12674.
[27] PERALTA D,CHAPLAIS G,SIMON-MASSERON A,BARTHELET K,CHIZALLET C,QUOINEAUD A A,PIRNGRUBER G D.Comparison of the behavior of metal-organic framew orks and zeolites for hydrocarbon separations[J]. J Am Chem Soc,2012,134(19):8115-8126.
[28] STRELKO V V,KUTS V S,THROWER P A. On the mechanism of possible influence of heteroatoms of nitrogen,boron and phosphorus in a carbon matrix on the catalytic activity of carbons in electron transfer reactions[J]. Carbon,2000,38(10):1499-1503.
[29] LIU L,DENG Q F,HOU X X,YUAN Z Y. User-friendly synthesis of nitrogen-containing polymer and microporous carbon spheres for efficient CO2capture[J]. J M ater Chem,2012,22(31):15540-15548.