硅胶嵌入多孔纸基对苯蒸气吸附性能
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摘要
苯蒸气作为一种典型的有害VOC污染物,研究对其的高效净化处理具有重要意义。纸基材料是一种密度小、孔隙率高、机械强度高的多孔材料,分析以木浆纤维纸、陶瓷纤维纸作为多孔基材,通过多次硅溶胶浸泡的方法制得硅胶嵌入多孔纸基吸附材料样片。通过扫描电镜SEM研究两种纸基材料表面的形貌及结构,采用重量法蒸气吸附仪对不同上胶次数的两种基材样片进行吸附性能测试。测试结果表明:木浆纤维纸和陶瓷纤维纸6次上胶率高达3.38 g/g和8.66 g/g; 0.1分压苯蒸气下30 min样片吸附量即可达到最大吸附量的80%;两种硅胶嵌入多孔纸基样片吸附容量在0.8分压苯蒸气下均超过100 mg/g;在4次上胶时样片表现出最佳的苯蒸气吸附性能。此外,通过对实验结果进行分段拟合得到吸附特征曲线。
As a typical harmful VOC pollutant, benzene vapor is of great significance for its efficient purification treatment. Benzene vapor is a typical contaminant of VOCs which is the culprit of various diseases, so it is very meaningful to research how to purify the benzene vapor efficiently. Paper material is a kind of porous material with low density, high porosity and high mechanical strength. In this paper, two different kinds of paper, WFP(wood fiber paper) and CFP(ceramic fiber paper), are used as the porous substrates. Paper based silica gel adsorbent was made by gluing repeatedly, immersing the paper porous substrate in JN-30 silica sol and then drying them in oven several times. The surface morphology and structure of two kinds of paper materials were observed by the scanning electron microscopy(SEM). The adsorption properties of the samples which are made from WFP and CPF are tested by using the multi station absorption apparatus. The results show that the two porous substrates are of strong adhesive ability of silica, and the silica adhesive rate of the WFP and CFP reaches 3.38 g/g and 8.66 g/g after 6 times gluing. With the increase of gluing times, the silica adhesive rate of both materials is increasing, but after the gluing times reaches 4 times, growth of silica adhesive rate becomes significantly lower. The adsorption performance test results show the strong adsorption ability of the paper-based silica adsorbents on benzene vapor, both a good adsorption rate and adsorption capacity: it takes less than 30 min to achieve 80% of maximum adsorption capacity under 0.1 benzene vapor partial pressure, and the maximum adsorption capacity reaches 100 mg/g under 0.8 benzene vapor partial pressure. With the increase of the gluing times, the paper-based silica gel adsorbents' adsorption capacity of benzene vapor first rises and then drop. In addition, the dynamic adsorption model of the paper-based silica gel adsorbents was fitted by the piecewise dynamic adsorption model. It was found that the dynamic adsorption process under the low pressure was divided into 2 stages: the early stage and later stage. In the early stage of adsorption, the adsorption capacity of materials is strong and adsorption quantity increases rapidly; in the later stage of adsorption, adsorption quantity increases much slower and gradually reaches saturation. By comparing isothermal adsorption curves of two different paper-based silica gel adsorbents, it can be found that, with the increase of gluing times, adsorption capacity of the WFP based silica gel adsorbents increases first and then decreases and it reaches the maximum at 4 times gluing. In contrast, the isothermal adsorption ability of CFP based silica gel adsorbents is basically unchanged after 4 times of gluing. Based on the fitting study of the adsorption isotherm with the Langmuir equation and the D-R equation, it was found that the adsorption isotherm was also divided into 2 parts: the low-pressure area and the high-pressure area. In addition, the adsorption characteristic curve is obtained by segmentation fitting the experimental results.
As a typical harmful VOC pollutant, benzene vapor is of great significance for its efficient purification treatment. Benzene vapor is a typical contaminant of VOCs which is the culprit of various diseases, so it is very meaningful to research how to purify the benzene vapor efficiently. Paper material is a kind of porous material with low density, high porosity and high mechanical strength. In this paper, two different kinds of paper, WFP(wood fiber paper) and CFP(ceramic fiber paper), are used as the porous substrates. Paper based silica gel adsorbent was made by gluing repeatedly, immersing the paper porous substrate in JN-30 silica sol and then drying them in oven several times. The surface morphology and structure of two kinds of paper materials were observed by the scanning electron microscopy(SEM). The adsorption properties of the samples which are made from WFP and CPF are tested by using the multi station absorption apparatus. The results show that the two porous substrates are of strong adhesive ability of silica, and the silica adhesive rate of the WFP and CFP reaches 3.38 g/g and 8.66 g/g after 6 times gluing. With the increase of gluing times, the silica adhesive rate of both materials is increasing, but after the gluing times reaches 4 times, growth of silica adhesive rate becomes significantly lower. The adsorption performance test results show the strong adsorption ability of the paper-based silica adsorbents on benzene vapor, both a good adsorption rate and adsorption capacity: it takes less than 30 min to achieve 80% of maximum adsorption capacity under 0.1 benzene vapor partial pressure, and the maximum adsorption capacity reaches 100 mg/g under 0.8 benzene vapor partial pressure. With the increase of the gluing times, the paper-based silica gel adsorbents' adsorption capacity of benzene vapor first rises and then drop. In addition, the dynamic adsorption model of the paper-based silica gel adsorbents was fitted by the piecewise dynamic adsorption model. It was found that the dynamic adsorption process under the low pressure was divided into 2 stages: the early stage and later stage. In the early stage of adsorption, the adsorption capacity of materials is strong and adsorption quantity increases rapidly; in the later stage of adsorption, adsorption quantity increases much slower and gradually reaches saturation. By comparing isothermal adsorption curves of two different paper-based silica gel adsorbents, it can be found that, with the increase of gluing times, adsorption capacity of the WFP based silica gel adsorbents increases first and then decreases and it reaches the maximum at 4 times gluing. In contrast, the isothermal adsorption ability of CFP based silica gel adsorbents is basically unchanged after 4 times of gluing. Based on the fitting study of the adsorption isotherm with the Langmuir equation and the D-R equation, it was found that the adsorption isotherm was also divided into 2 parts: the low-pressure area and the high-pressure area. In addition, the adsorption characteristic curve is obtained by segmentation fitting the experimental results.
引文
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[21]Ncube T,Reddy K S K,Shoaibi A S A,et al.Benzene,toluene,mxylene adsorption on silica based adsorbents[J].Energy&Fuels,2017,31(2):1882-1888.
[22]赵振国.吸附作用应用原理[M].北京:化学工业出版社,2005:364-384.Zhao Z G.Principle of Adsorption Application[M].Beijing:Chemical Industry Press,2005:364-384.
[23]Hen W,Zhang J S S,Zhang Z B.Performance of air cleaners for removing multi-volatile organic compounds in indoor air[J].ASHRAE Transactions,2005,111(1):1101-1114.
[24]罗益锋.主要特种纤维及其复合材料的研发现状及发展前景[J].高科技纤维与应用,2014,39(4):8-17.Luo Y F.Present conditions and developing prospect of main specialty fibers and their composite materials[J].Hi-Tech Fiber&Application,2014,39(4):8-17.
[25]杨启荣.复合型除湿材料的制备及性能研究[D].广州:华南理工大学,2015:21-29.Yang Q R.Preparation and performance analysis of composite desiccant material[D].Guangzhou:South China University of Technology,2015:21-29.
[26]方玉堂,丁静,范娟,等.以陶瓷纤维为基材的硅胶吸附材料的制备与性能[J].离子交换与吸附,2004,20(2):97-103.Fang Y T,Ding J,Fan J,et al.Preparation and properties of silica gel functional sheet[J].Ion Exchange and Adsorption,2004,20(2):97-103.
[27]Zhang Y,Mo J,Li Y,et al.Can commonly-used fan-driven air cleaning technologies improve indoor air quality?A literature review[J].Atmospheric Environment,2011,45(26):4329-4343.
[28]Chung T W,Ghosh T K,Hines A L,et al.Dehumidification of moist air with simultaneous removal of selected indoor pollutants by triethylene glycol solutions in a packed-bed absorber[J].Separation Science and Technology,1995,30(7/8/9):1807-1832.
[29]张舸.硅胶转轮的空气净化能力研究[D].天津:天津大学,2007.Zhang G.Study on the air cleaning effect of silica gel rotors[D].Tianjin:Tianjin University,2007.
[30]Dubinin M M.The potential theory of adsorption of gases and vapors for adsorbents with energetically nonuniform surfaces[J].Chemical Reviews,1960,60(2):235-241.
[31]Dubinin M M,Zaverina E D,Radushkevich L V.Sorption and structure of active carbons(Ⅰ):Adsorption of organic vapors[J].Zhurnal Fizicheskoi Khimii,1947,21(3):151-162.
[32]李荣年,郑鹏遵,王虹.国内外除湿转轮用吸湿纸的发展[J].中国造纸,2013,32(4):63-65.Li R N,Zheng P Z,Wang H.Development of absorbent paper used for rotary dehumidifier at home and abroad[J].China Pulp&Paper,2013,32(4):63-65.
[33]近藤精一,石川达雄,安部郁夫.吸附科学[M].北京:化学工业出版社,2006:102-103.Kondo S,Ishikawa T,Abe I.Adsorption Science[M].Beijing:Chemical Industry Press,2006:102-103.
[34]Giles C H,Smith D,Huitson A.A general treatment and classification of the solute adsorption isotherm(Ⅰ):Theoretical[J].Journal of Colloid&Interface Science,1974,47(3):766-778.
[35]Langmuir I.The adsorption of gases on plane surface of glass,mica and platinum[J].Journal of Physical Chemistry C,1918,40(12):1361-1403.
[2]Nevers N D.Air Pollution Control Engineering[M].New York:McGraw-Hill,2000:336
[3]吴超.气升式生物反应器处理多组分VOCs废气的关键技术研究[D].杭州:浙江大学,2017.Wu C.Key techniques for treating a complex VOC mixture in airlift bioreactors[D].Hangzhou:Zhejiang University,2017.
[4]莫金汉.光催化降解室内有机化学污染物的若干重要机理问题研究[D].北京:清华大学,2009.Mo J H.Research on some key fundamental problems in the photocatalytic oxidation of indoor volatile organic compounds[D].Beijing:Tsinghua University,2009.
[5]刘鹏,周湘梅.VOC的回收与处理技术简介[J].石油化工环境保护,2001,3(3):39-42.Liu P,Zhou X M.Recycle of VOC and its treatment technology[J].Environment Protection in Petrochemical Industry,2001,3(3):39-42.
[6]Armand B L,Uddholm H B,Vikstroem P T.Absorption method to clean solvent-contaminated process air[J].Industrial&Engineering Chemistry Research,2002,29(3):436-439.
[7]Feng X,Sourirajan S,Tezel H,et al.Separation of organic vapor from air by aromatic polyimide membranes[J].Journal of Applied Polymer Science,2010,43(6):1071-1079.
[8]郑新,李红旗,张伟,等.冷凝法甲苯回收系统性能研究与优化[J].低温与超导,2015,43(2):67-73.Zheng X,Li H Q,Zhang W,et al.Performance research and optimization on toluene condensation recovery system[J].Cryogenics and Superconductivity,2015,43(2):67-73.
[9]Chiang C Y,Liu Y,Chen Y S,et al.Absorption of hydrophobic volatile organic compounds by a rotating packed bed[J].Industrial&Engineering Chemistry Research,2012,51(27):9441-9445.
[10]Foster K L,Fuerman R G,Economy J,et al.Adsorption characteristics of trace volatile organic compounds in gas streams onto activated carbon fibers[J].Chemistry of Materials,1992,4(5):1068-1073.
[11]Foster K L,Fuerman R G,Economy J,et al.Adsorption characteristics of trace volatile organic compounds in gas streams onto activated carbon fibers[J].Chemistry of Materials,1992,4(5):1068-1073.
[12]Cal M P,Larson S M,Rood M J.Experimental and modeled results describing the adsorption of acetone and benzene onto activated carbon fibers[J].Environmental Progress&Sustainable Energy,2010,13(1):26-30.
[13]Cal M P,Rood M J,Larson S M.Removal of VOCs from humidified gas streams using activated carbon cloth[J].Gas Separation&Purification,1996,10(10):117-121.
[14]Mangun C L,Daley M A,Braatz R D,et al.Effect of pore size on adsorption of hydrocarbons in phenolic-based activated carbon fibers[J].Carbon,1998,36(1/2):123-129.
[15]Lillo-Ródenas M A,Cazorla-Amorós D,Linares-Solano A.Behaviour of activated carbons with different pore size distributions and surface oxygen groups for benzene and toluene adsorption at low concentrations[J].Carbon,2005,43(8):1758-1767.
[16]Bilic A,Jeffrey R,Hush N,et al.Adsorption of benzene on copper,silver,and gold surfaces[J].Journal of Chemical Theory and Computation,2006,2(4):1093-1105.
[17]Ene A B,Archipov T,Roduner E.Competitive adsorption and interaction of benzene and oxygen on Cu/HZSM5 zeolites[J].Journal of Physical Chemistry C,2011,115(9):3688-3694.
[18]Steinberg S M,Swallow C E,Ma W K.Vapor phase sorption of benzene by cationic surfactant modified soil[J].Chemosphere,1999,38(38):2143-2152.
[19]苏玉红,沈学优,朱利中.苯蒸气在有机膨润土上的吸附动力学[J].环境化学,2001,20(5):455-459.Su Y H,Shen X Y,Zhu L Z.Kinetics of benzene vapor sorption onto organ bentonites[J].Environmental Chemistry,2001,20(5):455-459.
[20]Wang G,Dou B,Zhang Z,et al.Adsorption of benzene,cyclohexane and hexane on ordered mesoporous carbon[J].Acta Scientiae Circumstantiae,2015,30(4):65-73.
[21]Ncube T,Reddy K S K,Shoaibi A S A,et al.Benzene,toluene,mxylene adsorption on silica based adsorbents[J].Energy&Fuels,2017,31(2):1882-1888.
[22]赵振国.吸附作用应用原理[M].北京:化学工业出版社,2005:364-384.Zhao Z G.Principle of Adsorption Application[M].Beijing:Chemical Industry Press,2005:364-384.
[23]Hen W,Zhang J S S,Zhang Z B.Performance of air cleaners for removing multi-volatile organic compounds in indoor air[J].ASHRAE Transactions,2005,111(1):1101-1114.
[24]罗益锋.主要特种纤维及其复合材料的研发现状及发展前景[J].高科技纤维与应用,2014,39(4):8-17.Luo Y F.Present conditions and developing prospect of main specialty fibers and their composite materials[J].Hi-Tech Fiber&Application,2014,39(4):8-17.
[25]杨启荣.复合型除湿材料的制备及性能研究[D].广州:华南理工大学,2015:21-29.Yang Q R.Preparation and performance analysis of composite desiccant material[D].Guangzhou:South China University of Technology,2015:21-29.
[26]方玉堂,丁静,范娟,等.以陶瓷纤维为基材的硅胶吸附材料的制备与性能[J].离子交换与吸附,2004,20(2):97-103.Fang Y T,Ding J,Fan J,et al.Preparation and properties of silica gel functional sheet[J].Ion Exchange and Adsorption,2004,20(2):97-103.
[27]Zhang Y,Mo J,Li Y,et al.Can commonly-used fan-driven air cleaning technologies improve indoor air quality?A literature review[J].Atmospheric Environment,2011,45(26):4329-4343.
[28]Chung T W,Ghosh T K,Hines A L,et al.Dehumidification of moist air with simultaneous removal of selected indoor pollutants by triethylene glycol solutions in a packed-bed absorber[J].Separation Science and Technology,1995,30(7/8/9):1807-1832.
[29]张舸.硅胶转轮的空气净化能力研究[D].天津:天津大学,2007.Zhang G.Study on the air cleaning effect of silica gel rotors[D].Tianjin:Tianjin University,2007.
[30]Dubinin M M.The potential theory of adsorption of gases and vapors for adsorbents with energetically nonuniform surfaces[J].Chemical Reviews,1960,60(2):235-241.
[31]Dubinin M M,Zaverina E D,Radushkevich L V.Sorption and structure of active carbons(Ⅰ):Adsorption of organic vapors[J].Zhurnal Fizicheskoi Khimii,1947,21(3):151-162.
[32]李荣年,郑鹏遵,王虹.国内外除湿转轮用吸湿纸的发展[J].中国造纸,2013,32(4):63-65.Li R N,Zheng P Z,Wang H.Development of absorbent paper used for rotary dehumidifier at home and abroad[J].China Pulp&Paper,2013,32(4):63-65.
[33]近藤精一,石川达雄,安部郁夫.吸附科学[M].北京:化学工业出版社,2006:102-103.Kondo S,Ishikawa T,Abe I.Adsorption Science[M].Beijing:Chemical Industry Press,2006:102-103.
[34]Giles C H,Smith D,Huitson A.A general treatment and classification of the solute adsorption isotherm(Ⅰ):Theoretical[J].Journal of Colloid&Interface Science,1974,47(3):766-778.
[35]Langmuir I.The adsorption of gases on plane surface of glass,mica and platinum[J].Journal of Physical Chemistry C,1918,40(12):1361-1403.