室内挥发性有机物的净化技术研究进展

doi:10.16085/j.issn.1000-6613.2017-0218

摘要/Abstract

摘要： 因其显著威胁人体健康，挥发性有机物已成为影响室内空气质量的关键因素，亟需有效处理。本文回顾了目前净化室内挥发性有机物的主要技术，包括绿色植物法、吸附法、低温等离子体技术、金属催化氧化法、光催化氧化法等的研究成果，对各种净化技术的原理、影响因素进行了总结，并对其优缺点及未来需要解决的问题进行了分析。指出绿色植物法仅适于处理低浓度污染，一般作为辅助手段；吸附法的核心在于吸附剂，需考虑吸附剂的更换和再生问题；低温等离子体技术去除率较高，但成本也较高；金属催化氧化法需开发廉价且高效的金属氧化物催化剂；光催化氧化法的研究多集中于TiO₂的改性，以期提高其光转化效率。本文同时简述了目前室内空气净化器市场的发展及各技术在市场应用中的占比情况，指出了各项净化技术在未来的热点研究领域。

关键词: 室内挥发性有机物, 净化技术, 机理, 催化剂

Abstract: Volatile organic compounds(VOCs),which seriously threaten human health,have been the key factor influencing indoor air quality,and need to be treated effectively. In this paper,the main purification technologies of indoor VOCs were reviewed,including green plants,adsorption,non-thermal plasma(NTP),metal catalytic oxidation,and photocatalytic oxidation. The principles and influence factors of the purification technologies were summarized,and the merits and faults of each technology and problems need to be resolved in the future were analyzed. Green plants are just suitable for low concentration pollutants,and are usually used as supplementary means. The core of adsorption is the adsorbent,and the replacement of regeneration of adsorbent should be considered. For non-thermal plasma,the removal efficiency of VOCs by NTP technology is high,but the cost is high. As for metal catalytic oxidation method,the metal oxide catalysts with low price and high efficiency are needed to be developed. For photocatalytic oxidation technology,the current study is focused on the modification of TiO₂ and improvement of light conversion efficiency. This paper also briefly presents the current situation of the air purifier market and the proportion of various technologies in the market. Then the technical research hot spots in the future were proposed.

Key words: indoor volatile organic compounds(VOCs), purification technologies, mechanism, catalyst

中图分类号:

X511

申亮杰, 程荣, 陈怡晖, 郑祥, 刘鹏, 石磊. 室内挥发性有机物的净化技术研究进展[J]. 化工进展, 2017, 36(10): 3887-3896.

SHEN Liangjie, CHENG Rong, CHEN Yihui, ZHENG Xiang, LIU Peng, SHI Lei. Research progress on the purification technologies of indoor volatile organic compounds[J]. Chemical Industry and Engineering Progress, 2017, 36(10): 3887-3896.

参考文献

[1] OUSMANE M,LIOTTA L F,CARLO G D,et al.Supported Au catalysts for low-temperature abatement of propene and toluene,as model VOCs:support effect[J].Applied Catalysis B:Environmental,2011,101(3/4):629-637.
[2] AYDOGAN A,MONTOYA L D.Formaldehyde removal by common indoor plant species and various growing media[J].Atmospheric Environment,2011,45(16):2675-2682.
[3] LIU Y,MU Y.Which ornamental plant species effectively remove benzene from indoor air[J].Atmospheric Environment,2007(41):650-654.
[4] 程胜高,但德盅.环境与健康[M].北京:中国环境科学出版社,2006:266.CHENG Shenggao,DAN Dezhong.Environment and health[M].Beijing:China environmental Science Press,2006:266.
[5] 江浩芝,赵婉君.室内甲醛的危害及其污染现状[J].广东化工,2016,43(11):189-201.JIANG Haozhi,ZHAO Wanjun.The harm of indoor formaldehyde and its pollution[J].Guangdong Chemical Industry,2016,43(11):189-201.
[6] 张淑娟,苏志锋,林泽健,等.广东省室内空气污染现状及特征分析[J].中山大学学报(自然科学版),2011,50(2):139-142.ZHANG Shujuan,SU Zhifeng,LIN Zejian,et al.Research of actuality and characters of indoor air pollution in Guangdong Province[J].Acta.Sci.Nat.Univ.Sunyatseni,2011,50(2):139-142.
[7] 樊巍巍,孙竹.西安市室内醛酮类化合物风险研究[J].科技创新与应用,2013(20):33-34.FAN Weiwei,SUN Z.Study on the risk of aldehyde and ketone compounds in Xi'an[J].Technology Innovation and Application,2013(20):33-34.
[8] WOLVERTON B C,JOHNSON A,BOUNDS K.Interior landscape plants for indoor air pollution abatement[C]//NASA,Stennis Space Center,1989.
[9] WOLVERTON B C,WOLVERTON J D.Plants and soil microorganisms:removal of formaldehyde,xylene,and ammonia from the indoor environment[J].Journal of the Mississippi Academy of Sciences,1993,38(2):11-15.
[10] 王兵,王丹,任宏洋,等.不同植物和吸附剂对室内甲醛的去除效果[J].环境工程学报,2015(3):1343-1348.WANG B,WANG D,REN Hongyang,et al.Removal effects of plants and adsorbents for indoor formaldehyde[J].Chinese Journal of Environmental Engineering,2015(3):1343-1348.
[11] XU Zhongjun,WANG L,HOU Haiping.Formaldehyde removal by potted plant-soil systems[J].Journal of Hazardous Materials,2011,192:314-318.
[12] XU Z,WANG L,HOU H.Formaldehyde removal by potted plant-soil systems[J].Journal of Hazardous Materials,2011,192:314-318.
[13] TRESSUBASUNTORN C,THIRAVETYAN P.Removal of benzene from indoor air by dracaena sanderiana effect of wax and stomata[J].Atmospheric Environment,2012,57:317-321.
[14] 黄海凤,褚翔,卢晗锋,等.两种介孔分子筛动态吸附VOCs的研究[J].中国环境科学,2010(4):442-447.HUANG Haifeng,CHU X,LU Hanfeng,et al.Dynamic adsorption of volatile organic compounds on two kinds of mesoporous molecular sieve[J].China Environmental Science,2010(4):442-447.
[15] 杨全,张俊香,杨俊.Mn改性活性炭吸附VOCs性能[J].环境工程学报,2015(6):2963-2966.YANG Q,ZHANG Junxiang,YANG J.Adsorption of VOCs on activated carbon modified by Mn[J].Chinese Journal of Environmental Engineering,2015(6):2963-2966.
[16] 张俊香,黄学敏,曹利,等.负载Cu改性活性炭吸附VOCs性能的研究[J].环境工程,2015,33(1):95-99.ZHANG Junxiang,HUANG Xuemei,CAI L,et al.Adsorption of VOCs on modified activated carbon by supported Cu[J].Environmental Engineering,2015,33(1):95-99.
[17] LI S,TIAN S,FENG Y,et al.A comparative investigation on absorption performances of three expanded graphite-based complex materials for toluene[J].Journal of Hazardous Materials,2010,183(1/2/3):506-511.
[18] ZAITAN H,MANERO M H,VALD?S H.Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination[J].Journal of Environmental Sciences,2016,41:59-68.
[19] LIN F,ZHU G,SHEN Y,et al.Study on the modified montmorillonite for adsorbing formaldehyde[J].Applied Surface Science,2015,356:150-156.
[20] 吴利瑞,张蓝心,于飞,等.氨基化碳纳米管/石墨烯气凝胶对甲醛吸附研究[J].中国环境科学,2015(11):3251-3256.WU Lirui,ZHANG Lanxin,YU F,et al.Facile composite of amino carbon nanotubes/graphene:preparation and adsorption for gaseous formaldehyde[J].China Environmental Science,2015(11):3251-3256.
[21] WANG H,ZHU T,FAN X,et al.Adsorption and desorption of small molecule volatile organic compounds over carbide-derived carbon[J].Carbon,2014,67:712-720.
[22] LE Y,GUO D,CHENG B,et al.Bio-template-assisted synthesis of hierarchically hollow SiO₂ microtubes and their enhanced formaldehyde adsorption performance[J].Applied Surface Science,2013,274:110-116.
[23] RAMOS M E,BONELLI P R,CUKIERMAN A L,et al.Adsorption of volatile organic compounds onto activated carbon cloths derived from a novel regenerated cellulosic precursor[J].Journal of Hazardous Materials,2010,177(1/2/3):175-182.
[24] 李慧芳,徐海,赵勤,等.几种分子筛对甲醛气体吸附性能的研究[J].硅酸盐通报,2014,33(1):122-126.LI H F,XU H,ZHAO Q,et al.Adsorption performance of formaldehyde on molecular sieve[J].Bulletin of the Chinese Ceramic Society,2014,33(1):122-126.
[25] VAN BAVEL E,MEYNEN V,COOL P,et al.Adsorption of hydrocarbons on mesoporous SBA-15 and PHTS materials[J].Langmuir,2005,21(6):2447-2453.
[26] HUSSEIN M S,AHMED M J.Fixed bed and batch adsorption of benzene and toluene from aromatic hydrocarbons on 5A molecular sieve zeolite[J].Materials Chemistry and Physics,2016,181:512-517.
[27] CELEBIOGLU A,SEN H S,DURGUN E,et al.Molecular entrapment of volatile organic compounds(VOCs) by electrospun cyclodextrin nanofibers[J].Chemosphere,2016,144:736-744.
[28] ZHU X,GAO X,QIN R,et al.Plasma-catalytic removal of formaldehyde over Cu-Ce catalysts in a dielectric barrier discharge reactor[J].Applied Catalysis B:Environmental,2015,170/171:293-300.
[29] AUBRY O,CORMIER J.Improvement of the diluted propane efficiency treatment using a non-thermal plasma[J].Plasma Chemistry and Plasma Processing,2009,29(1):13-25.
[30] MARGUREANU M,MANDACHE N B,ELOY P,et al.Plasma-assisted catalysis for volatile organic compounds abatement[J].Applied Catalysis B:Environmental,2005,61(1/2):12-20.
[31] MOZGINE O,KOUTSOSPYROS A,GERSHMAN S,et al.Plasmochemical degradation of volatile organic compounds(VOC)in a capillary discharge plasma reactor[J].IEEE Transactions on Plasma Science,2009,37(6):905-910.
[32] QIN C,HUANG X,DANG X,et al.Toluene removal by sequential adsorption-plasma catalytic process:effects of Ag and Mn impregnation sequence on Ag-Mn/γ-Al₂O₃[J].Chemosphere,2016,162:125-130.
[33] NORSIC C,TATIBOUET J,BATIOT-DUPEYRAT C,et al.Non thermal plasma assisted catalysis of methanol oxidation on Mn,Ce and Cu oxides supported on γ-Al₂O₃[J].Chemical Engineering Journal,2016,304:563-572.
[34] GANDHI M S,MOK Y S.Non-thermal plasma-catalytic decomposition of volatile organic compounds using alumina supported metal oxide nanoparticles[J].Surface and Coatings Technology,2014,259:12-19.
[35] VAN DURME J,DEWULF J,DEMEESTERE K,et al.Post-plasma catalytic technology for the removal of toluene from indoor air:effect of humidity[J].Applied Catalysis B:Environmental,2009,87(1/2):78-83.
[36] CARABINEIRO S A C,CHEN X,MARTYNYUK O,et al.Gold supported on metal oxides for volatile organic compounds total oxidation[J].Catalysis Today,2015,244:103-114.
[37] CHEN B,ZHU X,WANG Y,et al.Gold stabilized on various oxide supports catalyzing formaldehyde oxidation at room temperature[J].Chinese Journal of Catalysis,2016,37(10):1729-1737.
[38] CHEN B,ZHU X,CROCKER M,et al.FeO_x-supported gold catalysts for catalytic removal of formaldehyde at room temperature[J].Applied Catalysis B:Environmental,2014,154/155:73-81.
[39] MA Y,ZHANG G.Sepiolite nanofiber-supported platinum nanoparticle catalysts toward the catalytic oxidation of formaldehyde at ambient temperature:efficient and stable performance and mechanism[J].Chemical Engineering Journal,2016,288:70-78.
[40] ZIELINSKA-JUREK A,ZALESKA A.Ag/Pt-modified TiO₂ nanoparticles for toluene photooxidation in the gas phase[J].Catalysis Today,2014,230:104-111.
[41] PHAM T,LEE B,LEE C.The advanced removal of benzene from aerosols by photocatalytic oxidation and adsorption of Cu-TiO₂/PU under visible light irradiation[J].Applied Catalysis B:Environmental,2016,182:172-183.
[42] QIAN X,YUE D,TIAN Z,et al.Carbon quantum dots decorated Bi₂WO₆ nanocomposite with enhanced photocatalytic oxidation activity for VOCs[J].Applied Catalysis B:Environmental,2016,193:16-21.
[43] HUANG Q,MA W,YAN X,et al.Photocatalytic decomposition of gaseous HCHO by Zr_xTi_1-xO₂ catalysts under UV-Vis light irradiation with an energy-saving lamp[J].Journal of Molecular Catalysis A:Chemical,2013,366:261-265.
[44] YAN Z,XU Z,YU J,et al.Enhanced formaldehyde oxidation on CeO₂/AlOOH-supported Pt catalyst at room temperature[J].Applied Catalysis B:Environmental,2016,199:458-465.
[45] AKIRA F,KENICHI H.Lectrochemical photolysis of water at a semiconductor electrode[J].Nature,1972,5358(238):37-38.
[46] SIRISUK A,HILL C G,ANDERSON M A.Photocatalytic degradation of ethylene over thin films of titania supported on glass rings[J].Catalysis Today,1999,54:159-164.
[47] NISCHK M,MAZIERSKI P,GAZDA M,et al.Ordered TiO₂ nanotubes:the effect of preparation parameters on the photocatalytic activity in air purification process[J].Applied Catalysis B:Environmental,2014,144:674-685.
[48] JANSSON I,SUÁREZ S,GARCIA-GARCIA F J,et al.Zeolite-TiO₂ hybrid composites for pollutant degradation in gas phase[J].Applied Catalysis B:Environmental,2015,178:100-107.
[49] ŠULIGOJ A,ŠTANGAR U L,RISTI? A,et al.TiO₂-SiO₂ films from organic-free colloidal TiO₂ anatase nanoparticles as photocatalyst for removal of volatile organic compounds from indoor air[J].Applied Catalysis B:Environmental,2016,184:119-131.
[50] GUO T,BAI Z,WU C,et al.Influence of relative humidity on the photocatalytic oxidation(PCO) of toluene by TiO₂ loaded on activated carbon fibers:PCO rate and intermediates accumulation[J].Applied Catalysis B:Environmental,2008,79(2):171-178.
[51] FENG Y,LI L,LI J,et al.Synthesis of mesoporous BiOBr 3D microspheres and their photodecomposition for toluene[J].Journal of Hazardous Materials,2011,192(2):538-544.
[52] LIU L,ZHAO J.Formaldehyde adsorption and decomposition on rutile (110):a first-principles study[J].Surface Science,2016,652:156-162.
[53] OUSMANE M,LIOTTA L F,CARLO G D,et al.Supported Au catalysts for low-temperature abatement of propene and toluene,as model VOCs:support effect[J].Applied Catalysis B:Environmental,2011,101(3/4):629-637.
[54] 张荣,李娟,宋莉,等.V/Ce共掺杂TiO₂光催化降解甲醛的实验研究[J].环境工程学报,2011(9):2095-2100.ZHANG R,LI J,SONG L,et al.Experimental research on degradation of formaldehyde by photocatalysis of V/Ce co-doped TiO₂[J].Chinese Journal of Environmental Engineering,2011(9):2095-2100.
[55] SELISHCHEV D S,KOLOBOV N S,PERSHIN A A,et al.TiO₂ mediated photocatalytic oxidation of volatile organic compounds:formation of CO as a harmful by-product[J].Applied Catalysis B:Environmental,2017,200:503-513.
[56] DU Y,TANG D D,ZHANG G K.Facile synthesis of Ag₂O-TiO₂/sepiolite composites with enhanced visible-light photocatalytic properties[J].Chinese Journal of Catalysis,2015,36:2219-2228.
[57] DANIELS S L.Air ionization of indoor environments for control of volatile and particulate contaminants with nonthermal plasmas generated by dielectric-barrier discharge[J].IEEE Transactions on Plasma Science,2002,30(4):1471-1481.