强电场电离放电先进氧化技术研究
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摘要
先进氧化工艺是二十世纪80年代开始形成的有毒污染物处理技术，目前在环保领域已成为国内外研究的热点之一。由于现有的先进氧化方法存在羟基产生浓度偏低、运行成本过高、受反应条件限制适用范围窄等缺点，难以满足环境污染工程治理的需求。为了将先进氧化技术推向工程化应用，并拓宽其研究及应用领域，本文结合国家自然科学基金重点资助项目“高气压下强电场电离气体的方法及其应用的基础研究(60031001)”和国家自然科学基金资助项目“气体电离放电治理外来生物入侵性传播研究(60371035)”，运用强电离放电方法和高效气液溶解技术实现了工程化制取高浓度羟基溶液，并成功应用于船舶压载水工程治理。研究取得的主要成果如下：
1．实现高气压(＞0.1MPa)条件下强电场电离放电加速电子及激励气体分子。在反应腔体内形成折合电场强度E／n≥400Td，电子平均能量＞10eV，电子浓度＞10~(15)／cm~3的强电离放电，将水和氧分子合成高浓度、大产生量羟基自由基，具有不用催化剂，无副产品、无废料和零污染的特点。
2．采用强电场电离放电方法和高效气液溶解技术制取的羟基药剂浓度高达20mg／L，制取量大、运行成本低，满足了先进氧化技术工程化应用的需求。
3．强电场电离放电制取羟基治理船舶压载水的实验结果表明：羟基药剂可在小剂量条件下快速氧化分解有机体和杀灭微生物，并将其最终分解成二氧化碳、水和无机盐，剩余羟基则转化为无害的H_2O和O_2，反应后无有害残留物，治理过程清洁，是一项绿色的先进氧化技术。
强电场电离放电是目前工程化制取羟基的唯一有效方法，克服了限制先进氧化技术工程化应用的主要难点，使先进氧化工艺朝工程化应用方向迈出了关键性的一步。
The Advanced Oxidation Technologies, which have been applied to treat hazardous pollutants since the 1980s, have currently become one of the hot subjects in the environmental protection field both at home and abroad. But the methods available could not be applied to the environmental pollution control engineering by reason of low generating concentration of hydroxyl radicle, high operation cost and rigid reaction conditions. In order to broaden the research and application realm of AOTs and put to engineering use, a new approach was investigated producing high-concentration hydroxyl solution by strong-field ionization discharge and high-efficiency gas-liquid dissolution technique based on the key NSFC Project "Studies of Method and Application of Gas Molecules Ionized with Strong Electric Field at High Pressure" (No "60031001) and the NSTF Project "Studies on Treating Invasive Spread of the Introduced Species by Gas Ionization Discharge" (No.: 60371035), and was successfully applied to treat ship's ballast w
ater. The main achievements are as follows:
1. Activating gas molecules with accelerated electrons was realized by strong-field ionization discharge at atmospheric pressure. In the discharge chamber, the reduced electric field strength was E/n>400Td, the average energy of electrons was more than 10eV, the concentration of electrons over 1015/cm3. With this means, high-concentration and great-yield hydroxyl radicle could be produced by mixed gas of H2O and O2. This technology had the advantages of without catalyst, no byproducts and wastes.
2. The obtained concentration of hydroxyl solution reached 20mg/L by strong-field ionization discharge and high-efficiency dissolution method, which met the need of engineering applications for its low operation cost and power consumption.
3. The results of a series of experiments indicated that hydroxyl radicle could oxidize organic compounds and kill off microorganisms rapidly under low dose and ultimately discompose them into CO2, H2O and inorganic salts, the surplus hydroxyl radicle degenerated into H2O and O2, and that no harmful residue was left after the treatment. It
was considered a green AOT by virtue of its clean treating process. It was regarded at present as the most efficient method producing high concentration hydroxyl radicle by strong-field ionization discharge, which overcame the main obstacles limiting the industrial applications of AOTs, and took a critical step toward engineerization.
1．实现高气压(＞0.1MPa)条件下强电场电离放电加速电子及激励气体分子。在反应腔体内形成折合电场强度E／n≥400Td，电子平均能量＞10eV，电子浓度＞10~(15)／cm~3的强电离放电，将水和氧分子合成高浓度、大产生量羟基自由基，具有不用催化剂，无副产品、无废料和零污染的特点。
2．采用强电场电离放电方法和高效气液溶解技术制取的羟基药剂浓度高达20mg／L，制取量大、运行成本低，满足了先进氧化技术工程化应用的需求。
3．强电场电离放电制取羟基治理船舶压载水的实验结果表明：羟基药剂可在小剂量条件下快速氧化分解有机体和杀灭微生物，并将其最终分解成二氧化碳、水和无机盐，剩余羟基则转化为无害的H_2O和O_2，反应后无有害残留物，治理过程清洁，是一项绿色的先进氧化技术。
强电场电离放电是目前工程化制取羟基的唯一有效方法，克服了限制先进氧化技术工程化应用的主要难点，使先进氧化工艺朝工程化应用方向迈出了关键性的一步。
The Advanced Oxidation Technologies, which have been applied to treat hazardous pollutants since the 1980s, have currently become one of the hot subjects in the environmental protection field both at home and abroad. But the methods available could not be applied to the environmental pollution control engineering by reason of low generating concentration of hydroxyl radicle, high operation cost and rigid reaction conditions. In order to broaden the research and application realm of AOTs and put to engineering use, a new approach was investigated producing high-concentration hydroxyl solution by strong-field ionization discharge and high-efficiency gas-liquid dissolution technique based on the key NSFC Project "Studies of Method and Application of Gas Molecules Ionized with Strong Electric Field at High Pressure" (No "60031001) and the NSTF Project "Studies on Treating Invasive Spread of the Introduced Species by Gas Ionization Discharge" (No.: 60371035), and was successfully applied to treat ship's ballast w
ater. The main achievements are as follows:
1. Activating gas molecules with accelerated electrons was realized by strong-field ionization discharge at atmospheric pressure. In the discharge chamber, the reduced electric field strength was E/n>400Td, the average energy of electrons was more than 10eV, the concentration of electrons over 1015/cm3. With this means, high-concentration and great-yield hydroxyl radicle could be produced by mixed gas of H2O and O2. This technology had the advantages of without catalyst, no byproducts and wastes.
2. The obtained concentration of hydroxyl solution reached 20mg/L by strong-field ionization discharge and high-efficiency dissolution method, which met the need of engineering applications for its low operation cost and power consumption.
3. The results of a series of experiments indicated that hydroxyl radicle could oxidize organic compounds and kill off microorganisms rapidly under low dose and ultimately discompose them into CO2, H2O and inorganic salts, the surplus hydroxyl radicle degenerated into H2O and O2, and that no harmful residue was left after the treatment. It
was considered a green AOT by virtue of its clean treating process. It was regarded at present as the most efficient method producing high concentration hydroxyl radicle by strong-field ionization discharge, which overcame the main obstacles limiting the industrial applications of AOTs, and took a critical step toward engineerization.
引文
[1] 孙贤波，赵庆样，曹同民等．先进氧化法的特性及其应用．中国给水排水，2002，18(5)：33-35
[2] 孙德智．环境工程中的高级氧化技术[M]．北京：化学工业出版社．2002：47
[3] 孙存普，张建中，段绍瑾．自由基生物学导论[M]．合肥：中国科技大学出版社，1999：31-197
[4] Hardweick T J. The free radical mechanism in the reactions of hydrogen peroxide[J]. Can. J. Chem., 1957, 35(3): 428
[5] Weiss J. Investigation on the Radical HO_2 in Solution[J]. Trans. Faraday Soc., 1935, 31(3): 668
[6] Mattews R W. Photooxidation of Organic Material in Aqueous Suspensions of Titanium Dioxide[J]. Water Res., 1990, 24(5): 653
[7] Prengle H W. Experimental Rate Constant and Reactor Considerations for the Destruction of Micropollutants and Trihalomethane Precursors by Ozone with UV Radiations[J]. Environ. Sci. & Tech., 1983, 17(4): 743
[8] Hoigne J, Bader H. The Role of Hydroxyl Radical Reactions in Ozonation Processes in Aqueous Solutions[J]. Water Res., 1976, 10(2): 377
[9] Bernie M. PENETRANTE, J. Norman BARDSLEY, Mark C. HSIAO. Kinetic Analysis of Non-Thermal Plasmas Used for Pollution Control. Jpn. J. Appl. Phys, 1997, 36(7B): 5007-5017
[10] Glaze W H, Kang J W, Chapin D H. The Chemistry of Water Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation[J]. Ozone Sci. & Eng., 1987, 9(4): 335.
[11] Duguet J P. Application of Combined Ozone-Hydrogen Peroxide for the Removal of Aromatic Compounds from a Groundwater[J]. Ozone Sci. & Eng., 1990, 12(3): 281
[12] Staehelin J, Hoigne J. Decomposition of Ozone in Water: Rate of Initiation by Hydroxide Ion and Hydrogen Peroxide[J]. Environ. Sci. & Tech., 1982, 16(3): 676
[13] Okamoto K I, Yamamoto Y, Tanaka H, et al. Heterogeneous Photocatalytic Decomposition of Phenol over Tio_2 Powder[J]. Bull Chem. Soc., Japan, 1995, 58(10): 2015
[14] Pettier C, Lamy M L, Francony A, et al. Sonochemical Degradation of Phenol in Dilute Aqueous Solutions: Comparison of the Reaction Rates at 20 and 487kHz[J]. J. Phys. Chem., 1994,98(5): 1051
[15] Fujii H, Ohtaki M, Eguchi K et al. J. Mater. Sci. Lett. 1997, 16:1086
[16] Peyton G R, Glaze W H. Environ. Sci. Technol. 1988, 22(7): 761
[17] Cheuront DA et al. Environ. Prog. 1990, 9:143
[18] 钟理，陈建军．先进氧化处理有机污水技术进展[J]．工业水处理，2002，22(1)：1-5
[19] 叶向群．绿色化学与绿色化学设计．环境污染与防治．2002．24(3)：190-192
[20] 梁文平，唐晋．当代化学的一个重要前沿—绿色化学．化学进展，2000，12(2)：228—230
[21] 朱清时．绿色化学．化学进展，2000，12(4)：410-414
[22] 白希尧，张芝涛，白敏冬等．高气压强电离放电等离子体学科的形成与应用．自然杂志，22(3)，2000：156-160
[23] Gregory M. Ruiz etc. Global spread of microorganisms by ships. Nature, 2000, 408: 49-50
[24] BAl Xiyao, ZHANG Zhitao, HAN Hui, et al. Research Situation and Progress of Non-equilibrium Plasma Chemistry[J]. Chinese Science Bulletin, 2002, 47(7): 529-530
[25] J. R. Roth. Industrial Plasma Engineering/Vol. 1: Principles, IOP Publishing Ltd, 1995
[26] Blaustein B D, Fu Y C. Hydrocarbons from H_2+CO and H_2+CO_2 in Microwave Discharge: Le Chatelier's Principle in Discharge Reactors of a Circulation System. lbid, 53(10), 1979:1448～1450
[27] I. Maezono, J. S. Chang. Reduction of CO_2 from combustion gases by DC corona torches, IEEE Trans. Ind. Applicat, 26(4), 1990: 651-655
[28] Yong Zhang, Wei Chu, Weimin Cao and el al. A Plasma-Activated Ni/α-Al_2O_3 Catalyst for the conversion of CH_4 to syngas, Plasma chemistry and Plasma Processing. 2000: 137～144
[29] Baldur Eliasson, Ulrich Kogelschatz. IEEE Trans on Plasma Sci, 1991, 19(6): 1063
[30] S. Tanaka, H. Uyama, O. Matsumoto. Plasma Chem. and Plasma Process, 1994, 14(4): 491
[31] H. V. Boenig. Fundamentals of Plasma Chemistry and Technology. Lancaster, UK: Technomic, 1988
[32] 水野彰．放电排处理技术．静电气会志[J]19(4)，1995：289～295
[33] Chemla D S. Zyss et al. Optical Properties Organic Molecules and Crystals. New York: 1987, Vols, landz
[34] 白春礼，苏明．世界科技研究与发展，2000，21(4)：12
[35] B Eliasson, M Hirth, U Kogelschatz. Ozone synthesis from oxygen in dielectric barrier discharges. J. Phys. D: Appl. Phys, 20, 1987:1421～1437
[36] Ostenfeld, C. H. On the Immigration of Biddulphia sinensis Grev. and its Occurrence in the North Sea during 1903-1907. Medd. Komm. Havunders., Ser. Plankton, 1908, 1(6): 1-46
[37] 白希尧，白敏冬，周晓见等．羟基及其药剂制取方法研究．化工时刊，2002，16(4)：1-7
[38] M.Roustan, J.Mallevialle, H.Roques, et al. Mass transfer of ozone to water: A fundamental study. Ozone: Sci & Eng., 1981, 2: 337-344
[39] Cohen AN. 1998. Ships, Ballast Water and the Introduction of Exotic Organisms into the San Francisco Estuary.Current Status of the Problem and Options for Management. San Francisco Estuary Institute: Richmond, CA
[40] Mackenzie etc. Alien invaders. New Scientist, 1999, 162: 18-19
[41] Geoff Rigby. From Ballast to Bouillabaisse. Science, 2000, 289:241
[42] Donald M.Anderson. Turning back the harmful red tide. Nature, 1997, 388:513-514
[43] 胡承兵．阻止“搭乘”于压载水中的外来生物入侵者．交通环保，1999，20(4)：35-39
[44] Hallegraeff G. M. & Bolch C. J. Transport of Diatom and Dinoflagellate Resting Spores in Ships' Ballast Water: Implications for Plankton Biogeography and Aquaculture. J. Plankton Res, 1992, 14, (8): 1067-1084
[45] Carlton, J. T. Biological Invasions and Biodiversity in the Sea: The Ecological and Human Impacts of Non-indigenous Marine and Estuarine Organisms. Proc. Conf. Wkshop. NOAA, 1994: 5-11
[46] Holmes, J. M. C. & Minchin, D. Two Exotic Copepods Imported into Ireland with the Pacific Oyster Crassostrea gigas (Thunberg). Ir. Nat. J., 1995, 25: 17-20
[47] 全球压载水管理项目中国国家项目实施小组．全球更换压载水管理项目．交通环保，2001，专版1期：1-4
[48] 李世信，王学忠．IMO海上环境保护委员会第45届会议．中国船检，2000，1：36-37
[49] K. Yamamoto. Development of High Concentration Ozone Water. J. Institute Electrost. Japan, 22(4), 1998: 180-183
[2] 孙德智．环境工程中的高级氧化技术[M]．北京：化学工业出版社．2002：47
[3] 孙存普，张建中，段绍瑾．自由基生物学导论[M]．合肥：中国科技大学出版社，1999：31-197
[4] Hardweick T J. The free radical mechanism in the reactions of hydrogen peroxide[J]. Can. J. Chem., 1957, 35(3): 428
[5] Weiss J. Investigation on the Radical HO_2 in Solution[J]. Trans. Faraday Soc., 1935, 31(3): 668
[6] Mattews R W. Photooxidation of Organic Material in Aqueous Suspensions of Titanium Dioxide[J]. Water Res., 1990, 24(5): 653
[7] Prengle H W. Experimental Rate Constant and Reactor Considerations for the Destruction of Micropollutants and Trihalomethane Precursors by Ozone with UV Radiations[J]. Environ. Sci. & Tech., 1983, 17(4): 743
[8] Hoigne J, Bader H. The Role of Hydroxyl Radical Reactions in Ozonation Processes in Aqueous Solutions[J]. Water Res., 1976, 10(2): 377
[9] Bernie M. PENETRANTE, J. Norman BARDSLEY, Mark C. HSIAO. Kinetic Analysis of Non-Thermal Plasmas Used for Pollution Control. Jpn. J. Appl. Phys, 1997, 36(7B): 5007-5017
[10] Glaze W H, Kang J W, Chapin D H. The Chemistry of Water Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation[J]. Ozone Sci. & Eng., 1987, 9(4): 335.
[11] Duguet J P. Application of Combined Ozone-Hydrogen Peroxide for the Removal of Aromatic Compounds from a Groundwater[J]. Ozone Sci. & Eng., 1990, 12(3): 281
[12] Staehelin J, Hoigne J. Decomposition of Ozone in Water: Rate of Initiation by Hydroxide Ion and Hydrogen Peroxide[J]. Environ. Sci. & Tech., 1982, 16(3): 676
[13] Okamoto K I, Yamamoto Y, Tanaka H, et al. Heterogeneous Photocatalytic Decomposition of Phenol over Tio_2 Powder[J]. Bull Chem. Soc., Japan, 1995, 58(10): 2015
[14] Pettier C, Lamy M L, Francony A, et al. Sonochemical Degradation of Phenol in Dilute Aqueous Solutions: Comparison of the Reaction Rates at 20 and 487kHz[J]. J. Phys. Chem., 1994,98(5): 1051
[15] Fujii H, Ohtaki M, Eguchi K et al. J. Mater. Sci. Lett. 1997, 16:1086
[16] Peyton G R, Glaze W H. Environ. Sci. Technol. 1988, 22(7): 761
[17] Cheuront DA et al. Environ. Prog. 1990, 9:143
[18] 钟理，陈建军．先进氧化处理有机污水技术进展[J]．工业水处理，2002，22(1)：1-5
[19] 叶向群．绿色化学与绿色化学设计．环境污染与防治．2002．24(3)：190-192
[20] 梁文平，唐晋．当代化学的一个重要前沿—绿色化学．化学进展，2000，12(2)：228—230
[21] 朱清时．绿色化学．化学进展，2000，12(4)：410-414
[22] 白希尧，张芝涛，白敏冬等．高气压强电离放电等离子体学科的形成与应用．自然杂志，22(3)，2000：156-160
[23] Gregory M. Ruiz etc. Global spread of microorganisms by ships. Nature, 2000, 408: 49-50
[24] BAl Xiyao, ZHANG Zhitao, HAN Hui, et al. Research Situation and Progress of Non-equilibrium Plasma Chemistry[J]. Chinese Science Bulletin, 2002, 47(7): 529-530
[25] J. R. Roth. Industrial Plasma Engineering/Vol. 1: Principles, IOP Publishing Ltd, 1995
[26] Blaustein B D, Fu Y C. Hydrocarbons from H_2+CO and H_2+CO_2 in Microwave Discharge: Le Chatelier's Principle in Discharge Reactors of a Circulation System. lbid, 53(10), 1979:1448～1450
[27] I. Maezono, J. S. Chang. Reduction of CO_2 from combustion gases by DC corona torches, IEEE Trans. Ind. Applicat, 26(4), 1990: 651-655
[28] Yong Zhang, Wei Chu, Weimin Cao and el al. A Plasma-Activated Ni/α-Al_2O_3 Catalyst for the conversion of CH_4 to syngas, Plasma chemistry and Plasma Processing. 2000: 137～144
[29] Baldur Eliasson, Ulrich Kogelschatz. IEEE Trans on Plasma Sci, 1991, 19(6): 1063
[30] S. Tanaka, H. Uyama, O. Matsumoto. Plasma Chem. and Plasma Process, 1994, 14(4): 491
[31] H. V. Boenig. Fundamentals of Plasma Chemistry and Technology. Lancaster, UK: Technomic, 1988
[32] 水野彰．放电排处理技术．静电气会志[J]19(4)，1995：289～295
[33] Chemla D S. Zyss et al. Optical Properties Organic Molecules and Crystals. New York: 1987, Vols, landz
[34] 白春礼，苏明．世界科技研究与发展，2000，21(4)：12
[35] B Eliasson, M Hirth, U Kogelschatz. Ozone synthesis from oxygen in dielectric barrier discharges. J. Phys. D: Appl. Phys, 20, 1987:1421～1437
[36] Ostenfeld, C. H. On the Immigration of Biddulphia sinensis Grev. and its Occurrence in the North Sea during 1903-1907. Medd. Komm. Havunders., Ser. Plankton, 1908, 1(6): 1-46
[37] 白希尧，白敏冬，周晓见等．羟基及其药剂制取方法研究．化工时刊，2002，16(4)：1-7
[38] M.Roustan, J.Mallevialle, H.Roques, et al. Mass transfer of ozone to water: A fundamental study. Ozone: Sci & Eng., 1981, 2: 337-344
[39] Cohen AN. 1998. Ships, Ballast Water and the Introduction of Exotic Organisms into the San Francisco Estuary.Current Status of the Problem and Options for Management. San Francisco Estuary Institute: Richmond, CA
[40] Mackenzie etc. Alien invaders. New Scientist, 1999, 162: 18-19
[41] Geoff Rigby. From Ballast to Bouillabaisse. Science, 2000, 289:241
[42] Donald M.Anderson. Turning back the harmful red tide. Nature, 1997, 388:513-514
[43] 胡承兵．阻止“搭乘”于压载水中的外来生物入侵者．交通环保，1999，20(4)：35-39
[44] Hallegraeff G. M. & Bolch C. J. Transport of Diatom and Dinoflagellate Resting Spores in Ships' Ballast Water: Implications for Plankton Biogeography and Aquaculture. J. Plankton Res, 1992, 14, (8): 1067-1084
[45] Carlton, J. T. Biological Invasions and Biodiversity in the Sea: The Ecological and Human Impacts of Non-indigenous Marine and Estuarine Organisms. Proc. Conf. Wkshop. NOAA, 1994: 5-11
[46] Holmes, J. M. C. & Minchin, D. Two Exotic Copepods Imported into Ireland with the Pacific Oyster Crassostrea gigas (Thunberg). Ir. Nat. J., 1995, 25: 17-20
[47] 全球压载水管理项目中国国家项目实施小组．全球更换压载水管理项目．交通环保，2001，专版1期：1-4
[48] 李世信，王学忠．IMO海上环境保护委员会第45届会议．中国船检，2000，1：36-37
[49] K. Yamamoto. Development of High Concentration Ozone Water. J. Institute Electrost. Japan, 22(4), 1998: 180-183