WO2006134149A1 - Procede et systeme pour epurer par photocatalyse des eaux usees et de l'air vicie - Google Patents

Procede et systeme pour epurer par photocatalyse des eaux usees et de l'air vicie Download PDF

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Publication number
WO2006134149A1
WO2006134149A1 PCT/EP2006/063248 EP2006063248W WO2006134149A1 WO 2006134149 A1 WO2006134149 A1 WO 2006134149A1 EP 2006063248 W EP2006063248 W EP 2006063248W WO 2006134149 A1 WO2006134149 A1 WO 2006134149A1
Authority
WO
WIPO (PCT)
Prior art keywords
air
titanium dioxide
ozone
gaseous
photocatalytically active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2006/063248
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German (de)
English (en)
Inventor
Detlev MÖLLER
Siegfried Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Brandenburgische Technische Universitaet Cottbus
Original Assignee
Brandenburgische Technische Universitaet Cottbus
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Brandenburgische Technische Universitaet Cottbus filed Critical Brandenburgische Technische Universitaet Cottbus
Publication of WO2006134149A1 publication Critical patent/WO2006134149A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to a process for oxidizing and removing environmentally harmful substance components from gaseous and / or aqueous phases using the photocatalytic effect of titanium dioxide.
  • the method is particularly suitable for the purification of air, preferably for the production of pure internal air, but also exhaust air or exhaust gases, for the elimination of odors and purification of waste water.
  • the invention also provides a cleaning system for carrying out the method.
  • Areas of application are preferably the cleaning of indoor air in private and public building areas, the production of sterile air in hospital, especially operating areas and the production of clean air for special production processes.
  • an application for exhaust air purification is possible.
  • the process principle is also suitable for the purification of waste water, in particular those that are contaminated with organic pollutants and germs.
  • Ozone generators filter systems, air ionizers, air scrubbers and UV rays have long been used to clean indoor air. This procedure are based on mechanical-physical effects (particle separation by filters with partially preceding electrostatic charging), the washing out of air components by absorption liquids (scrubbers) or a chemical transformation (oxidation), initiated by ozone, ionized oxygen and UV light.
  • Filter systems are basically only for the separation of particulate coarser air components (dust, pollen, microorganisms). They have the disadvantage that the filters must be regularly replaced or regenerated, but are characterized by high separation efficiency (the
  • Air ionizers which are based on the formation of excited oxygen molecules and possibly "active" oxygen (eg O radicals), do not show a high chemical efficiency even for theoretical reasons, but can possibly charge and precipitate dusts.Ozone generators and UV irradiation have in The air purification is not proven since ozone in the gas phase reacts only with a few organic compounds (olefins) and photochemical conversions remain low in the available times scrubbers are basically effective methods for
  • Air purification they are industrially used mainly for the purification of exhaust air); they can be selectively designed for individual trace substances.
  • the prerequisite for effective air purification is always a good absorption of the trace substance to be removed in the washing liquid.
  • the disadvantage is the treatment of the wastewater, which requires separate additional facilities.
  • Filters and scrubbers are used in particular for the purification of exhaust air.
  • This process which belongs to the Advanced Oxidation Processes (AOPs), is becoming increasingly important for mineralizing toxic or biologically poorly degradable organic water and air constituents with the aid of hydroxyl radicals (Schiavello, M., ed. (1997) Heterogeneous photocatalysis. Vol. 3 Wiley Series in Photosciences and Photoengineering, Wiley, Chichester).
  • AOPs Advanced Oxidation Processes
  • TiO 2 is a semiconductor material with a band gap of 3.2 eV
  • light in the wavelength range between 200 nm and about 400 nm can initiate these photochemical reactions, ie, in addition to artificial light sources, the UV-A radiation of the sun (300 - 300 nm). 400 nm) can be effectively used.
  • This special form of photocatalysis is called "solar-catalytic water or air purification”.
  • the invention therefore an object of the invention to provide a method by which the purification of air and water can be carried out quickly and environmentally friendly and environmentally harmful substance components can be almost completely removed under extensive Ausoxidieren.
  • This object is achieved by a method for oxidizing and removing environmentally harmful substance components from gaseous and / or aqueous phases using the photocatalytic effect of titanium dioxide.
  • the gaseous and / or aqueous phases to be purified are reacted in a reaction space with a photocatalytically active titania Surface be brought into contact.
  • a photocatalytically active titania Surface be brought into contact.
  • the reaction space are preferably plates and / or packing, which have titanium dioxide coated surfaces and are shown in a system so constructive that they ensure a high surface / volume ratio. They are available in any geometric shapes.
  • a high or high surface / volume ratio (which serves as a measure of the amount of a material that is used per volume of space) is preferably 10 m 2 / m 3 to 1000 m 2 / m 3 , preferably from 500 m 2 / m 3 in front.
  • the catalytically active surface is designed in particular as a packing of different geometric shapes.
  • Geometric shapes can e.g. Be balls or calipers.
  • an aqueous liquid film is produced on the photocatalytically active surface.
  • the photocatalytically active surfaces are sprayed continuously with a rinsing liquid (for cleaning gaseous phases) or directly with the aqueous phase to be purified.
  • the photochemically catalyzed radical reaction is initiated with a light source.
  • Light source according to the invention may be the sunlight or any other radiation sources that are capable of generating radicals.
  • ozone generated at the same time in a gas phase is supplied for the purpose of intensifying radical formation, which can be produced with an upstream ozone generator.
  • ozone and the radiation necessary for photocatalysis can also be generated by a common radiation source in the reaction space.
  • the rinsing liquid used preferably water, is preferably recycled. To increase the efficiency of the process, both the
  • Rinsing liquid and the wastewater to be treated additional chemical substances are added, which influence the pH and thus the reaction process and / or generate other reactive radicals that react with the trace substances or can initiate further radical processes.
  • chemical substances are added which lead to an increase in the oxidation capacity.
  • oxidants which are selected as a function of the pH.
  • acidic pH Areas pH ⁇ 6
  • metal ions eg, Fe 2+ or Mn 2+ , etc.
  • reaction space further preferably comprises at least one UV lamp in addition to the photocatalytic surface.
  • the process is carried out in such a way that the liquids are preferably introduced into the reaction space via a spray device.
  • a spray device This can be located outside the reaction space, or in another embodiment, the reaction space for the purification of gaseous phases, the catalytically active surfaces have designed as contact surfaces of various types in a spray absorber.
  • the method can be carried out with the supply of sound waves, wherein sound generators are used, which initiate an increased mass transport of the reactive and degradable species to the photocatalytically active surfaces and tribochemical effects, in particular due to acoustic coagulation.
  • the process is carried out under ultrasonic conditions.
  • the process can take place under pressure (high pressure).
  • pressure high pressure
  • concentration of ozone and the rate of pollutant oxidation dependent thereon are increased.
  • an increase in pressure facilitates the overcoming of process-related flow resistance.
  • the process according to the invention has proven to be suitable for oxidizing and removing environmentally harmful components in the form of organic compounds, sulfite, reduced heavy metals, sulfur dioxide, reduced sulfur compounds, nitrogen oxides, bacteria or germs.
  • special pollutants can be isolated, such as organic pollutants in the neutral pH range with addition of ozone, sulfur dioxide eg in the alkaline range with ozone and nitrogen oxides eg in the pH range 6 to 8 with Fe 2+ ions.
  • electrons are activated by light on a Ti ⁇ 2 surface.
  • the inventive method combines in a simple manner known per se phenomena of independent primary formation of two oxidants - O 2 " on the photocatalytic TiO 2 surface and O 3 in the gas phase by UV radiation.
  • the superoxide radicals initially formed on the catalytic surface react rapidly with ozone in the aqueous phase.
  • a radical formation occurs as a result of O 3 -fallfall in aqueous solutions.
  • the radical chains formed thereby enable a radical regeneration, in particular by the conversion OH ⁇ HO 2 in the OH-attack on organic substances. From the HO 2 O 2 " is again formed (pH equilibrium) which in turn reacts with O 3 , etc.
  • the process represents a chemical two-phase system and allows a significant acceleration of the trace gas oxidation and thus purification of the air or water.
  • Essential to the invention is the presence of an aqueous liquid film on the photocatalytic surface, in (and at) the pollutant degradation takes place with simultaneous ozone supply.
  • the waste water i.d.R. even the liquid phase.
  • the primary oxidation products formed from the air pollutants are much more water-soluble than the starting materials, so that a large proportion of the surface remains or is dissolved and further to mineral Residues can be implemented or removed by water renewal with the sewage flow.
  • the process is a multiple combination.
  • radical chemical reactions take place in the gas phase as a result of ozone formation and UV radiation, which leads to the neutralization of trace substances, exhaust gas and wastewater components.
  • bacteria, viruses u.a. Killed microorganisms As a result, bacteria, viruses u.a. Killed microorganisms.
  • all soluble trace substances can be washed out by water sprinkling and oxidized in the liquid phase.
  • the method has the following advantages over previously described methods:
  • the process can be used in combination with other air purification and treatment systems (eg filters, air conditioners). 5.
  • the method can also be used on a mobile basis, so that a
  • the method can also be used for effective exhaust air purification with appropriate dimensioning.
  • the process is suitable for both air and water purification in the same system.
  • the method can be adapted to the removal of specific trace substances in the case of modular adaptation.
  • the inventive method thus allows environmentally harmful substances to be removed quickly and almost completely.
  • the method according to the invention can also be used only with sunlight (no special UV light is necessary), which recommends the method, in particular in a special variant for rapid water treatment.
  • the invention also provides a cleaning system which comprises the following devices and can also be configured as a mobile device: a) at least one reaction space with a photocatalytically active titanium dioxide surface which consists of a system of differently or identically arranged plates and / or random packings b) a spraying device and c) an ozone generator, d) optionally a light source and / or e) optionally a sound generator.
  • the cleaning system can be coupled to an air conditioning system and / or a further air entrainment system and be operated stationary.
  • it is used for exhaust air and water purification.
  • a container is provided with catalytically active TiO 2 -coated plates in such a way that the incoming air stream to be cleaned has to travel as far as possible in relation to a small reactor volume.
  • the Catalyst plate surfaces are continuously wetted from above via a distribution system with an aqueous rinsing liquid in the form of a thin film, wherein the rinsing liquid flows in the circuit.
  • the container surface is internally provided with a system of UV lamps, which both generate ozone and trigger the photocatalytic effect.
  • the oxidation of the air pollutants takes place in the liquid film, wherein the products are largely absorbed and oxidized using the cycle principle over a long period of time completely harmless mineral products and discharged as such.
  • the rinsing liquid enriched with the dissolved mineral residues must be replaced. This point in time can be determined by a simple salinity measurement and the detergent change is fully automatic.
  • the waste water is no further environmental hazard because it consists of natural inorganic substances that are diluted rapidly in the municipal sewage system.
  • a cylindrical container is filled with optically permeable Ti ⁇ 2 -coated packings, for example Raschig rings, and is wetted with water via a spraying system located on the ceiling.
  • a spraying system located on the ceiling.
  • the ceiling lamps are installed, which ensure a photocatalytic excitation.
  • the air is supplied via an ozone generator.
  • the ozone-enriched polluted air flows past the packing and reacts on the wet surface with formed OH radicals, resulting in a fast and effective air purification.
  • the devices described in the aforementioned embodiments can be combined with a superior air filter for coarse cleaning of particulate trace substances. Both devices can also be installed in existing systems for air treatment, in particular systems for room and building air conditioning.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biomedical Technology (AREA)
  • Toxicology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)

Abstract

L'invention concerne un procédé pour oxyder et extraire des éléments de matières polluantes hors de phases gazeuses et/ou aqueuses en utilisant les effets photocatalytiques de l'oxyde de titane. Selon l'invention, les phases gazeuses et/ou aqueuses à épurer sont mises en contact avec une surface d'oxyde de titane photocatalytique dans un espace réactionnel, avec introduction simultanée d'ozone généré en phase gazeuse. La surface d'oxyde de titane photocatalytique est aspergée en continu d'un fluide de lavage ou de la phase aqueuse à épurer. Ce procédé est particulièrement adapté pour nettoyer l'air, de préférence pour purifier l'air intérieur, mais aussi pour nettoyer un air d'évacuation ou des gaz d'échappement, pour éliminer des odeurs et épurer des eaux usées. La présente invention porte également sur un système d'épuration pour réaliser ce procédé.
PCT/EP2006/063248 2005-06-15 2006-06-15 Procede et systeme pour epurer par photocatalyse des eaux usees et de l'air vicie Ceased WO2006134149A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005028660.7 2005-06-15
DE200510028660 DE102005028660A1 (de) 2005-06-15 2005-06-15 Verfahren zur photokatalytischen Luft- und Abwasserreinigung

Publications (1)

Publication Number Publication Date
WO2006134149A1 true WO2006134149A1 (fr) 2006-12-21

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011028478A1 (fr) * 2009-08-25 2011-03-10 Fahs Stagemyer Llc Procédés et utilisations de molécules à dissociation
EP2234650A4 (fr) * 2007-12-21 2012-10-10 Kimberly Clark Co Système de traitement du gaz
US8658101B1 (en) 2012-01-19 2014-02-25 Dust Free, Lp Photocatalytic device with curved reflectors
US8926899B1 (en) 2013-01-10 2015-01-06 Dust Free, Lp Photocatalytic devices
US9011780B1 (en) 2012-05-30 2015-04-21 Dust Free, Lp Photocatalytic device for ductless heating and air conditioning systems
US9073766B2 (en) 2009-08-25 2015-07-07 Fahs Stagemyer, Llc Methods for the treatment of ballast water
US9205169B1 (en) 2013-01-10 2015-12-08 Dust Free, Lp Photocatalytic devices
CN105157130A (zh) * 2015-10-19 2015-12-16 董练昌 一种空气净化方法
US9782510B1 (en) 2013-01-18 2017-10-10 Dust Free, Lp Photocatalytic device with multi-metallic catalysts
US10010644B2 (en) 2012-05-30 2018-07-03 Dust Free, Lp Photocatalytic device for ductless heating and air conditioning systems
CN110882624A (zh) * 2018-09-10 2020-03-17 黄骅市鑫通机械设备有限公司 光氧催化废气净化器
US10814030B1 (en) 2018-04-06 2020-10-27 Dust Free, Lp Hybrid full spectrum air purifier devices, systems, and methods
DE102020118636A1 (de) 2020-07-15 2022-01-20 Sterilair Ag Transportband mit photokatalytischem Effekt
CN114191907A (zh) * 2022-01-13 2022-03-18 卓宇轩 一种异味处理系统
CN117164121A (zh) * 2023-11-01 2023-12-05 北京世纪农丰土地科技有限公司 一种富养化黑臭水体生态浮岛修复系统

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DE102011121910A1 (de) * 2011-12-21 2013-06-27 Ultrasonic Systems Gmbh Verfahren zur Behandlung sulfidhaltiger Ablauge
EP2674208A1 (fr) 2012-06-17 2013-12-18 UV-Consulting Peschl e. K. Module d'émetteur UV pour un dispositif d'évacuation d'air, de gaz d'échappement ou d'épuration de l'air ambiant
DE102016209952A1 (de) * 2016-06-07 2017-12-07 Robert Bosch Gmbh Filtervorrichtung
DE102020126529A1 (de) 2020-10-09 2022-04-14 TruTraTec GmbH Reaktor zur Abwasserbehandlung

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2234650A4 (fr) * 2007-12-21 2012-10-10 Kimberly Clark Co Système de traitement du gaz
US10287193B2 (en) 2009-08-25 2019-05-14 Fahs Stagemyer Llc Systems and methods for the treatment of ballast water
US9334183B2 (en) 2009-08-25 2016-05-10 Fahs Stagemyer, Llc Methods for the treatment of ballast water
US8202500B2 (en) 2009-08-25 2012-06-19 Fahs Stagemyer, Llc Processes and uses of dissociating molecules
JP2013503036A (ja) * 2009-08-25 2013-01-31 ファーズ ステージマイヤー エルエルシー 分子を解離するプロセスおよび使用
US8440154B2 (en) 2009-08-25 2013-05-14 Fahs Stagemyer, Llc Processes and uses of dissociating molecules
WO2011028478A1 (fr) * 2009-08-25 2011-03-10 Fahs Stagemyer Llc Procédés et utilisations de molécules à dissociation
US9073766B2 (en) 2009-08-25 2015-07-07 Fahs Stagemyer, Llc Methods for the treatment of ballast water
CN102574705A (zh) * 2009-08-25 2012-07-11 法斯-施塔格迈尔有限责任公司 离解分子的方法和用途
US8658101B1 (en) 2012-01-19 2014-02-25 Dust Free, Lp Photocatalytic device with curved reflectors
US9011780B1 (en) 2012-05-30 2015-04-21 Dust Free, Lp Photocatalytic device for ductless heating and air conditioning systems
US10010644B2 (en) 2012-05-30 2018-07-03 Dust Free, Lp Photocatalytic device for ductless heating and air conditioning systems
US8926899B1 (en) 2013-01-10 2015-01-06 Dust Free, Lp Photocatalytic devices
US9205169B1 (en) 2013-01-10 2015-12-08 Dust Free, Lp Photocatalytic devices
US9782510B1 (en) 2013-01-18 2017-10-10 Dust Free, Lp Photocatalytic device with multi-metallic catalysts
CN105157130A (zh) * 2015-10-19 2015-12-16 董练昌 一种空气净化方法
US10814030B1 (en) 2018-04-06 2020-10-27 Dust Free, Lp Hybrid full spectrum air purifier devices, systems, and methods
CN110882624A (zh) * 2018-09-10 2020-03-17 黄骅市鑫通机械设备有限公司 光氧催化废气净化器
DE102020118636A1 (de) 2020-07-15 2022-01-20 Sterilair Ag Transportband mit photokatalytischem Effekt
CN114191907A (zh) * 2022-01-13 2022-03-18 卓宇轩 一种异味处理系统
CN117164121A (zh) * 2023-11-01 2023-12-05 北京世纪农丰土地科技有限公司 一种富养化黑臭水体生态浮岛修复系统
CN117164121B (zh) * 2023-11-01 2024-02-27 北京世纪农丰土地科技有限公司 一种富养化黑臭水体生态浮岛修复系统

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