WO2005097213A1 - Dispositif et procede d'epuration de liquides - Google Patents
Dispositif et procede d'epuration de liquides Download PDFInfo
- Publication number
- WO2005097213A1 WO2005097213A1 PCT/EP2005/003678 EP2005003678W WO2005097213A1 WO 2005097213 A1 WO2005097213 A1 WO 2005097213A1 EP 2005003678 W EP2005003678 W EP 2005003678W WO 2005097213 A1 WO2005097213 A1 WO 2005097213A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- liquid
- substances
- reactor
- gas
- Prior art date
Links
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/14—Plasma, i.e. ionised 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
Definitions
- the present invention relates to an apparatus and a method for cleaning liquids.
- liquids such as, for example, endocrine-disrupting substances, bioactive substances, environmental toxins, pesticides, herbicides, X-ray contrast agents, medicaments, solvents and other substances which are difficult to decompose or oxidize.
- This ge ' -. happens with the help of radicals that are generated by electron transfer.
- electrons can be formed, for example, by plasmas, electron beams, corona discharge and electromagnetic waves.
- plasmas are used, for example, in wear-free switches. These are mainly used where very high currents have to be switched.
- Another area of application is surface technology. With the help of plasmas, surfaces are cleaned, functionalized or coated.
- a common application in this field is sputtering, in which atoms are removed from an existing precious metal electrode and a wide variety of materials can be coated with the precious metal (e.g. gold-plating of plastics).
- sputtering in which atoms are removed from an existing precious metal electrode and a wide variety of materials can be coated with the precious metal (e.g. gold-plating of plastics).
- Another common use is the manufacture of semiconductors. In this application, semiconductor surfaces are etched with the help of plasmas and special process gases, whereby certain component functions can be created (transistors).
- a pulsed corona discharge is generated with the help of two immersed electrodes under alternating high voltage.
- This short circuit reaction means that a very high voltage (up to 100 kV) is briefly applied to the medium, but which only lasts at intervals of just a few ms? can be maintained.
- oxygen is also injected into the liquid medium to increase cleaning performance.
- the object of the present invention is therefore to provide a device and a method for cleaning liquids, with which a highly effective, effective and complete cleaning of liquids is possible. This object is achieved by the device according to claim 1 and the method according to claim 23.
- Advantageous developments of the device according to the invention and of the method according to the invention are given in the respective dependent claims.
- Starting point of the present invention is to generate in a reactor or reactor vessel above the liquid to be purified a plasma or Coro 'naent- charge.
- a plasma or Coro 'naent- charge For this purpose, only one electrode is immersed in the liquid to be cleaned and the other electrode is arranged outside in the gas atmosphere above the liquid.
- the two electrodes now generate an electron flow across the barrier or atmosphere between the liquid medium and the second electrode. This results in a combination of anodic oxidation, ozonization and corona discharge due to the high voltage applied - it is not only the formation of ozone, but also the formation of radicals of the ozone and other reactions, which in turn lead to a breakdown of the substances to be broken down lead on the liquid surface.
- the effect according to the invention can be further enhanced by injecting air, oxygen, ozone or other gases into the liquid or gas.
- catalysts can be used which are introduced into the medium, or catalytic membranes or electrodes can be used.
- substances such as endocrine-disrupting substances can now use solvents! and other difficult-to-decompose substances from the liquid speed can be removed with the help of this electrode arrangement and free electrons.
- This also makes it possible to safely eliminate substances that are difficult to degrade, such as X-ray contrast media, even in the trace area, without generating new harmful substances.
- Electrodes such as precious metals, metal oxides or conductive diamond coatings are suitable as electrodes. These can lead to an increase in the rate of degradation.
- radicals can also be formed in the liquid phase by the presence of free electrons and the voltage applied to the electrodes.
- the immersed electrode can also be made of a different material, for example IrO, TiO, diamond or some other material with a catalytic effect, than the counter electrode, which, as described above, can consist of a stainless steel.
- Various methods can now be implemented, for example the generation of a low pressure plasma, a microwave plasma or a barrier discharge.
- Other types of plasma generation for generating the plasma in the gas phase can also be used.
- the barrier is discharged, the plasma is also generated in the gas phase and thus an adjacent liquid is treated.
- This fluid is connected to an electrode or barrier in contact or there is an electrode or a barrier in 'being immersed, or the liquid medium itself acts as an electrode.
- the immersed electrode is made of a material with a catalytic effect, e.g. Iridium oxide, titanium, diamond and the like consist or may contain, the counter electrode, for example, made of a stainless steel or a barrier electrode.
- the counter electrode for example, made of a stainless steel or a barrier electrode.
- 2 shows an atmospheric pressure reactor with barrier discharge
- 3 shows the structure of tubular reactors for barrier discharges
- FIG. 5 shows a combination of (electric) cross-flow filters with an electron reactor according to the invention.
- FIG. 1 now shows a low-pressure plasma or corona reactor with a reactor vessel 1, into which a liquid 2 is filled. Above the liquid 2 with an interface 4 to it there is a gas 3 in which the plasma is generated. Furthermore, a first electrode 5 is immersed in the liquid via an inlet 7a, which is closed with a stopper 8a. Above the liquid 2 in the gas space 3 there is another electrode 6, e.g. an anode. This further electrode 6 is introduced into the reactor 1 via an inlet 7c, which in turn is closed with a plug 8c. The reactor 1 has a further inlet 7b, which is also closed with a stopper 8b. Through the plug 8b, a pipe 10 leads to a vacuum pump
- the liquid 2 is either filled in beforehand via one of the inlet openings 7a, 7b or 7c or injected later or passed as a film over the wall of the reactor 2.
- the liquid 2 is treated in batches, but a continuous reactor construction is also possible.
- the first electrode 5 and the second electrode S are now subjected to high voltage of different voltage levels and geometries, but advantageously DC voltage, and generate a plasma in the gas 3.
- these polarities of the electrodes 5 and 6 can also be interchanged, or it can be ensured that other electrode geometries and electrode materials are used or that the electrodes only partially come into contact with the gas 3 or the liquid 2.
- the electrodes 5 and 6 and / or the inner wall of the reactor vessel 1 can contain, contain or consist of catalyst materials, among other materials, all metals such as iridium, stainless steel, titanium, platinum, their oxides or carbon, such as graphite or diamond ,
- the geometry of the voltage curve is variable.
- the current profile is also variable and is approx. 10 mA. This leads to a plasma in which gas 3 on the surface 4 of the liquid 2, so that substances in the liquid 2 are broken down.
- FIG. 2 shows an atmospheric pressure corona reactor 1 with a barrier discharge.
- the barrier discharge can be operated at atmospheric pressure.
- the basic structure of such a reactor 1 is explained below.
- a thin water film 2 flows over an electrode 5, which can be catalytically active and whose material properties can vary (the base itself can serve as an electrode) or a catalytically active wall 5 (whose material properties can vary) consist of a catalytic material or have a catalytic coating on their surface facing the water film 2, for example a diamond coating or iridium oxide coating.
- an electrode 5 which can be catalytically active and whose material properties can vary (the base itself can serve as an electrode) or a catalytically active wall 5 (whose material properties can vary) consist of a catalytic material or have a catalytic coating on their surface facing the water film 2, for example a diamond coating or iridium oxide coating.
- the water film may through a flow or a
- a gap 25 which can either be filled with air 3 or a process or inert gas.
- the corona discharge with which the water 2 is treated takes place in this gap 25.
- the barrier electrode 6 is located above the gap 25, the material properties of which vary and can also be catalytically active. This electrode is created the corona discharge.
- the gap distance between the electrodes 5 and 6 is advantageously between 0.5 mm and 10 mm in small-scale applications, and the gap distance can be up to several cm in large-scale applications. These heights vary depending on the application.
- Advantageous voltages for small-scale plants are between 500 V and 50 kV, for large-scale plants the voltage can rise to several 100 kV. These heights vary depending on the application.
- the arrangement can also be designed such that the barrier is arranged below the water film and the spray electrode 6 has no barrier.
- the gases generated during the corona discharge e.g. Ozone is sucked off during the process and thus the fluorescence 2 to be cleaned is pretreated or aftertreated either before or after the corona treatment.
- FIG. 3 shows in FIGS. 3A-C and FIG. 3D each show a further arrangement of a tube reactor, which is also used to generate a plasma or a corona discharge via barrier discharge.
- the central electrode 5 is provided with a dielectric barrier layer 18.
- a liquid film 2 in which the degradation processes are to take place is passed over the container wall 17.
- the container wall 17 also serves as a further electrode, for example as an anode, while the first electrode 5, for example as a cathode, is arranged in the center of the tube reactor.
- Both the wall 17 or the wall electrode and the center electrode 5 can consist of catalytic material.
- the distance between the electrodes is advantageously between 0.5 mm and 10 mm in small-scale applications, and the gap distance can be up to several cm in large-scale applications. These distances vary depending on the application.
- Advantageous voltages are between 500 V and 50 kV in small-scale systems, and in large-scale systems the voltage can rise to several 100 kV. Depending on the application, the size of the voltage and the gap distance vary.
- Figs. 3D-3F is in longitudinal section (Fig. 3D), in
- FIG. 3E Cross section
- FIG. 3F side view
- the dielectric barrier layer 18 is applied to the inside of the reactor wall 17 instead of to the center electrode 5.
- the process vessel itself can also serve as a barrier instead of a barrier layer.
- the barrier can also be arranged above the liquid medium, on the counter electrode or between the medium and counter electrode 5.
- FIG. 4 shows a further reactor 1, which is designed as a flow-through reactor with an inlet 7a and an outlet 7b.
- the wall 17 serves as a cathode, the wall 17 being provided with a dielectric barrier 18 on its inside.
- the wall 17 can be designed as a catalyst become.
- a liquid film 2 now forms on this wall, which encloses the interior of the reactor 1, which is filled with gas 3.
- a magnetron 19, with which a microwave plasma is generated in the gas 3, is arranged in the middle between the inlet 7a and the outlet 7b.
- a further possibility for improving the method according to the invention is that the electron reactor 1 according to the invention is combined with an upstream electrical cross-flow filtration.
- the electro cross current filtration generates depending on the desired solids separation (pore size of the membrane), the electrons used and the electrode polarity etc. a pre-cleaned and with dissolved
- Permeate mixed with chlorine and hydrogen peroxide This is particularly useful where normal membrane filtration inserts are currently in use, such as drinking water and process water treatment.
- FIG. 5 shows such a device with an electrical cross-flow filter 20 with an inlet 21 for raw water and an outlet 23 for retentate.
- the filtration permeate is fed to the reactor vessel 1 via an outlet 22 which is connected to the inlet 7a of the reactor vessel 1.
- a reactor as in FIG. 4 is used in FIG. 5, although all other reactor types can also be used.
- Catalytic materials can also be used in electrofiltration to increase the production of desired electrode products.
- all metals are suitable for this such as iridium, stainless steel, titanium, platinum, their oxides or carbon, such as graphite or diamond.
- the substances to be degraded can be specifically or non-specifically concentrated and then degraded in the electron reactor. This is particularly useful if the complete or almost complete breakdown of certain substances is desired.
- Such an arrangement could e.g. be designed such that the corona reactor is arranged behind an existing biological wastewater treatment system.
- the pollutants to be treated are concentrated with the help of a filtration before the corona treatment and the treated water is returned to the biological cleaning after the corona treatment.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200410017509 DE102004017509A1 (de) | 2004-04-08 | 2004-04-08 | Vorrichtung und Verfahren zur Reinigung von Flüssigkeiten |
DE102004017509.8 | 2004-04-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005097213A1 true WO2005097213A1 (fr) | 2005-10-20 |
Family
ID=34963609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/003678 WO2005097213A1 (fr) | 2004-04-08 | 2005-04-07 | Dispositif et procede d'epuration de liquides |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE102004017509A1 (fr) |
WO (1) | WO2005097213A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007048806A1 (fr) * | 2005-10-25 | 2007-05-03 | Aseptix Technologies B.V. | Procede de preparation de solutions aqueuses biocides activees |
CN105036251A (zh) * | 2015-06-26 | 2015-11-11 | 南京大学 | 一种电晕放电等离子体高效降解高浓度有机污染废水的装置 |
US20210221706A1 (en) * | 2021-01-14 | 2021-07-22 | Burak Karadag | Plasma-Based Water Treatment Apparatus |
US12116292B2 (en) * | 2021-01-14 | 2024-10-15 | Burak Karadag | Plasma-based water treatment apparatus |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4440813A1 (de) * | 1993-11-15 | 1995-05-18 | Fraunhofer Ges Forschung | Verfahren zur Behandlung von Flüssigkeiten |
US5876663A (en) * | 1995-11-14 | 1999-03-02 | The University Of Tennessee Research Corporation | Sterilization of liquids using plasma glow discharge |
RU2174103C1 (ru) * | 2000-01-10 | 2001-09-27 | Ивановский государственный химико-технологический университет | Способ очистки воды |
WO2002046103A1 (fr) * | 2000-12-08 | 2002-06-13 | Battelle Memorial Institute | Procede et dispositif de traitement par decharge corona pour modifier des composes contenant du carbone |
WO2002059046A2 (fr) * | 2001-01-25 | 2002-08-01 | Water Works Global, Inc. | Procede d'activation d'eau potable et chimiquement pure |
KR20030024938A (ko) * | 2001-09-19 | 2003-03-28 | 김석현 | 광 촉매 수 처리 장치 및 그에 의한 수 처리 방법 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3304465A (en) * | 1962-06-25 | 1967-02-14 | Hans W Hendel | Ignition of electric arc discharge devices |
US4982410A (en) * | 1989-04-19 | 1991-01-01 | Mustoe Trevor N | Plasma arc furnace with variable path transferred arc |
US5537009A (en) * | 1990-10-03 | 1996-07-16 | Chukanov; Kiril B. | Transition of a substance to a new state through use of energizer such as RF energy |
WO1997022556A1 (fr) * | 1995-12-20 | 1997-06-26 | Alcan International Limited | Reacteur thermique a plasma et procede de traitement d'eau de decharge |
EP1061119A1 (fr) * | 1999-06-17 | 2000-12-20 | Abb Research Ltd. | Craquage par décharge à barrière diélectrique |
-
2004
- 2004-04-08 DE DE200410017509 patent/DE102004017509A1/de not_active Ceased
-
2005
- 2005-04-07 WO PCT/EP2005/003678 patent/WO2005097213A1/fr active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4440813A1 (de) * | 1993-11-15 | 1995-05-18 | Fraunhofer Ges Forschung | Verfahren zur Behandlung von Flüssigkeiten |
US5876663A (en) * | 1995-11-14 | 1999-03-02 | The University Of Tennessee Research Corporation | Sterilization of liquids using plasma glow discharge |
RU2174103C1 (ru) * | 2000-01-10 | 2001-09-27 | Ивановский государственный химико-технологический университет | Способ очистки воды |
WO2002046103A1 (fr) * | 2000-12-08 | 2002-06-13 | Battelle Memorial Institute | Procede et dispositif de traitement par decharge corona pour modifier des composes contenant du carbone |
WO2002059046A2 (fr) * | 2001-01-25 | 2002-08-01 | Water Works Global, Inc. | Procede d'activation d'eau potable et chimiquement pure |
KR20030024938A (ko) * | 2001-09-19 | 2003-03-28 | 김석현 | 광 촉매 수 처리 장치 및 그에 의한 수 처리 방법 |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 200174, Derwent World Patents Index; Class D15, AN 2001-646922, XP002331629 * |
DATABASE WPI Section Ch Week 200360, Derwent World Patents Index; Class D15, AN 2003-632846, XP002331628 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007048806A1 (fr) * | 2005-10-25 | 2007-05-03 | Aseptix Technologies B.V. | Procede de preparation de solutions aqueuses biocides activees |
CN105036251A (zh) * | 2015-06-26 | 2015-11-11 | 南京大学 | 一种电晕放电等离子体高效降解高浓度有机污染废水的装置 |
US20210221706A1 (en) * | 2021-01-14 | 2021-07-22 | Burak Karadag | Plasma-Based Water Treatment Apparatus |
US12116292B2 (en) * | 2021-01-14 | 2024-10-15 | Burak Karadag | Plasma-based water treatment apparatus |
Also Published As
Publication number | Publication date |
---|---|
DE102004017509A1 (de) | 2005-11-17 |
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