WO1996017667A2 - Vorrichtung zur spaltung von öl-in-wasser-emulsionen mittels elektrokoagulation - Google Patents
Vorrichtung zur spaltung von öl-in-wasser-emulsionen mittels elektrokoagulation Download PDFInfo
- Publication number
- WO1996017667A2 WO1996017667A2 PCT/DE1995/001717 DE9501717W WO9617667A2 WO 1996017667 A2 WO1996017667 A2 WO 1996017667A2 DE 9501717 W DE9501717 W DE 9501717W WO 9617667 A2 WO9617667 A2 WO 9617667A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrodes
- electrocoagulation
- electrode devices
- coagulation
- electrode
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/06—Separation of liquids from each other by electricity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C11/00—Separation by high-voltage electrical fields, not provided for in other groups of this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D3/00—Differential sedimentation
- B03D3/02—Coagulation
-
- 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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C2201/00—Details of magnetic or electrostatic separation
- B03C2201/02—Electrostatic separation of liquids from liquids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4611—Fluid flow
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/02—Fluid flow conditions
- C02F2301/022—Laminar
Definitions
- the invention relates to a device for splitting oil-in-water emulsions by means of electrocoagulation.
- Large quantities of oily waste water are produced in industrial production processes.
- oil and water form an emulsion, i.e. the oil is in the form of microdroplets in the water.
- These oil droplets carry surface electrical charges, which causes these drops to distribute evenly in the water.
- An additional and often decisive stabilization of the oil-water emulsion is carried out by wetting agents, such as those that are part of cleaning agents.
- the charges of the oil droplets coated with these surfactants prevent the droplets from flowing together and rising to the surface.
- the disposal of oil-water emulsions, which are highly polluted waste is becoming an increasingly important factor in production costs.
- the ever stricter environmental protection legislation requires the avoidance or reduction of waste materials. For this reason, processes are becoming more and more important economically that enable a circulation of cleaning water in particular.
- splitting agents are only insufficiently removed with the oil.
- the disadvantages of these processes include the introduction of fission chemicals or their reaction products into the water, which means that the water can only be reused to a limited extent.
- the use of inorganic splitting agents usually leads to the salting of the water. With the widespread use of hydroxide-forming metal salts, large quantities of sludge are also formed, the disposal of which is becoming increasingly difficult.
- Electrode surfaces This reduces the current flow, the process comes to a standstill. The result is that the electrodes have to be cleaned frequently.
- a major disadvantage of this process is the large amounts of hydroxide sludge that is difficult to dispose of.
- electrocoagulation as described in PS 37 39 580 C2
- the surface charge of the oil drops is used for phase separation. Under the influence of an electric field between two electrodes, the negatively charged droplets migrate to the positive electrode and coagulate into larger drops, which can then be separated by decanting.
- the gas formation by electrolysis of the water supports the oil / water separation.
- the disadvantage of this principle of oil / water separation is the long treatment times, which is why this method has so far found little practical application.
- a significant reduction in the treatment times for emulsion splitting by electrocoagulation is achieved by entering coagulation kernels in the oil-water mixture to be split.
- the coagulation nuclei are usually microscopic, inorganic structures on which the Coagulation of the oil droplets discharged at the electrodes takes place. Cores of this type reduce the energy barrier of surface tension and the steric effects created by surfactants. This makes it easier for the droplets discharged in the electric field to flow together. For these reasons, the presence of a sufficient amount of coagulation cores is of crucial importance for the emulsion splitting according to the principle of electrocoagulation.
- a further disadvantage is that emulsions or aqueous cleaning media with different or fluctuating properties or compositions can only be prepared with difficulty, inter alia in that the necessary modification to achieve a change in the area ratio of the electrodes requires a great deal of effort.
- the limited formation of coagulation nuclei and their difficult ability to influence leads to a limited use of this method.
- the object of the invention was to expand the field of use of electrocoagulation and to increase flexibility, and to minimize disposal costs by reducing the quantities of waste material that had to be disposed of.
- a device for splitting emulsions and for regenerating cleaning and degreasing baths is assumed, in particular by electrocoagulation in an electrophysical cell, in which, according to the invention, at least two mutually independent electrode devices, each with its own circuit, are arranged. This means that each circuit can be regulated independently of the other. In this way, both the formation of the coagulation cores and the process of electrocoagulation can be adapted and optimized independently of one another to the respective operating conditions.
- the separate circuits for the two electrode devices offer the possibility of using small distances between the electrodes, low voltages and high current densities to form coagulation cores on the soluble electrodes, and with larger distances, high voltages, high field strengths, small current densities and low gas generation for electrocoagulation to operate the durable electrodes.
- Reversible polarity electrode devices are arranged in the electrophysical cell, the cathode and anode of each electrode device being made of the same material. This has the advantage that the formation of coagulation nuclei on the one hand and the process of electrocoagulation on the other hand is stabilized at a high level by the, in particular periodic, change in the current direction.
- the cathode of an electrode device becomes the anode and vice versa. This advantageously prevents the formation of electrically non-conductive layers on the electrodes, which lead to a reduced current density with the result of poor coagulation.
- the arranged electrode devices are equipped with voltage supplies for clocked and variably adjustable Voltage, especially DC voltage connected.
- At least two of the mutually independent electrode devices consist of different materials.
- the one intended for the formation of coagulation nuclei advantageously consists of a metal which leads to the formation of hydroxides, insoluble salts, etc. through the electrolysis.
- these electrodes made of an aluminum alloy can be used, which counteract passivation of the surface.
- An insoluble or insoluble material is preferably used for another electrode device provided for the process of electrocoagulation. This serves to optimize the implementation of the process and leads to a long service life.
- high-alloy steel preferably V4A, material number 1.4576 can be used as the electrode material.
- the electrode devices with different material compositions are arranged in an interlocking manner.
- the interlocking construction is preferably used with an average power consumption of less than or equal to 2 kWh / m 3 . It is advantageous that the formation of coagulation nuclei, the confluence of the oil droplets and the oil separation supported by flotation take place in one cell. This allows a very compact design that can be used in confined spaces.
- the electrode devices with different material compositions are arranged spatially separated from one another. High power consumption (preferably greater than 2 kWh / m 3 ) during the splitting process leads to intensive gas formation with the consequence of turbulent flows in the cell, which negatively influence the process of coagulation and can be avoided with the proposed arrangement, since the medium flowing through the cell first the soluble and then the insoluble
- Electrode arrangement (6) generated gas arranged.
- This constructive design of electrode devices and housings advantageously ensures that a largely laminar flow is generated between the electrodes and a turbulent flow, convection currents or a
- Electrode devices can be prevented effectively.
- Figure 2 shows an electrophysical cell with two
- Electrode devices each with 4 electrodes, which are arranged in an interlocking manner, and
- Figure 3 shows the formation of baffles in an electrophysical cell.
- Figure 1 shows a housing 3 of an electrophysical cell with a baffle 4 and an electrode device for the Coagulation core formation 6 and an electrode device for electrocoagulation 5, both of which have their own controllable current sources.
- a current source is connected to the alternating and symmetrically arranged anodes 7 or cathodes 8 of the electrode device for electrocoagulation 5, another to the also alternately and symmetrically arranged anodes 9 or cathodes 10 of the electrode device for coagulation core formation 6.
- the Reverse polarity of the soluble metal electrodes of the coagulation core formation electrodes 2 is the controlled dissolution of deposits or their prevention, which enables continuous coagulation core formation.
- the polarity reversal of the permanent electrodes 1 of the electrode device for the electrocoagulation 5 is preferably carried out in periods between 1 s and 100 min.
- the frequency of the clocked DC voltage, in particular at the electrode device for electrocoagulation 5, is preferably between 1 and 1000 Hertz.
- the emulsion splitting is preferably carried out in the pH range 7 to 12 and at temperatures between 1 ° C. and 100 ° C.
- the emulsion to be split is introduced into the electrolysis cell in task 13 and is split up in the area of the electrode devices 6 and 5, the gas bubbles formed on the electrodes floating free and demulsified oil as well as flotatable metal hydroxides and solid particles in the oil layer 14. There, the oil and the flotatable solids are removed via the oil drain 12, while sedimentable substances accumulate on the bottom of the secondary clarification zone 15 and are removed if necessary.
- the treatment times of the emulsion are preferably in the range between 10 s and 60 min, the energy requirement being between 0.1 and 50 kWh / m 3 .
- FIG. 2 shows the interlocking arrangement of the electrode devices, which can be used particularly advantageously due to its compact design.
- FIG. 3 shows a particularly advantageous variant of the arrangement of guide plates 4 in the housing of the electrophysical cell 3, which guide the emulsion to be treated or its fission products in a flow that is as uniform as possible.
- gas formation necessarily results from the electrolysis of the water. Gas formation generally leads to turbulent flow, with the result that the coagulation process is disturbed. This is therefore avoided by the arrangement of the electrode devices 5 and 6 according to FIG. 3, in which the electrolysis gas is derived from the soluble electrodes 1 by a suitable design of the housing 3 and the guide plates 4.
- Electrodes 5, 6 So far, only two electrode devices 5, 6 have been shown. Arrangements with multiple electrode devices are expedient as required, in particular in order to increase the throughput and the separation quality. Blocks of electrode devices can be formed (5,5,5,5 ...; 6,6,6,6 ...) as well as alternating arrangements (5, 6, 5, 6).
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrostatic Separation (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95940126A EP0742736A1 (de) | 1994-12-06 | 1995-12-04 | Vorrichtung zur spaltung von öl-in-wasser-emulsionen mittels elektrokoagulation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4443297.6 | 1994-12-06 | ||
DE4443297A DE4443297C1 (de) | 1994-12-06 | 1994-12-06 | Vorrichtung zur Spaltung von Öl-in-Wasser-Emulsionen mittels Elektrokoagulation |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1996017667A2 true WO1996017667A2 (de) | 1996-06-13 |
WO1996017667A3 WO1996017667A3 (de) | 1996-08-15 |
Family
ID=6534989
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE1995/001717 WO1996017667A2 (de) | 1994-12-06 | 1995-12-04 | Vorrichtung zur spaltung von öl-in-wasser-emulsionen mittels elektrokoagulation |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0742736A1 (de) |
DE (1) | DE4443297C1 (de) |
WO (1) | WO1996017667A2 (de) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999043617A1 (en) * | 1998-02-27 | 1999-09-02 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US6746593B2 (en) | 2002-01-18 | 2004-06-08 | Robert J. Herbst | High volume electrolytic water treatment system and process for treating wastewater |
US7211185B2 (en) | 1998-02-27 | 2007-05-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
RU2333894C2 (ru) * | 2006-09-04 | 2008-09-20 | Олег Аркадьевич Бессонов | Способ очистки попутных вод нефтегазовых месторождений |
US7758742B2 (en) | 1998-02-27 | 2010-07-20 | Scott Wade Powell | Method and apparatus for separation of water from petroleum products in an electrocoagulation process |
US7981293B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
US7981301B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
US7998225B2 (en) | 2007-02-22 | 2011-08-16 | Powell Scott W | Methods of purifying biodiesel fuels |
US8048279B2 (en) | 1998-02-27 | 2011-11-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US10358361B2 (en) | 2013-02-22 | 2019-07-23 | Loren L. Losh | System and method for remediation of wastewater including aerobic and electrocoagulation treatment |
US10745299B2 (en) | 2013-02-22 | 2020-08-18 | NiBru Traka, Inc. | Struvite formation by precipitation of ammonia in electrocoagulation process |
US10918972B2 (en) | 2016-01-29 | 2021-02-16 | Borealis Ag | Methods for the separation of at least one emulsion by applying an electrical field and device for carrying out said method |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9713856D0 (en) * | 1997-07-01 | 1997-09-03 | Morgan Philip G | Tangential cross-flow electroflocculation |
EP1225156A1 (de) * | 2001-01-22 | 2002-07-24 | Enomoto Industry Co., Ltd. | Vorrichtung und Verfahren zur Entfernung von feinteiligen Metallpulvern aus Emulsionen auf elektrochemischem Weg |
US11046596B2 (en) | 2012-10-25 | 2021-06-29 | Hydrus Technology Pty. Ltd. | Electrochemical liquid treatment apparatus |
WO2015176137A1 (en) * | 2014-05-23 | 2015-11-26 | Hydrus Technology Pty. Ltd. | Electrochemical treatment methods |
US11046595B2 (en) | 2014-05-23 | 2021-06-29 | Hydrus Technology Pty. Ltd. | Electrochemical treatment methods |
EP3261996A1 (de) * | 2015-02-26 | 2018-01-03 | Sandonà, Roberto | Wässriger entfettender wäscher |
EP3904297A1 (de) * | 2020-04-27 | 2021-11-03 | ATB WATER GmbH | Fällmodul |
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DE1804060B2 (de) * | 1968-10-19 | 1971-02-18 | Metallgesellschaft AG, 6000 Frank fürt | Verfahren und Vorrichtung zur Be schleumgung der Trennung der Phasengeiu sehe bei der Flussig Flussig Extraktion |
AT305914B (de) * | 1970-06-02 | 1973-03-26 | Oesterr Alpine Montan | Verfahren und Vorrichtung zur Reinigung von Abwässern |
DE2617996A1 (de) * | 1976-04-24 | 1977-10-27 | Krugmann Citex Masch Alfred | Verfahren und vorrichtung zur abtrennung von fremdstoffen aus verunreinigtem wasser |
US4056451A (en) * | 1976-03-29 | 1977-11-01 | Maloney-Crawford Tank Corporation | Dual field electric treater |
EP0019640A1 (de) * | 1979-04-19 | 1980-12-10 | Petrolite Corporation | Vorrichtung zur Entwässerung und Entsalzung in mehreren Stufen in einem einzelnen Gefäss und Verfahren zur Entsalzung von Erdölen |
US4252631A (en) * | 1980-01-09 | 1981-02-24 | The United States Of America As Represented By The United States Department Of Energy | Electrostatic coalescence system with independent AC and DC hydrophilic electrodes |
US4308127A (en) * | 1980-03-17 | 1981-12-29 | Combustion Engineering, Inc. | Separation of emulsions with electric field |
CH646404A5 (en) * | 1980-09-05 | 1984-11-30 | Kh Motorostroitel Z Serp Molot | Plant for electrochemical purification of waste water |
AT391679B (de) * | 1984-05-08 | 1990-11-12 | Kh Polt I Im V I Lenina | Vorrichtung fuer die elektrochemische reinigung einer verschmutzten fluessigkeit |
DE3528197A1 (de) * | 1984-08-11 | 1987-03-19 | Edgar Dipl Ing Renzler | Verfahren zur spaltung von emulsionen, bei denen wasser als kontinuierliche phase vorliegt und vorrichtung zur durchfuehrung des verfahrens |
EP0220189B1 (de) * | 1984-08-11 | 1989-03-29 | RENZLER, Edgar | Verfahren zur regeneration von reinigungs- und entfettungsbädern und vorrichtung zur durchführung des verfahrens |
DE3717633A1 (de) * | 1987-05-26 | 1988-12-08 | Rwo Masch Armaturen App | Verfahren zum elektrolytischen trennen einer oel/wasser-emulsion |
-
1994
- 1994-12-06 DE DE4443297A patent/DE4443297C1/de not_active Expired - Fee Related
-
1995
- 1995-12-04 EP EP95940126A patent/EP0742736A1/de not_active Withdrawn
- 1995-12-04 WO PCT/DE1995/001717 patent/WO1996017667A2/de not_active Application Discontinuation
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8048279B2 (en) | 1998-02-27 | 2011-11-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US6139710A (en) * | 1998-02-27 | 2000-10-31 | Powell; Scott Wade | Apparatus for electrocoagulation of liquids |
US6488835B1 (en) | 1998-02-27 | 2002-12-03 | Scott Wade Powell | Method for electrocoagulation of liquids |
US7211185B2 (en) | 1998-02-27 | 2007-05-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US7758742B2 (en) | 1998-02-27 | 2010-07-20 | Scott Wade Powell | Method and apparatus for separation of water from petroleum products in an electrocoagulation process |
US8133382B2 (en) | 1998-02-27 | 2012-03-13 | Scott Powell | Method for electrocoagulation of liquids |
WO1999043617A1 (en) * | 1998-02-27 | 1999-09-02 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US6746593B2 (en) | 2002-01-18 | 2004-06-08 | Robert J. Herbst | High volume electrolytic water treatment system and process for treating wastewater |
RU2333894C2 (ru) * | 2006-09-04 | 2008-09-20 | Олег Аркадьевич Бессонов | Способ очистки попутных вод нефтегазовых месторождений |
US7998225B2 (en) | 2007-02-22 | 2011-08-16 | Powell Scott W | Methods of purifying biodiesel fuels |
US7981301B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
US7981293B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
US8192617B2 (en) | 2008-11-21 | 2012-06-05 | Powell Scott W | System for treatment of contaminated liquid |
US10358361B2 (en) | 2013-02-22 | 2019-07-23 | Loren L. Losh | System and method for remediation of wastewater including aerobic and electrocoagulation treatment |
US10745299B2 (en) | 2013-02-22 | 2020-08-18 | NiBru Traka, Inc. | Struvite formation by precipitation of ammonia in electrocoagulation process |
US11407660B2 (en) | 2013-02-22 | 2022-08-09 | Bio2 Pw Inc. | System and method for remediation of wastewater including aerobic and electrocoagulation treatment |
US10918972B2 (en) | 2016-01-29 | 2021-02-16 | Borealis Ag | Methods for the separation of at least one emulsion by applying an electrical field and device for carrying out said method |
US11224828B2 (en) | 2016-01-29 | 2022-01-18 | Borealis Ag | Methods for the separation of at least one emulsion by applying an electrical field and device for carrying out said method |
US11911715B2 (en) | 2016-01-29 | 2024-02-27 | Borealis Ag | Methods for the separation of at least one emulsion by applying an electrical field and device for carrying out said method |
Also Published As
Publication number | Publication date |
---|---|
DE4443297C1 (de) | 1996-03-07 |
WO1996017667A3 (de) | 1996-08-15 |
EP0742736A1 (de) | 1996-11-20 |
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