• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Device for treating a liquid (L) comprising an organic pollutant, said device comprising: - a cavitation generator capable of generating, by cavitation, bubbles within said liquid, - an implosion chamber of said bubbles, - a generator ferrous cation Fe2 +, - a device for injecting into the liquid, an oxygenated fluid containing an oxygenated component, the oxygenated component being able to react with ferrous Fe 2+ cations to generate hydroxyl radicals, the implosion chamber of cavitation bubbles being disposed in a region in which the liquid contains said ferrous cations.
    公开号:FR3016625A1
    申请号:FR1450489
    申请日:2014-01-21
    公开日:2015-07-24
    发明作者:Gregoire Profit；Alexandre Profit
    申请人:ISB WATER；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The invention relates to a device for treating a liquid containing an organic pollutant.
    [0002] And 2 C the technique Biological processes are widely used to treat liquids containing organic compounds. However, certain organic compounds, called "persistent organic pollutants" or "POPs", are refractory to biodegradation and may even be toxic to the microorganisms used and reduce the effectiveness of these processes.
    [0003] To eliminate these organic compounds, it is possible to carry out adsorption or chemical oxidation processes. In particular, "advanced oxidation processes" (or POAs), described by Glaze et al. [Glaze W H, Kang J. W. Chapin D. H, "The Chemistry of Water Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation. Ozone Sci. Eng. 9 (1987) 335-352], are water treatment processes operating at ambient temperature and pressure which lead to the formation in solution and in high quantity of very powerful oxidants, the hydroxide radicals (OH °). The POA processes may include electrochemical processes for producing OH ° at the surface of a high current oxygen high oxygen surge anode, for example, anodic oxidation processes in the presence of H 2 O 2.
    [0004] Hydroxyl radicals OH ° are advantageously highly reactive with organic compounds and thus capable, by radical oxidation, of breaking molecules of very stable organic compounds. To generate hydroxyl radicals, the method. Fenton in particular consists of a decomposition of the hydrogen peroxide (E1202) by ferrous cations, according to the following reaction: H 2 O 2 + Fe 2 Fe 3 + + OH "+ OH This process requires, in order to be effective, the maintenance of a pH between 2.0 and 4.0, with an optimum pH value of 2.8, and therefore a pH control device should be provided, such pH control is expensive, technically realize, and always requires additional precautions to protect the material and the environment, and ensure the safety of people.
    [0005] Moreover, the Fenton process involves the addition of H 2 O 2, which is expensive and complex. In addition, ferrous Fe2 ÷ cations are conventionally obtained by direct addition of a ferrous salt, especially FeSO4 or other solid compounds of iron oxides (II & III) such as hematite, goethite, and magnetite. Dedicated and complex technical subsystems must then be put in place. Finally, the efficiency of the Fenton process remains limited. There is therefore a need for a new processing solution to solve, at least p. one or more of the above problems.
    [0006] SUMMARY OF THE INVENTION According to the invention, this object is achieved by means of a device for treating a liquid comprising an organic pollutant, said device comprising: a cavitation generator capable of generating, by cavitation, bubbles within a liquid, an implosion chamber of said bubbles, a ferrous cation generator Fe2 +, a device for injecting into the liquid an oxygenated fluid containing an oxygenated component, the oxygenated constituent being able to react with the Fe2 + ferrous cations. to generate hydroxyl radicals.
    [0007] According to the invention, c. The implosion of the cavitation bubbles is arranged in a region in which the liquid contains said ferrous cations. As will be seen in more detail in the following description, surprisingly, such a device allows, in a simple and effective way, effectively treat the liquid with a reduced consumption of additives, or without the use of additives.
    [0008] The cavitation generator generates bubbles that implode creating a complex set of thermodynamic and chemical reactions. In particular, the implosion corresponds to a considerable local increase in temperature and concentrations. These local extreme conditions would, in an unexplained way, promote the generation of hydroxyl radicals by reacting ferrous Fe 2+ cations and the oxygenated component.
    [0009] A processing device according to the invention may also comprise one or more of the following optional features cavitation generator is configured so that more than 50% by number of generated cavitation bubbles have a diameter of between 40 Ftm and 5 mm, preferably between 20 and 2 mm; the cavitation generator is chosen from the group consisting of a passive reactor (that is to say that cavitation results from a sudden reduction of the pressure within the liquid by acceleration of this liquid), an ultrasonic generator and their combination; the cavitation generator does not have a motor. More preferably, it has no moving part; the implosion chamber is preferably located at a distance of less than 0.5 m, at 0.3 m, at 0.1 m, preferably immediately downstream of the ferrous cation generator Fe2 +; preferably, the cavitation bubble implosion chamber is disposed "a region in which the ferrous cations are generated; preferably, the implosion chamber is disposed downstream of the ferrous cation generator Fe2 +; the ferrous cation generator does not require any input of electrical energy to operate; the ferrous cation generator preferably comprises a "Daniell" type cell between iron and a first electrically conductive material having an electrode potential greater than iron; the first electrically conductive material is selected from the group consisting of stainless steels, nickel alloys, silver, platinum, gold; preferably, the first electrically conductive material is a stainless steel or a nickel-based alloy, in particular a hastelloy or inconel; the galvanic pair is obtained between two iron masses and said first electrically conductive material, respectively, electrically connected to each other exclusively via said liquid to be treated (constituting an electrolyte); the masses are preferably monoblock, that is to say are not powders; the ferrous cation generator is disposed, preferably downstream, at a distance of less than 2 meters, preferably less than 1 meter, preferably less than 0.5 meters, preferably less than 0.3 meters, preferably less than 0.1 meter of the cavitation generator, or even in contact with the cavitation generator; the oxygenated fluid is air and / or hydrogen peroxide and / or ozone; the oxygenated fluid is preferably gas, and / or an aqueous solution of hydrogen peroxide; the cavitation bubble implosion chamber is disposed in a region in which the liquid contains said oxygenated component; the injection device is disposed upstream of the cavitation generator and / or the ferrous cation generator Fe2 +; the injection device is preferably arranged at a distance less than 0.5 m, less than 0.3 m, less than 0.1 m, from the cavitation generator and / or the ferrous cation generator Fe2 + the device of injection is preferably a microbuller capable of introducing into the liquid microbubbles of the oxygenated fluid having a diameter of less than 100 μm, preferably less than 75 μm, preferably less than 50 μm, and preferably greater than 25 μm; the microbuller comprises a porous block and an injector adapted to inject said oxygenated fluid, through the porous block, into the liquid; the porous block is a sintered material, preferably made of stainless steel, for example PSSTM from Pall Corporation; the micro-bubble injection rate generated by the microbuller is greater than 0.01% and / or less than 1%, less than 0.5%, less than 0.1% (V / V) with respect to the flow rate of liquid to be treated; the cavitation generator and / or the implosion chamber and / or the ferrous cation generator are incorporated in a hydrodynamic reactor; preferably, the hydrodigable reactor comprises first channels, preferably delimited internally by a dielectric material, preferably further formed in a block of said dielectric material, which open downstream in an intermediate chamber, the passage of the liquid in the first channels causing its acceleration and the generation of said bubbles, said intermediate chamber consti. t said implosion chamber; preferably, and in particular if the intermediate chamber is not delimited internally by iron, the hydrodynamic reactor preferably comprises first channels, second channels internally delimited by iron; preferably, the hydrodynamic reactor comprises i housing constituted, at least p. e to said first electrically conductive material so as to form a galvanic couple with the iron; the first channels and / or the second channels have a convergent longitudinal section, then divergent; the hydrodynamic reactor comprises one, preferably two or more than two so-called "improved" reaction modules, each improved reaction module being constituted, from upstream to downstream, by an optional upstream chamber, a second block comprising a plurality of second channels internally bounded, at least partially, preferably completely, by iron, preferably an intermediate chamber, a first block having a plurality of first channels, the passage of the liquid in the first channels causing its acceleration and the generation of cavitation bubbles, and a downstream chamber, the passage The liquid in the downstream chamber causing its slowing down and the implosion of cavitation bubbles; the passage of liquid in said second channels causes the acceleration of the liquid and the generation of cavitation bubbles and, preferably, the second channels of an improved reaction module open into an intermediate chamber capable of imploding the cavitation bubbles generated in said second channels; preferably, the hydrodynamic reactor comprises several successive improved reaction modules so that the first channels of a first improved reaction module open into a downstream chamber constituting the upstream chamber of a second improved reaction module immediately downstream of the first module improved reaction; in one embodiment, the hydrodynamic reactor comprises one, preferably two or more than two so-called "simplified" reaction modules, each simplified reaction module consisting of upstream to downstream, by a block comprising channels at least partially, preferably completely, delimited by iron and shaped to cause the generation of cavitation bubbles, and an implosion chamber disposed downstream of said channels and shaped to cause implosion of cavitation bubbles; the housing defines at least partially an intermediate chamber and / or contains one, preferably all reaction modules, optionally simplified; the treatment device comprises a circulation pump driving the liquid through the microbuller and the reaction module (s), possibly simplified; the microbuller is disposed downstream of the circulation pump, at a distance from the pump preferably less than 1 meter, preferably less than 0.5 meter, preferably less than 0.3 meter, preferably less than 0.1 metre. The invention also relates to an installation for treating a liquid containing an organic pollutant, said installation comprising a circuit in which are inserted a target and a device for treating said liquid and said target, the treatment device being in accordance with the invention. 'invention. A treatment plant according to the invention may also include one or more of the following optional characteristics: The organic pollutant is chosen from the group formed by volatile organic compounds, semi-volatile, PCBs, pesticides, herbicides, dioxins, furans, explosive products and their degradation products, humic products, dyes; The liquid to be treated comes from the production of oil or gas, mining, hydraulic fracturing, counting or water treatment, drinking or not; The liquid to be treated has a chemical oxygen demand (COD) greater than 100 mg / l, greater than 1000 mg / l, greater than 5000 mg / l, greater than 50 000 mg / l, greater than 100 000 mg / l, even greater than 300 000 mg / l; In order for the liquid to be treated to be able to form an electrolyte between the first electrically conductive material and the iron, the electrical conductivity of the liquid to be treated is preferably greater than 300 μs / cm, greater than 700 μs / cm, greater than 1 mS. / cm, greater than 100 mS / cm, or even greater than 300 mS / cm. The target is chosen from the group formed by a reservoir and a basin; In one embodiment, the liquid circulates in a closed loop in the installation. The invention finally relates to a method for treating a liquid containing an organic pollutant, said method comprising a step of treating said liquid in a treatment plant according to the invention by circulating it in said treatment device under thermod conditions igues adapted to generate cavitation and ferrous cations in said treatment device. Definitions "Oxygen constituents" are those constituents containing oxygen and capable of reacting with ferrous cations to form hydroxyl radicals. By "organic pollutant" is meant a compound whose molecule comprises at least one carbon atom and one hydrogen atom, and can be decomposed under the action of hydroxyl radicals. Unless otherwise indicated, the iron is substantially pure. The "upstream" and "downstream" positions are determined with respect to the flow direction of the liquid during its treatment. The "equivalent diameter" of a section of area A is the diameter of a circular section of identical area A. For a circular section, the equivalent diameter is equal to the diameter. The term "transverse plane" is a plane perpendicular to the main flow direction of the liquid. By "comprising one" or "comprising one", it is appropriate to include "containing at least one", unless otherwise indicated. The terms "in particular" or "no" are synonymous and not limiting. BRIEF DESCRIPTION OF THE DRAWINGS Other features and advantages of the invention will become apparent on reading the detailed description which will follow and on examining the appended drawings, provided for illustrative and non-limiting purposes. In these drawings, Figure 1 shows schematically an example of a treatment plant according to the invention; Figures 2a and 2b, 4 and 5 show in longitudinal section examples of hydrodynamic reactors that can be used in a treatment device according to the invention; and FIG. 3 represents a microbuller that can be used in a treatment device according to the invention.
    [0010] In the different figures, identical or similar members have been identified with the same references. DETAILED DESCRIPTION FIG. 1 represents an installation 10 according to the invention comprising a closed circuit 12 in which a liquid L circulates. The liquid L, preferably aqueous, is charged with an organic pollutant to be decomposed. The organic pollutant may in particular be selected from the group consisting of acetylenes, alcohols, aldehydes, alkanes, aromatic compounds, carboxylic acids, alkenes, in particular chlorinated alkenes, ketones, nitrogenous organic compounds, olefins, phenols, sulfur-containing organic compounds, and mixtures thereof. The liquid may also contain medicinal products. A target 16, in this case a pond or a reservoir of polluted water, and a treatment device 20 according to the invention are inserted in a pipe 22 of the circuit 12. The circuit 12 can be open, semi-open, or closed, as shown, with or without additional liquid, with or without bringing the liquid into contact with the atmosphere. The target is not limited. The target may be in particular in an industrial building, residential or tertiary, for example a hospital, a school or a treatment plant. The treatment device 20 comprises, from upstream to downstream, a pump 23, a microbuller 25, a hydrodic reactor 30, and a filter 32. The pump 23 is inserted upstream or downstream of the hydrodynamic reactor 30, preferably upstream. It makes it possible to circulate the liquid L. FIG. 2a schematically represents an example of a hydrodynamic reactor 30 serving as a cavitation generator and a ferrous cation generator. The hydrodynamic reactor, of longitudinal axis X, comprises a housing 111 provided with an inlet 112 and an outlet 114. Preferably, it comprises connections allowing the connection of the inlet and / or the outlet to be connected. a pipe, for example a flange provided with bolt holes adapted to cooperate with a corresponding flange of said pipe, or a male or female part to be screwed on a female or male part, respectively, of said pipe. The housing 111 contains a first reaction module successively comprising, from upstream to downstream, a first block 116, preferably of a dielectric material, an intermediate chamber 124 and second block 118 comprising, preferably anode in iron. Preferably, the housing Ill is first electrically conductive material, preferably stainless steel, and is electrically insulated from the second block 118, for example by means of an elastomer seal 119. The first and second blocks are pierced longitudinally first and second second channels, referenced 120 and 122, respectively. The first channels are preferably parallel to each other, of axis X. They can be rectilinear or not. The number of first channels is preferably greater than 3, greater than 5, greater than 10, greater than 20, greater than 30 and / or less than 200, less than 150, less than 100, less than 80, preferably less than to 60. The cross section of the channels can be arbitrary, for example circular. In one embodiment, the first channels have a substantially constant cross section along their entire length. The equivalent inner diameter of the first channels is preferably greater than 2 mm, greater than 10 mm, even greater than 15 mm or greater than 20 mm and / or less than 50 mm, less than 40 mm, less than 35 mm. An equivalent inner diameter of about 30 mm is well suited. The length of the first channels is preferably greater than 20, greater than 30 mm and / or less than 50 mm, preferably less than 40 mm. The dielectric material is preferably a plastic, for example polytetrafluoroethylene (PTFE), nylon, polypropylene, polyvinyl chloride (PVC) or a mixture of these materials. Other dielectric materials, for example ceramics, can also be used. Preferably, these materials are chosen to generate, by the circulation of the liquid, a static electrical charge by triboelectrification. PTFE is the preferred dielectric material. This dielectric material in fact prevents the liquid solid from adhering to the surface of the dielectric material. The second channels may be rectilinear or not. In particular, they can extend along the long axis Lai c device. The number of second channels is preferably greater than 2, greater than 3, greater than 5, greater than 10, greater than 20, greater than 30 and / or less than 100, less than 80, less than 60. The cross section second channels can be any, for example circular. In one embodiment, the second channels have a substantially constant cross section throughout their Tae-77. The equivalent inner diameter of the second channels is preferably greater than 2 mm, greater than 4 mm, even greater than 5 mm and / or less than 15 mm, less than 13 mm, less than 10 mm, less than 8 mm, or even less than 7 mm. In one embodiment, the equivalent inner diameter of the second channels is greater, or even 1.1, 1.5, 2, or 3 times greater than that of the first channels. The length of the second channels is preferably greater than 20 mm, greater than 30 mm and / or less than 50 mm, less than 40 mm. The second channels are delimited by an inner wall of iron disposed along the path of the liquid so as to create, by galvanic effect, for example with the first electrically conductive material of the housing, oxidation-reduction phenomena making it possible to generate cations. ferrous allowing, by reaction with oxygenated constituents present in the liquid, to generate hydroxyl radicals. The person skilled in the art knows how to determine pairs of materials making it possible to obtain such a galvanic effect. More preferably, the second block is made of said iron. Preferably, it constitutes a sacrificial anode which preferably can be replaced. The first channels open upstream, towards the inlet 112, in the upstream chamber 123, through "upstream" openings 1201 and optionally, downstream, in an intermediate chamber 124, preferably cylindrical, through "downstream" openings 1202. The upstream chamber and / or the intermediate chamber are preferably common to several first channels, or even common to all the first channels. Preferably, the first channels do not open opposite the second channels, which prevents the liquid exiting a first c and having passed through the intermediate chamber 25 to enter a second channel following a straight path. The second channels 122 (preferably all second channels) open upstream -. s the intermediate chamber 124, through "upstream" openings 1221, and downstream, to the outlet 114, in a downstream chamber 125 through "downstream" openings 1222. Preferably, the upstream chamber and / or the housing intermediate and / or the downstream chamber are not delimited by iron likely to create, by galvanic effect, for example with the first electrically conductive material of the housing, redox phenomena. One or more of them may be in particular delimited by the housing. The diameter of the upstream chamber 123 and / or the intermediate chamber 124 and / or the downstream chamber may be for example 270 mm.
    [0011] Preferably, the length of the upstream chamber and / or the c. intermediate and / or downstream chamber, measured in the direction of flow, and in the reduced coordinate system of ELILER, is greater than 0.5 * L1 and / or less than 2 * 0.5 * L1 , L1 being the length of said channels downstream of the chamber in question. Preferably, the upstream chamber and / or the c. intermediate and / or c. downstream 10 have a volume greater than 0.0001 dm3, greater than 0.001 dm3, greater than 0.01 dm3, greater than 0.1 dm3 and / or less than 20 dm3, less than 10 dm3, less than 1 dm3. The S / E ratio may be greater than 2, greater than 5, greater than 10, greater than 20, greater than. 50, greater than 100, even greater than 200 and / or less than 10-, 0, less than 500, less than 400, or even less than 300, 15 S denoting the section of the chamber considered (the intermediate chamber or downstream chamber) measured in a transverse plane immediately downstream of the region in which the channels upstream of said c. bre opens in said c. bre; E denoting the sum of the cross sections of said measured channels a transverse plane immediately upstream of the region into which they open said chamber. A high ratio of STE advantageously allows the creation of a significant counter pressure at the mouth of said channels, very effective in removing the cavitation bubbles generated in said channels. To calculate the S / E ratio, all the channels that open into said c are taken into consideration. upstream of said chamber. The ratio S'I1 ', S' denoting the section of the chamber considered (upstream chamber or intermediate chamber), measured in a transverse plane Ps' immediately upstream of the "upstream" openings of the channels which open into said chamber, upstream of said chamber; where y 'denotes the sum of the cross-sections of said channels measured in transverse plane Pz' immediately downstream of these "upstream" openings, is preferably greater than 2, greater than 5, greater than 10, greater than 20, greater than 50, greater than 100, even greater than 200 and / or less than 1000, less than 500, less than 400, or even less than 300. A high ratio of S 7E 'advantageously allows a sudden acceleration of the liquid in said channels, which is very effective for generating cavitation. The intermediate member 124 being of constant cross section, S '= S. To calculate the ratio S '/ E', all channels involved are taken into consideration.
    [0012] If the hydrodynamic reactor comprises several reaction modules, all the beans of the hydrodynamic reactor can have a ratio S /) and / or Si 'substantially identical. The hydrodynamic reactor constitutes a cavitation generator because it allows a reduction of the passage section of the liquid capable of producing a strong turbulence and a very sudden drop in the pressure in the liquid and thus create, by cavitation, bubbles, in particular air bubbles. microbubbles. To create cavitation, the hydrodynamic reactors described in patent EP-B2-680 457 or in WO 2011 033476, or in the French application filed under number 13 50513, may be envisaged. All these documents are incorporated by reference.
    [0013] The hydrodynamic reactor is also a generator of ferrous cations and hydroxyl radicals because, thanks to its iron anode, it can generate ferrous cations capable of reacting with an oxygenated component to create hydroxyl radicals. The treatment device also comprises a device for injecting, into the liquid L, an oxygenated fluid intended to react with the ferrous cations to generate hydroxyl radicals. The oxygenated fluid is preferably air and / or oxygen and / or ozone, and / or an aqueous solution of hydrogen peroxide. Preferably, the liquid is accelerated upstream of the injection, for example by means of a diaphragm 156, the reduction of the passage section being adapted to ensure, by Venturi effect, a suitable injection flow rate. Preferably, the injection device is disposed downstream of the pump 23, at a hydrodynamic reactor distance of preferably less than 1 meter, preferably less than 0.5 meter, preferably less than 0.3 meter, preferably less than at 0.1 meters. Preferably, it is disposed immediately upstream of the hydrodynamic reactor. The injection device can in particular take the form of a microbuller 25, preferably disposed upstream of the hydrodynamic reactor. The microbuller 25 can be integrated in the housing 11 or not. As shown in FIG. 3, the microbuller may comprise a porous block 152, for example sintered, for example made of stainless steel, and an injector 154, the porous block being in contact with the liquid L and the injector 152 being arranged to allow an injection of an oxygenated gas O into the circuit 12. The porosity is preferably determined to size the injected microbubbles M to have a diameter of less than 100 μm, preferably less than 75 μm, preferably less than 50 μm. .tm, and / or preferably greater than 25 lm. A treatment device according to the invention may also comprise means for separating the particles in suspension, for example decanting means or a filter 32, preferably disposed downstream of the hydrodynamic reactor. Filtration eliminates products from mineralization and / or advanced oxidation. It improves the quality of the liquids, and thus protects the equipment and limits the risk of scaling, sludging and corrosion, as well as the bio-proliferation of micro-organisms such as algae or bacteria. The filter may in particular be chosen from the group formed by a brush filter, a disk filter, a granular media filter, an ultrafiltration membrane, a nanofiltration membrane, in particular alone or downstream of a membrane of ultrafiltration, and a reverse osmosis membrane. Operation The operation of the installation described above is as follows: The liquid L is entrained by the pump 23 in the circuit 12. At the pump outlet, it is loaded with microbubbles of oxygenated fluid by the microbuller 25. In a embodiment, only air is injected by the microbuller 25. Advantageously, the oxygenated fluid injection considerably increases the generation of hydroxyl radicals. The liquid L enters the casing 11 in which its flow is modified in order to create a turbulent flow capable of locally creating cavitation.
    [0014] More specifically, the liquid to be treated enters the housing 11 through the inlet 112 (arrow F shown in Figure 2a) and the upstream chamber 123. The liquid then passes through the first channels 120 formed in the first block 116. The entry into the first channels is accompanied by a sudden acceleration of the liquid and a decrease in pressure which lead to the appearance of cavitation. The operating conditions (flow, pressure) are determined so that the relaxation causes cavitation. With a hydrodynamic reactor IONSCALE BUSTERe, the speed of the hydrodynamic reactor inlet fluid (in the upstream 123) is preferably greater than 2 m / s and / or less than 15 / ms, less than 12 m / s, less than 10 m / s, less than 8 m / s, or even less than 6 m / s, or even less than 4 m / s, and the inlet pressure of the hydrodynamic reactor is preferably greater than 1 bar and / or less than 20 bar , less than 10 bar, or even less than 5 bar. Christopher Earls Brennen's book "CAVITATION D BUBBLE DYN ICS" published by Oxoford University Press, 1995 describes the conditions for obtaining hydrodynamic cavitation. Cavitation depends on many factors, the main ones being: the voltage of the dissolved gas (s) in the liquid; - the nature and physico-chemical characteristics of the gas or gases present in the liquid; The temperature of the liquid; - the pressure of the liquid; the geometry of the hydrodynamic reactor; - the flow rate or the rate of passage of the liquid. Cavitation leads to the formation of cavitation bubbles, filled with gas, inside the liquid and / or on the boundary layer of the hydrodynamic reactor walls. Preferably, the cavitation generator is configured to generate bubbles having, for more than 50% in number, a diameter of between 25 gm and 2 mm. Advantageously, the very intense local mechanical and thermodynamic conditions generated by cavitation also lead to a destruction of microorganisms, pathogenic or not, which could be present within the liquid. In the first channels, the liquid rubs on the dielectric material. The friction of the - on the dielectric material causes the accumulation of electrostatic charges on the surface of said dielectric material, thus generating a local electrostatic field capable of favoring the following reactions: physicochemical precipitation of certain ions such as certain metal oxides, carbonates, sulphates, or phosphates; - coagulation of some p. colloidal cules. Thanks to the presence of the electrostatic effect generated by the dielectric material and the coagulation of the colloidal particles which results, the size of the colloidal particle agglomerates can reach a size sufficient for them to be retained efficiently and economically in a filter.
    [0015] The two-phase fluid then opens into the intermediate chamber 124, constitutes an implosion chamber. Indeed, the entry in intermediate bre 124 leads to a decrease in speed, a sudden increase in pressure, and a condensation inside the cavitation bubbles, which causes the implosion of a majority cavitation bubbles.
    [0016] These very sudden implosions result in the formation of shock waves which in turn generate physico-chemical or thermodyn phenomena. e ics and mechanics, like the bursting of any material lying near the imploding bubbles. Thus, during the dislocation of cavitation bubbles, very high pressures and very high local temperatures are reached: The temperature in the bubbles can thus reach values of the order of 5000 ° C and the pressure to reach values of the order of 500 kg / cm 2 (KS Suslick, Science, Vol 247, March 23, 1990, p.1439-1445). Moreover, an emulsification, homogenization and dispersion process can be obtained thanks to the kinetic energy generated by the implosions of the cavitation bubbles. These temperature and pressure conditions activate, within a bubble or in the liquid in the vicinity of said bubble, physico-chemical and thermodynamic reactions, in particular the production of hydroxyl radicals and the precipitation of inorganic salts, and in particular carbonates, sulphates and phosphates. The hydrodynamic conditions prevailing in the intermediate chamber 124 also contribute to the coagulation by ensuring a high mixing of the liquid. It is therefore particularly advantageous for the intermediate cell to be downstream of the dielectric material, which initiates coagulation. The intermediate chamber 124 separates the "downstream" openings from the first channels of the "upstream" openings of the second channels. The liquid exiting the intermediate chamber 124 thus enters the second channels 122 of the second block 118. Preferably, however, the second channels are not aligned axially with the first channels to promote turbulence and subsequent precipitation. The penetration of the liquid in the second channels 122 leads to a sudden acceleration of its speed. The transition region between the intermediate chamber 124 and the second channels 122 therefore constitutes a region of acceleration of the flow, and preferably of cavitation appearance. The "Daniell" type "battery" effect generated by the iron-stainless steel electro-galvanic couple causes a release of ferrous Fe24 cations in the liquid, due to the electrolytic reaction which is established spontaneously between the anode of iron and metals less reducing the installation, in this case the stainless steel constituting the housing. Surprisingly also, the conditions created by the implosion of cavitation bubbles increase the generation of hydroxyl radicals, i.e., the efficiency of the reaction of ferrous cations with the oxygenated component. It is therefore advantageous that the implosion of the cavitation bubbles is carried out in a region in which the ferrous cations react with the oxygenated component. The inventors have found that the implosions in the intermediate chamber have an effect on the generation of hydroxyl radicals, although the intermediate chamber is in the second of the two regions in which the ferrous cations are generated. The effectiveness of the treatment device thus makes it possible to obtain Fenton-type reactions with a limited addition of hydrogen peroxide, or even without the addition of hydrogen peroxide, which is generally considered to be harmful to health and the environment. In addition, the ferrous cations can be advantageously generated without the addition of electrical energy. In one embodiment, however, the device comprises an electric generator capable of adding ferrous cations to the liquid. The effectiveness of the treatment is improved.
    [0017] The highly reactive hydroxyl radicals then react with the molecules of the organic compounds to dissociate them, and thus reduce pollution.
    [0018] In one embodiment, an installation according to the invention comprises, downstream, upstream or bypass of the treatment device according to the invention, a biological treatment unit to further reduce pollution. At the outlet of the second block 118, the liquid enters the downstream chamber 125, which again makes it possible to implode the cavitation bubbles. After having left the hydrodynamic reactor, the liquid passes through the filter 32, which makes it possible to retain, at least in part, the particles mineralized by the advanced oxidation carried out in the hydrodynamic reactor and other particulate pollutants which could be harmful to the reactor. installation. The liquid then continues on its way to the target 16. The treatment device shown in FIG. 2a is well suited when the liquid to be treated can pass through it several times. The liquid entering the first channels is then advantageously loaded with ferrous cations. The processing device shown in Fig. 2b is an improved processing module which is a variation of the processing device shown in Fig. 2a in which the first and second blocks are inverted. This embodiment is preferred because as soon as the first liquid passage, the liquid entering the first block to undergo cavitation is already loaded with ferrous cations. The treatment device according to the invention can be used in all applications in which a liquid comprises an organic pollutant, and in particular in the aforementioned applications or described in the aforementioned patents and patent applications. As now clearly apparent, the invention provides a treatment solution by limiting the use of chemical additives, and in particular hydrogen peroxide, iron sulphate and / or iron filings conventionally introduced in Fenton processes. This solution is applicable over a wide pH range of the liquid to be treated and has been found to be p. highly effective. In particular, the housing 111 could contain a plurality of improved reaction modules, the downstream chamber of a first improved reaction module corresponding to the upstream chamber of a second improved reaction module, located immediately downstream of the first improved reaction module. Figure 4 shows a particularly advantageous embodiment. According to this embodiment, the housing 111 comprises an improved reaction module 115 coronating a second block 118 and, downstream of the second block 118, a first block 116 ', preferably substantially identical to the first block 116. The intermediate chamber 124 serves as an upstream chamber for the first block 116 '. Downstream of the first block 116 ', the hydrodynamic reactor has a downstream core 114'.
    [0019] In this embodiment, the first channels and the second channels have a longitudinal section. . e convergent, then divergent, particularly effective. This embodiment also illustrates that the number of second blocks may be different from the number of first blocks. FIG. 5 illustrates another variant of a hydrodynamic reactor according to the invention. This reactor comprises three simplified reaction modules, each simplified reaction module comprising a second iron block, referenced 118, 118 'and 118 ", the second channels being shaped to create cavitation, and an intermediate chamber referenced 124, 124 and 124 ", respectively, constituting an implosion chamber of the cavitation bubbles created in said second channels.
    [0020] Of course, the present invention is however not limited to the embodiments described and shown. In p. In particular, the number or shape of the first channels may be different from those of the second channels, the number of first blocks may be the same or different from the number of second blocks, and the number and shape of the chambers may be varied.
    [0021] The second channels may constitute implosion cells. In one embodiment, the liquid leaving the first channels enters directly into the second channels, without passing through an intermediate chamber. However, the presence of the intermediate chamber is preferable because it promotes the implosion of cavitation bubbles. Preferably, entry into the second channels results in decompression (resulting from reduction of the passage section). Preferably, this decompression is sufficient for the production of cavitation bubbles, advantageously at the very place where the ferrous cations are generated. The first channels are not necessarily made of a dielectric material. In one embodiment, the first channels are internally bounded, at least partially, preferably completely, by iron.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Device for treating a liquid (L) comprising an organic pollutant, said device comprising: a cavitation generator capable of generating, by cavitation, bubbles within said liquid, an implosion chamber of said bubbles, a generator of Fe2 + ferrous cations, - a device for injecting into the liquid, an oxygenated fluid containing an oxygenated component, the oxygenated component being able to react with ferrous Fe2 ÷ cations to generate hydroxyl radicals, the implosion chamber cavitation bubbles being disposed in a region in which the liquid contains said ferrous cations.
    [0002]
    2. Treatment device according to the preceding claim, wherein the ferrous cation generator is a "Daniell" type battery between iron and a first electrically conductive material having an electrode potential greater than iron.
    [0003]
    3. Treatment device according to any one of the preceding claims, wherein the cavitation generator and / or the ferrous cation generator are incorporated in a hydrodynamic reactor (30) having first channels (120) which open downstream in a intermediate chamber, the passage of the liquid in the first channels causing its acceleration and the generation of said bubbles, said intermediate chamber constituting said implosion chamber; second cs. ux opening upstream in said intermediate chamber, the second channels being delimited internally by iron.
    [0004]
    4. Treatment device according to any one of the preceding claims, wherein the oxygenated fluid is air and / or hydrogen peroxide and / or ozone.
    [0005]
    5. Treatment device according to any one of the preceding claims, wherein the injection device is a microbuller capable of introducing into the microbubbles F. oxygenated fluid having a diameter less than 100 kim.
    [0006]
    6. Treatment device according to any one of the preceding claims, comprising a plurality of so-called "improved" reaction modules, each improved reaction module being constituted, from upstream to downstream, by an upstream chamber (123). ) a second block comprises a plurality of second channels internally delimited, at least partially, by iron, - optionally, an intermediate chamber, a first block comprises a plurality of first channels, the passage of the liquid in the first channels causing its acceleration and the generation of cavitation bubbles, and a downstream chamber, the passage of the liquid in the downstream chamber causing its slowdown and the implosion of cavitation bubbles.
    [0007]
    7. Treatment device according to any one of the preceding claims, comprising a so-called "simplified" reaction module consisting of upstream to downstream, by a block (118, 118 ', 118 ") having channels at least p. 'delimited by iron and shaped to cause the generation of cavitation bubbles, and a bre implosion (124, 124', 124 ") disposed downstream of said channels and shaped to cause implosion of said generated cavitation bubbles in said channels at least partially delimited by iron.
    [0008]
    8. Installation for treating a liquid containing an organic pollutant, said installation comprising a circuit in which is inserted a target (16) and a treatment device (20) of said liquid leaving said target, the treatment device being in accordance with any one of the preceding claims and the liquid to be treated containing an oxygenated component capable of reacting with said ferrous cations to generate hydroxyl radicals.
    [0009]
    9. Plant according to the preceding claim, wherein the organic pollutant is selected from the group consisting of volatile organic compounds, semi-volatile, PCBs, pesticides, herbicides, dioxins, furans, explosive products and their products. degradation, humic products, dyes; and / or li, to be treated is derived from the production of oil or gas, mining, hydraulic fracturing, counting or treatment of water, drinking or otherwise; and / or the liquid to be treated has a demand for oxygen greater than 100 mg / l.
    [0010]
    A method of treating a liquid containing an organic pollutant, said method comprising a step of treating said liquid in an installation according to any one of the two immediately preceding claims by circulating it in said treatment device under thermodynamic conditions. adapted to generate cavitation and ferrous cations.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3097055B1|2019-05-22|Method for treating a liquid containing an organic pollutant
    CA2683354C|2016-08-30|Method and device for purifying liquid effluents
    KR101510608B1|2015-04-08|Liquid treatment methods and apparatus
    US8673129B2|2014-03-18|High-throughput cavitation and electrocoagulation apparatus
    CA2752732A1|2010-08-19|Method and device for scrubbing effluents liquids
    EP2945910B1|2019-03-13|Liquid treatment device
    WO2015064382A1|2015-05-07|Liquid treatment apparatus and produced water treatment method
    JP2016528022A|2016-09-15|Purification method and system for contaminated liquid and mineral slurries
    US9409800B2|2016-08-09|Electric arc for aqueous fluid treatment
    US20200399147A1|2020-12-24|Systems and methods to treat pfas and other persistent organic compounds and oxidizable matter inaqueous fluids
    FR3012129A1|2015-04-24|PROCESS AND UNIT FOR TREATING AN AQUEOUS COMPOSITION COMPRISING AT LEAST ONE POLYMER
    EP2477949B1|2015-09-09|Activated sludge treatment plant and method to destruct filamentous bacteria
    EP0459928B1|1995-05-03|Plant for treating a liquid flux in one phase contactor and recirculation de-gassing device
    Vatanpour et al.2020|A comprehensive investigation of effective parameters in continuous submerged photocatalytic membrane reactors by RSM
    CA2337268A1|2000-01-20|Device for transforming chemical structures in a fluid comprising a solvent and salts by ultrasonic action
    WO2022008621A1|2022-01-13|Device for treating a liquid
    Rastgar et al.2020|Osmotic dewatering accelerates inherent sluggish kinetics of electro-Fenton process: Toward sustainable removal of organic contaminants
    NL2021149B1|2020-01-06|Method and system for the purification of contaminated water
    Vatanpour et al.2022|Investigation of using UV/H2O2 pre-treatment process on filterability and fouling reduction of PVDF/TiO2 nanocomposite ultrafiltration membrane
    BR112016016770B1|2022-01-18|PROCESS FOR THE TREATMENT OF AN AQUEOUS LIQUID CONTAINING AN ORGANIC POLLUTANT
    CN108840483A|2018-11-20|The method and system of hydrogen sulfide is removed from waste water
    Madhu et al.2011|Sonochemical degradation of methylene blue and p-nitrophenol in aqueous medium
    同族专利:
    公开号 | 公开日
    US10486988B2|2019-11-26|
    CN106414342A|2017-02-15|
    PT3097055T|2019-08-05|
    CN106414342B|2020-05-19|
    EP3097055B1|2019-05-22|
    WO2015110967A1|2015-07-30|
    EP3097055A1|2016-11-30|
    FR3016625B1|2021-07-02|
    ES2738703T3|2020-01-24|
    US20170008779A1|2017-01-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN201567249U|2009-12-02|2010-09-01|河南理工大学|Ultrasonic electrochemical wastewater treatment device|
    WO2012161366A1|2011-05-26|2012-11-29|서울대학교산학협력단|Device for generating minute bubbles having positive electric charges and water treatment device using same|
    FR1350513A|1963-03-15|1964-01-24|Skill game|
    WO1994017000A1|1993-01-25|1994-08-04|Ion Enterprises Ltd.|Fluid treatment device and method|
    US5937906A|1997-05-06|1999-08-17|Kozyuk; Oleg V.|Method and apparatus for conducting sonochemical reactions and processes using hydrodynamic cavitation|
    US7048863B2|2003-07-08|2006-05-23|Ashland Licensing And Intellectual Property Llc|Device and process for treating cutting fluids using ultrasound|
    FR2942220B1|2009-02-16|2011-04-08|Orege|METHOD AND DEVICE FOR PURIFYING LIQUID EFFLUENTS|
    FR2950047B1|2009-09-17|2013-02-22|Isb Water|PURIFYING STATION WITH ACTIVATED SLUDGE.|
    CN202864986U|2012-06-21|2013-04-10|济南大学|Cavitation-effect-based organic wastewater treatment device|
    CN102910711B|2012-11-20|2017-05-24|沈阳工业大学|Cavitation percussion flow micro-electrolysis reactor for treating waste water and treatment method|
    US9643140B2|2014-05-22|2017-05-09|MikroFlot Technologies LLC|Low energy microbubble generation system and apparatus|CN106007075A|2016-04-27|2016-10-12|中原特种车辆有限公司|Fracturing waste fluid treatment device and method|
    RU2662498C1|2017-07-14|2018-07-26|Виталий Иванович Кияница|Method for producing drinking water from natural fresh sources|
    CN107686156B|2017-10-25|2019-10-11|四川师范大学|A kind of Fenton method of efficient degradation organic pollutants|
    CN111735494A|2020-07-02|2020-10-02|中国科学院武汉岩土力学研究所|Method for monitoring permeation increasing process of low-permeability polluted site|
    FR3112340A1|2020-07-08|2022-01-14|Grégoire PROFIT|liquid treatment device|
    CN112657495B|2020-12-22|2021-12-21|同济大学|Nano ferroferric oxide/graphene composite Fenton catalytic membrane and preparation method and application thereof|
    法律状态:
    2016-01-29| PLFP| Fee payment|Year of fee payment: 3 |
    2017-01-31| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-30| PLFP| Fee payment|Year of fee payment: 5 |
    2020-01-28| PLFP| Fee payment|Year of fee payment: 7 |
    2021-01-28| PLFP| Fee payment|Year of fee payment: 8 |
    2021-04-06| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450489A|FR3016625B1|2014-01-21|2014-01-21|LIQUID TREATMENT DEVICE|FR1450489A| FR3016625B1|2014-01-21|2014-01-21|LIQUID TREATMENT DEVICE|
    PCT/IB2015/050464| WO2015110967A1|2014-01-21|2015-01-21|Device and method for treating a liquid containing an organic pollutant|
    CN201580015426.7A| CN106414342B|2014-01-21|2015-01-21|Apparatus and method for treating liquids containing organic contaminants|
    PT15705714T| PT3097055T|2014-01-21|2015-01-21|Method for treating a liquid containing an organic pollutant|
    US15/113,382| US10486988B2|2014-01-21|2015-01-21|Device and method for treating a liquid containing an organic pollutant|
    EP15705714.2A| EP3097055B1|2014-01-21|2015-01-21|Method for treating a liquid containing an organic pollutant|
    ES15705714T| ES2738703T3|2014-01-21|2015-01-21|Procedure for treating a liquid that contains an organic pollutant|
    [返回顶部]