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WO2012107914A1 - Decontamination and sterilization device and process, in particular for food or agricultural products, fluids or industrial materials - Google Patents

Decontamination and sterilization device and process, in particular for food or agricultural products, fluids or industrial materials Download PDF

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Publication number
WO2012107914A1
WO2012107914A1 PCT/IB2012/050646 IB2012050646W WO2012107914A1 WO 2012107914 A1 WO2012107914 A1 WO 2012107914A1 IB 2012050646 W IB2012050646 W IB 2012050646W WO 2012107914 A1 WO2012107914 A1 WO 2012107914A1
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WO
WIPO (PCT)
Prior art keywords
decontamination
membranes
generator
plates
fluids
Prior art date
Application number
PCT/IB2012/050646
Other languages
French (fr)
Inventor
Marc Bonneau
Marguerite Calone-Bonneau
Original Assignee
Marc Bonneau
Marguerite Calone-Bonneau
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Marc Bonneau, Marguerite Calone-Bonneau filed Critical Marc Bonneau
Publication of WO2012107914A1 publication Critical patent/WO2012107914A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00Preservation of foods or foodstuffs, in general
    • A23B2/60Preservation of foods or foodstuffs, in general by treatment with electric currents without heating effect
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B11/00Preservation of milk or dairy products
    • A23B11/10Preservation of milk or milk preparations
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B11/00Preservation of milk or dairy products
    • A23B11/10Preservation of milk or milk preparations
    • A23B11/18Preservation of milk or milk preparations by addition of preservatives
    • A23B11/182Inorganic compounds, e.g. lactoperoxidase - H2O2 systems
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00Preservation of foods or foodstuffs, in general
    • A23B2/70Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729Organic compounds; Microorganisms; Enzymes
    • A23B2/783Microorganisms; Enzymes
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12HPASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/12Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation
    • C12H1/14Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation with non-precipitating compounds, e.g. sulfiting; Sequestration, e.g. with chelate-producing compounds
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12HPASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/12Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation
    • C12H1/16Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages without precipitation by physical means, e.g. irradiation
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y101/00Oxidoreductases acting on the CH-OH group of donors (1.1)
    • C12Y101/03Oxidoreductases acting on the CH-OH group of donors (1.1) with a oxygen as acceptor (1.1.3)
    • C12Y101/03004Glucose oxidase (1.1.3.4)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y106/00Oxidoreductases acting on NADH or NADPH (1.6)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y111/00Oxidoreductases acting on a peroxide as acceptor (1.11)
    • C12Y111/01Peroxidases (1.11.1)
    • C12Y111/01006Catalase (1.11.1.6)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y111/00Oxidoreductases acting on a peroxide as acceptor (1.11)
    • C12Y111/01Peroxidases (1.11.1)
    • C12Y111/01007Peroxidase (1.11.1.7), i.e. horseradish-peroxidase
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y302/00Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01023Beta-galactosidase (3.2.1.23), i.e. exo-(1-->4)-beta-D-galactanase

Definitions

  • the present invention relates to a device and a method for decontamination and sterilization, in particular for food or agricultural products, fluids or industrial equipment.
  • the present invention aims to overcome these disadvantages.
  • the device according to the invention comprises:
  • a first enzymatic catalysis generator arranged according to the format of a microfiltration plane module comprising an inlet and an outlet and consists of a successive and alternating stack of support plates able to support membranes, and membranes, these plates; and these membranes being clamped between the two end plates of a press filter, the faces of the support plates having grooves facilitating the turbulence of the fluids and the collection of the filtrate.
  • a second electromagnetic field generator comprising at least one magnet either in the form of plates or cartridges generating constant magnetic fields, or a solenoid electromagnet producing pulsed magnetic fields,
  • said first and second generators being configured to co-produce, particularly simultaneously or sequentially, liquid or gaseous flows of transition ionized molecules and / or free chemical radicals.
  • the invention thus consists in implementing in a combined manner a biochemical process and an electromagnetic process.
  • the inventor has thus been able to note, surprisingly, that the synergy that results from the combination of these biochemical and electromagnetic mechanisms makes it possible to obtain substrates that are practically sterile on the sanitary level.
  • This sterilization is in particular due to the hyperactive biocidal fluxes produced by the device according to the invention.
  • said first generator is an enzymatic catalysis generator, containing in fixed form enzymes belonging to the group of oxidoreductases, and producing transition ionized molecules and / or free oxygenated chemical radicals in liquid or gaseous flows.
  • Said second generator may in particular comprise at least one magnet in the form of a plate or cartridge capable of generating constant magnetic fields.
  • said second generator may comprise at least one solenoid solenoid coil capable of generating variable magnetic fields.
  • the present invention relates in particular to the use of enzymes belonging to the group of oxidoreductases.
  • peroxidases and especially lactoperoxidase (EC No. 1.1.1.7), have particularly interesting biological properties.
  • Lactoperoxidase (LP) is the essential element of a potent natural antimicrobial system which comprises two complementary components: the thiocyanate ion (SCN "), oxidizable natural substrate and hydrogen peroxide (H2O2) oxygen supplier.
  • lactoperoxidase catalyzes from hydrogen peroxide, the production of oxygen radicals and oxidized substrates according to the following reaction:
  • Oxythiocyanate + Peroxide -> Thiocyanate The super oxide anion O2 ⁇ is a powerful oxidizing agent which leads to the generation of new free radicals such as hydroxyl radicals (OH '), hydroxy-peroxyl (O2H) trioxide (O3) which are themselves converted to H2O2.
  • the oxythiocyanate OSCN "product is in equilibrium with its acid form HOSCN. In the presence of sufficient quantities of hydrogen peroxide, the oxidation reaction of the thiocyanate ion continues towards even more oxidized oxy acid derivatives according to the following reactions:
  • lactoperoxidase system has antimicrobial activities against various microorganisms such as bacteria (Staphylococci, Listeria, Colibacillus, Salmonella, Pseudomonas, Mycoplasma), protozoa (Cryptosporidia, Amoebae), and viruses (Bacteriophages).
  • One modality is to add, to the foods to be protected, the complete L.P. system, preformed with a peroxide-providing substrate, or with a complementary enzymatic system producing.
  • the application of these biocidal formulations takes place externally in the form of watering, spraying, spraying or dusting the products to be treated.
  • US Pat. No. 5,389,369 describes a bactericidal system based on the contact of a halo peroxidase with the microorganisms in the presence of hydrogen peroxide, chlorine or bromine and amino acids. The different components are prepared and stored separately until their final mixture in solution at the time of use.
  • Said first enzymatic catalysis generator entering the arrangement of the device preferably comprises synthetic membranes carrying immobilized enzymes, for example glucose-oxidase type (EC.no 1 .3.4), or catalase type (EC. No. 1 .1 1 .1 .6), or beta-galactosidase type (EC.no 3.2.1 .23), or nitrate oxidoreductase-NADPH type (EC.no.1.6.6.2.), or type xanthine oxidase (EC No. 1 .1 .3.22) or lactoperoxidase type (EC No. 1 .1 1 .1 .7.).
  • immobilized enzymes for example glucose-oxidase type (EC.no 1 .3.4), or catalase type (EC. No. 1 .1 1 .1 .6), or beta-galactosidase type (EC.no 3.2.1 .23), or nitrate oxidoreductas
  • said first generator entering the arrangement of the device comprises and furnishes, unitarily or in associated forms, one or more associated oxygen supplier compounds such as, for example, and without limitation:
  • Said second magnetic field generator produces either constant magnetic fields of intensities chosen between 0.2 to 2 Tesla or pulsed magnetic fields of variable intensities of 0.2 to 50 Tesla, with pulse frequencies of 0.2 to 500 kHz.
  • the implementation of said enzymatic catalysis generator also comprises the introduction into the chamber of one or more associated substrates such as, for example and non-exclusively, sodium iodide (NaSCN) or potassium thiocyanate (KSCN), or variously associated solutions of chemical antiseptics (hypochlorites, permanganate, sulphites, nitrites, ...) and biological antimicrobials (lysozyme, nisin, ”).
  • the enzymatic catalysis generator according to the invention is characterized by the fact that its implementation produces free radicals, alone or mixed, such as for example and without limitation:
  • This enzymatic catalysis generator according to the invention makes it possible to produce, at an acceptable cost by the industry, a continuous stream of free radicals and oxygenated chemical substrates with compositions adapted to specific applications.
  • CE P. Electric Fields Pulsed
  • C.M.C Constant Magnetic Fields
  • Pulsed C.M.P.
  • Bacterial spores appear to be more resistant than vegetative forms.
  • CMC Constant Magnetic Field
  • CM Pulsed Magnetic Field
  • CMP magnetic fields
  • CM. P. of high intensity from 5 to 50 T, and a pulse frequency between 5 and 500 kHz, allow to obtain reductions of at least 2 log of microbial populations studied in different foods (milk, yoghurt, bread ).
  • CMs. P. The energy released by the CMs. P. leads to breaks in the bonds of the molecules constituting high molecular weights (AD N), at the start of cell death and death (HOFMANN - 1 985).
  • AD N high molecular weights
  • HOFMANN - 1 985 The application of C Ms. P. Penicillium spore population growth results in changes in colony appearance, but Listeria, Escherichia and Bacillus populations show no change after the same treatment (CAUBET - 1999).
  • No. WO 85/02094 (G. HOFMANN) describes the use of pulsed magnetic fields of 5 to 50 Tesla, with a pulse frequency of 5 to 500 kHz, which significantly reduce (1, 4 to 3 , 6 log.) The number of microorganisms inoculated into food. The total exposure time is between 25 s and 10 ms. Each pulse consists of 10 oscillations. Beyond this, the intensity of the field is reduced too much (-10% after each oscillation). The observed temperature increase is 5 ° C, and the organoleptic qualities of the food are unchanged.
  • the new decontamination and sterilization device is characterized by the fact that the com bination of the enzymatic generator with the magnetic field generator makes it possible to produce liquid or gaseous flows. transitional chemical elements (ionized molecules, oxygenated free radicals and oxidized substrates) with powerful synergistic biocidal activities against viruses, bacteria, spores, fungi and protozoa.
  • biomagnetic device makes it possible to develop a new process for the decontamination and sterilization of food or agricultural products, fluids or industrial equipment, comprising the following steps:
  • transition chemical elements b) - amplifying, by fixed or continuous electromagnetic fields, the specific chemical and biological reactivities of transition chemical elements, c) - applying said transition elements, with amplified and synergistic chemical reactivities, for:
  • the device comprises a closed chamber provided with at least one enzymatic catalysis generator and at least one permanent magnetic field generator, and through which various mineral and / or organic products in liquid solutions.
  • the enzymatic generator is arranged according to the format of a microfiltration plane module comprising an inlet 1 and an outlet 5 and consists of a successive and alternating stack of support plates 2 able to support membranes. , and membranes 3, these plates 2 and these membranes 3 being clamped between the two end plates of a filter press.
  • the faces of the support plates 2 comprise grooves facilitating the turbulence of the fluids and the collection of the filtrate.
  • the membranes 3 fixed on the support plates 2 of the device according to the invention may be, preferably but not exclusively, hydrophilic nylon microfiltration membranes previously activated by a covalent grafting of enzymes.
  • the support plates 2 are preferably made of synthetic material.
  • the magnetic field generator comprises permanent magnets of two Tesia in the form of plates 6 arranged axially in a synthetic cartridge 7 having an outlet 8, and an inlet 9 connected to the output 5 of the catalytic generator. .
  • the device which is the subject of the invention makes it possible to obtain in particular a concentrated and continuous outflow of free radicals with high oxidative power and high biocidal activities with respect to microorganisms (protozoa, bacteria, viruses, fungi and molds). ) and usable for the sterilizing decontamination of various tools and industrial surfaces.
  • the inner walls of the enzymatic catalysis generator (FIG. 1) are covered with at least one nylon membrane 3 carrying immobilized enzymes in a mixture, of beta-galactosidase, glucose oxidase type. and lactoperoxidase.
  • the enzymatic mixture retained generates, from lactose, hydrogen peroxide (H2O2) according to the following reaction:
  • Glucose + Gucose oxidase -> D.gluconolactone + H2O2 Each nylon membrane carrying galactosidase, glucose oxidase and grafted peroxidase is inserted between two plates (2) (see Figurel). The membranes are permanently fixed on the plates by bringing together and pressing the end plates of the filter press. The introduction of a given volume of cow's milk, preheated to 10 degrees C, activates the enzymatic system "Galactosidase + Glucose oxidase" by endogenous milk lactose and leads to the catalytic oxidation of sodium thiocyanate (NaSCN) and potassium (KSCN) naturally present in the milk.
  • NaSCN sodium thiocyanate
  • KSCN potassium
  • OSCN oxythiocyanate
  • CMC Constant Magnetic Field
  • This embodiment of the invention and its application make it possible to obtain a prolonged storage of the milk of 12 days on average at 10 ° C.
  • the device thus constituted can be used repeatedly over several successive batches of milk for several weeks. It is easily regenerable by renewal of active membranes which makes it an effective and inexpensive device for treating and sanitizing liquid foods such as milks and dairy products, fruit juices and drinking water.
  • a possible variant of the treatment mode described above is to use radionuclides of the above-mentioned ingredients (lactoperoxidase, glucose oxidase, xanthine oxidase, etc.). from compounds supplying oxygen peroxide (glucose, sodium percarbonate, etc.) and added with nisin and then overactivated by the magnetic fields generated by the device according to the invention.
  • radionuclides of the above-mentioned ingredients lactoperoxidase, glucose oxidase, xanthine oxidase, etc.
  • the device comprises a closed chamber in which at least one generator of sulphites and free radicals, associated with at least one pulsed electric field generator (CE), is located. generated by said at least one pulsed electric field generator being of very high intensity (of the order of 35 kV / cm), in the form of pulses of very short durations (of the order of one microsecond).
  • CE pulsed electric field generator
  • the device and method according to the invention based on the use of ionic radicals and ions associated with a pulsed electric field make it possible to obtain a cold pasteurization of various liquid foodstuffs.
  • the device comprises a closed chamber in which at least one enzymatic catalysis generator is associated with at least one pulsed magnetic field generator (CM, P.) with electromagnets of variable intensity. from 5 to 50 Tesla, with a pulse frequency of 5 to 500 kHz, said enclosure being configured for a variety of fluids, solutions and products charged with free radicals to pass therethrough.
  • CM pulsed magnetic field generator
  • the flow of oxygen radicals by activated CMP obtained according to this embodiment are applied to the washing and disinfecting fruits and vegetables (including the 4 th range), herbal tea, seeds, fungi and sanitary decontamination of carcass surfaces and slaughter meat products.
  • the washing and decontamination of 4 th range salads made at 1 shower plant for 5 minutes at 10 ° C with 5 vol u my a ground ution aq ssen 2% oxidized radicals (percarbonate + thiocyanate) activated by CMP for 1 volume of plants make it possible to obtain respective reductions of 5 and 7 log. of the population of resident (Pseudomonas 105 CFU / ml) or experimental bacterial contaminants (Listeria 10.7 CFU / ml) against 3 log. on average for salads treated with CMP or washed with chlorinated water.
  • CM. P. oxidative free radicals
  • solutions of sulfur free radicals obtained by catalysis and overactivated by CM. P. can be used for spraying on the leaves of vines and potatoes, on seeds and vegetable seeds and on fruits to fight against bacteria and molds on the surface and to treat the various seasonal fungal diseases (powdery mildew, mildew , etc.).
  • CMs. P. are able to partially inactivate certain microorganisms in food.
  • CMs. P. combined with the ionized molecules and free radicals according to the invention have several technological advantages: sterilizing efficacy, low temperature increase, few organoleptic alterations, possibility of treatment through the packaging.
  • the electromagnetic generator entering the arrangement of the device according to the invention can produce either a constant magnetic field CMC (magnets in plates or cartridges), or a pulsed electric field (CEP) variable (solenoid coils of electromagnets, etc.).
  • CMC constant magnetic field
  • CEP pulsed electric field
  • the biophysical device according to the invention makes it possible to obtain a concentrated, hyperactive and continuous outflow of ionized molecules and free radicals with high oxidative power and with complete sterilizing activities for a wide range of spectrum of microorganisms (protozoa, bacteria, viruses, fungi and molds) and used in particular for the decontamination of food products (milk and milk products, meat, fruits and vegetables, drinks, ..)
  • microorganisms protozoa, bacteria, viruses, fungi and molds
  • a variant of the device according to the invention and in particular of the enzymatic generator of free radicals is also indicated in a nonlimiting manner hereinafter. It consists in using synthetic membranes carrying an enzyme mixture consisting of horseradish plant peroxidase (HRPEC No. 1 .1 .1 .1 .7), nitrate reductase (EC No. 1 .9.6.1) and nitric oxide synthetase (EC No. 1, 14.13.39).
  • the planar module comprises a proximal series of grafted nitrate reductase membrane support plates, a median series of grafted nitric oxide synthetase membrane support plates, and a terminal series of grafted peroxidase membrane support plates. .
  • the planar module is continuously fed by a pump injecting, at the inlet of the apparatus, under a pressure of 0.2 bar, a specific solution of substrates, of the following formulation:
  • KNO2 Potassium Nitrite
  • the flux coming out of the module subjected to an electromagnet CMP, of variable intensity from 5 to 50 Tesia, with a pulse frequency of 5 to 500 kHz, consists of water, hydrogen peroxide H2O2 and various radicals.
  • oxidized nitrogen such as nitrite ion (NO2 " ), nitric oxide NO “ , dinitrated trioxide (N2O3), nitrated dioxide (NO2), peroxynitrite (ONOO), hydroperoxynitrite (ONHO2), oxypermanganate MnO 5 ).
  • viruses herpes, pox, influenza, retrovirus, enterovirus, hepatitis, etc.
  • bacteria staphylococci, streptococci, listeria, E. coli, pseudomonas, lesions, bacilli, spores Certainly, fungi (fungi and molds), protozoa (amoebae, cryptosporidia, etc.).
  • the outflow also induces an oxidative reaction of the organic and metallic micropollutants and a bleaching of the organic substrates contained in the liquid effluents and in the sewage sludge.
  • the outflow can also be applied by sprinkling on fatty organic solid waste from purification plants which it causes degradation by accelerated oxidation.
  • the above device is advantageously used to oxidize volatile aromatic compounds and inorganic compounds present in fumes and industrial gases.
  • This type of application consists of injecting and diffusing and bubbling the polluted fumes and gases into a chamber through an aqueous solution of oxygen radicals. Accelerated oxidation leads to the degradation and partial or total decrease of aromatic compounds and minerals present.
  • the device according to the invention used for the treatment of natural waters polluted by agricultural pesticides such as atrazine and simazine, makes it possible to obtain an effective radical oxidation of these pollutants as well as their significant decrease in water.
  • the results obtained indicate that a single treatment of water with ozone (3 minutes at 4 mg / L) reduces the initial atrazine content by 50%.
  • the apparatus thus obtained is intended for the treatment of raw water or the regeneration and decontamination of wastewater.
  • the device according to the invention is used in circuit connected to pre-existing installations of a water treatment chain.
  • the complementary combination of the device according to the invention with these installations leads to accelerated production of oxygen free radicals and catalytic oxidation of organic and metallic micropollutants.
  • the flow of water out of the unit can be connected to an activated carbon device that fixes and retains residual organic compounds and metal oxides.
  • the generator of transition chemical elements associated with the generator of electromagnetic fields in the device according to the invention makes it possible to produce in a practical manner, from various specific chemical compositions, a continuous and hyperactive flow.
  • oxygenated radicals and oxidized substrates in the vapor or liquid phase, which can be used for the aseptization of different liquids (milk, wine, fruit juice, ovo products, water, etc.), and for the cleaning and decontamination of agricultural products, surfaces and industrial equipment as well as for the detoxification and remediation of polluted fluids (water and air) and for the destructive treatment and recycling of sewage sludge and organic waste.
  • the intensity of the magnetic fields is chosen so as to amplify the specific chemical and biological reactivities of the molecules and / or radicals generated by the generator of ionized molecules and / or free chemical radicals.

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  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The objective of the invention is to provide a device and a process for obtaining substrates that are virtually sterile in sanitary terms. To this effect, the device according to the invention comprises: - a first generator of enzymatic catalysis arranged according to the format of a flat microfiltration module comprising an inlet (1) and an outlet (5) and consisting of a successive and alternating stack of support plates (2) capable of supporting membranes, and of membranes (3), these plates (2) and these membranes (3) being squeezed between the two end plates of a filter press, the faces of the support plates (2) comprising grooves which facilitate the turbulence of the fluids and the collection of the filtrate; - a second generator of electromagnetic fields, comprising at least one magnet, either in the form of plates or cartridges producing constant magnetic fields, or a solenoid electromagnet producing pulsed magnetic fields, said first and second generators being configured so as to produce in combination, in particular simultaneously or sequentially, liquid or gas flows of ionized transition molecules and/or of free chemical radicals.

Description

DISPOSITIF ET PROCÉDÉ DE DÉCONTAMINATION ET DE STÉRILISATION, NOTAMMENT POUR DES PRODUITS ALIMENTAIRES OU AGRICOLES, DES  DEVICE AND METHOD FOR DECONTAMINATION AND STERILIZATION, IN PARTICULAR FOR FOOD OR AGRICULTURAL PRODUCTS,

FLUIDES OU DES MATÉRIELS INDUSTRIELS  FLUIDS OR INDUSTRIAL MATERIALS

La présente invention concerne un dispositif et un procédé de décontamination et de stérilisation, notamment pour des produits alimentaires ou agricoles, des fluides ou des matériels industriels.  The present invention relates to a device and a method for decontamination and sterilization, in particular for food or agricultural products, fluids or industrial equipment.

En agroalimentaire, la demande sans cesse plus pressante pour des aliments et boissons frais et naturels, dont l'innocuité est parfaitement garantie, est à l'origine du développement de nouveaux procédés physiques de stabilisation microbiologique.  In agri-food, the ever-increasing demand for fresh and natural foods and beverages, the safety of which is perfectly guaranteed, is at the origin of the development of new physical processes for microbiological stabilization.

II existe à ce jour différents dispositifs ou procédés permettant de décontaminer des produits alimentaires ou agricoles, des fluides ou des matériels industriels.  There are to date various devices or processes for decontaminating food or agricultural products, fluids or industrial equipment.

Cependant, ces dispositifs ou procédés connus ne permettent généralement pas d'éliminer la totalité des contaminants, microbiens et chimiques, éventuellement présents dans ces produits/fluides ou sur ces matériels, ou alors ne permettent d'éliminer efficacement qu'un ou plusieurs types de ces contaminants.  However, these known devices or methods generally do not allow the elimination of all the microbial and chemical contaminants possibly present in these products / fluids or on these materials, or they can effectively eliminate only one or more types of these contaminants.

La présente invention a pour objectif de remédier à ces inconvénients.  The present invention aims to overcome these disadvantages.

A cet effet, le dispositif selon l'invention comprend :  For this purpose, the device according to the invention comprises:

- un premier générateur de catalyse enzymatique agencé selon le format d'un module plan de microfiltration comportant une entrée et une sortie et est constitué d'un empilement successif et alterné de plaques de support aptes à supporter des membranes, et de membranes, ces plaques et ces membranes étant serrées entre les deux plateaux terminaux d'un filtre presse, les faces des plaques de support comportant des rainures facilitant la turbulence des fluides et la collecte du filtrat.  a first enzymatic catalysis generator arranged according to the format of a microfiltration plane module comprising an inlet and an outlet and consists of a successive and alternating stack of support plates able to support membranes, and membranes, these plates; and these membranes being clamped between the two end plates of a press filter, the faces of the support plates having grooves facilitating the turbulence of the fluids and the collection of the filtrate.

- un deuxième générateur de champs électromagnétiques, comprenant au moins un aimant soit sous forme de plaques ou de cartouches productrices de champs magnétiques constants, soit un électro aimant solénoïde producteur de champs magnétiques puisés,  a second electromagnetic field generator, comprising at least one magnet either in the form of plates or cartridges generating constant magnetic fields, or a solenoid electromagnet producing pulsed magnetic fields,

lesdits premier et deuxième générateurs étant configurés pour produire de manière combinée, notamment de façon simultanée ou séquentielle, des flux liquides ou gazeux de molécules ionisées de transition et/ou de radicaux chimiques libres. said first and second generators being configured to co-produce, particularly simultaneously or sequentially, liquid or gaseous flows of transition ionized molecules and / or free chemical radicals.

L'invention consiste ainsi à mettre en œuvre de manière combinée un processus biochimique et un processus électromagnétique. L'inventeur a ainsi pu constater, de manière surprenante, que la synergie qui résulte de la combinaison de ces mécanismes biochimique et électromagnétique permet d'obtenir des substrats pratiquement stériles sur le plan sanitaire. The invention thus consists in implementing in a combined manner a biochemical process and an electromagnetic process. The inventor has thus been able to note, surprisingly, that the synergy that results from the combination of these biochemical and electromagnetic mechanisms makes it possible to obtain substrates that are practically sterile on the sanitary level.

Cette stérilisation est notamment due aux flux biocides hyperactifs produits par le dispositif selon l'invention.  This sterilization is in particular due to the hyperactive biocidal fluxes produced by the device according to the invention.

De préférence, ledit premier générateur est un générateur de catalyse enzymatique, contenant sous forme fixée des enzymes appartenant au groupe des oxydoréductases, et produisant des molécules ionisées de transition et/ou des radicaux chimiques libres oxygénés en flux liquides ou gazeux.  Preferably, said first generator is an enzymatic catalysis generator, containing in fixed form enzymes belonging to the group of oxidoreductases, and producing transition ionized molecules and / or free oxygenated chemical radicals in liquid or gaseous flows.

Ledit deuxième générateur peut notamment comprendre au moins un aimant sous forme de plaque ou de cartouche apte à générer des champs magnétiques constants.  Said second generator may in particular comprise at least one magnet in the form of a plate or cartridge capable of generating constant magnetic fields.

De manière alternative, ledit deuxième générateur peut comprendre au moins une bobine solénoïde d'électro aimant apte à générer des champs magnétiques variables.  Alternatively, said second generator may comprise at least one solenoid solenoid coil capable of generating variable magnetic fields.

a) Le générateur de catalyse enzymatique des molécules ionisées de transition et/ou des radicaux chimiques libres.  a) The enzymatic catalysis generator of transition ionized molecules and / or free chemical radicals.

Parmi les nombreuses molécules anti microbiennes proposées sur le marché, la présente invention concerne en particulier l'utilisation des enzymes appartenant au groupe des oxydoréductases. Parmi ces enzymes les peroxydases - et notamment la lactoperoxydase (E.C. N° 1 .1 1 .1 .7), possèdent des propriétés biologiques particulièrement intéressantes. La lactoperoxydase (L.P.) constitue l'élément essentiel d'un puissant système antimicrobien naturel qui comporte deux composantes complémentaires : l'ion thiocyanate (SCN"), substrat naturel oxydable et le peroxyde d'hydrogène (H2O2) fournisseur d'oxygène. Among the many antimicrobial molecules available on the market, the present invention relates in particular to the use of enzymes belonging to the group of oxidoreductases. Among these enzymes, peroxidases, and especially lactoperoxidase (EC No. 1.1.1.7), have particularly interesting biological properties. Lactoperoxidase (LP) is the essential element of a potent natural antimicrobial system which comprises two complementary components: the thiocyanate ion (SCN "), oxidizable natural substrate and hydrogen peroxide (H2O2) oxygen supplier.

Dans ce système, en milieu liquide, la lactoperoxydase catalyse à partir du peroxyde d'hydrogène, la production de radicaux oxygénés et de substrats oxydés selon la réaction suivante :  In this system, in liquid medium, lactoperoxidase catalyzes from hydrogen peroxide, the production of oxygen radicals and oxidized substrates according to the following reaction:

SCN + H2O2 (+ L.P.) OSCN + H2O SCN + H 2 O 2 (+ LP) OSCN + H 2 O

Thiocyanate + Peroxyde -> Oxythiocyanate  Thiocyanate + Peroxide -> Oxythiocyanate

OSCN" + H2O2 + (L.P.) SCN" + H2O2 + O2 " OSCN " + H 2 O 2 + (LP) SCN " + H 2 O 2 + O 2 "

Oxythiocyanate + Peroxyde -> Thiocyanate L'anion super oxyde O2~ est un agent oxydant puissant qui conduit à la génération de nouveaux radicaux libres tels que les radicaux hydroxyles (OH"), hydroxyle-peroxyle (O2H), trioxyde (O3) qui sont eux mêmes convertis en H2O2. L'oxythiocyanate OSCN" produit est en équilibre avec sa forme acide HOSCN. En présence de quantités suffisantes de peroxyde d'hydrogène, la réaction d'oxydation de l'ion thiocyanate se poursuit vers des dérives oxyacides encore plus oxydées selon les réactions suivantes : Oxythiocyanate + Peroxide -> Thiocyanate The super oxide anion O2 ~ is a powerful oxidizing agent which leads to the generation of new free radicals such as hydroxyl radicals (OH '), hydroxy-peroxyl (O2H) trioxide (O3) which are themselves converted to H2O2. The oxythiocyanate OSCN "product is in equilibrium with its acid form HOSCN. In the presence of sufficient quantities of hydrogen peroxide, the oxidation reaction of the thiocyanate ion continues towards even more oxidized oxy acid derivatives according to the following reactions:

O2-SCN" + H2O2 O3-SCN" + H2O O2-SCN " + H2O2 O3-SCN " + H 2 O

Superoxythiocyanate + Peroxyde -> Trioxythiocyanate  Superoxythiocyanate + Peroxide -> Trioxythiocyanate

Les radicaux libres produits ainsi que les substrats oxydés interagissent fortement avec les composants biochimiques des microorganismes. Le système lactoperoxydase présente des activités antimicrobiennes vis à vis de différents microorgan ismes tels q ue des bactéries (Staphylocoques, Listeria , Col ibacil les, Salmonelles, Pseudomonas, Mycoplasmes), des protozoaires (Cryptosporidies, Amibes), et des virus (Bactériophages).  Free radicals produced as well as oxidized substrates interact strongly with the biochemical components of microorganisms. The lactoperoxidase system has antimicrobial activities against various microorganisms such as bacteria (Staphylococci, Listeria, Colibacillus, Salmonella, Pseudomonas, Mycoplasma), protozoa (Cryptosporidia, Amoebae), and viruses (Bacteriophages).

Ce système antimicrobien naturel a été repris comme modèle de préservation et de conservation du lait et des produits fromagers. Ainsi diverses modalités de conservation des produits laitiers, objets de brevets, ont été décrites au cours des dernières décennies :  This natural antimicrobial system has been used as a model for preserving and preserving milk and cheese products. Thus, various methods of preserving dairy products, patent objects, have been described in recent decades:

Une modalité consiste à ajouter, aux aliments à protéger, le système L.P. complet, préformé avec un substrat fournisseur de peroxyde, ou avec un système enzymatique complémentaire producteur. L'application de ces formulations biocides intervient de man ière extem poranée sous formes de ba in , d'aspersion , de vaporisation ou de saupoudrage des produits à traiter.  One modality is to add, to the foods to be protected, the complete L.P. system, preformed with a peroxide-providing substrate, or with a complementary enzymatic system producing. The application of these biocidal formulations takes place externally in the form of watering, spraying, spraying or dusting the products to be treated.

Ces modalités nécessitent l'utilisation de quantités d'enzymes proportionnelles aux surfaces ou aux volumes à traiter et se révèlent onéreuses et incompatibles avec les contraintes économ iques du marché. La variabil ité des d ivers paramètres environnementaux (pH, température, salinité, oxygénation) limite fortement la mise en œuvre pratique du système ainsi que son efficacité locale.  These methods require the use of amounts of enzymes proportional to the surfaces or volumes to be treated and are expensive and incompatible with the economic constraints of the market. The variability of the various environmental parameters (pH, temperature, salinity, oxygenation) strongly limits the practical implementation of the system as well as its local efficiency.

Pour pallier ces difficultés, des formulations différentes et des méthodes d'applications nouvelles ont été proposées au cours des dernières années.  To overcome these difficulties, different formulations and methods of new applications have been proposed in recent years.

• Le document N° US 5,389,369 décrit un système bactéricide basé sur le contact d'une halo peroxydase avec les micro-organismes en présence de peroxyde d'hydrogène, de chlore ou de brome et d'acides aminés. Les différentes composantes sont préparées et stockées séparément jusqu'à leur mélange final en solution au moment de l'emploi. US Pat. No. 5,389,369 describes a bactericidal system based on the contact of a halo peroxidase with the microorganisms in the presence of hydrogen peroxide, chlorine or bromine and amino acids. The different components are prepared and stored separately until their final mixture in solution at the time of use.

Le document N° WO 96/38548 décrit des compositions de peroxydases et des méthodes pour produire des solutions désinfectantes et stérilisantes stockées en containers anaérobies pressurisés et activables par l'oxygène de l'air au moment de l'emploi. Document No. WO 96/38548 describes peroxidase compositions and methods for producing disinfecting and sterilizing solutions stored in anaerobic containers pressurized and activated by oxygen in the air at the time of use.

Le document N° WO 97/15661 décrit une substance micro poreuse qui emprisonne sélectivement les micro-organismes pathogènes du sang pour les soumettre à une activité biocide de proximité générée par un système oxydatif lié à la substance micro poreuse. Document No. WO 97/15661 describes a microporous substance that selectively traps pathogenic microorganisms of the blood to subject them to a biocidal activity of proximity generated by an oxidative system linked to the microporous substance.

Ledit premier générateur de catalyse enzymatique entrant dans l'agencement du dispositif comporte de préférence des membranes synthétiques porteuses d'enzymes immobilisées, par exemple de type glucose-oxydase (EC.no 1 .1 .3.4), ou de type catalase (EC.no 1 .1 1 .1 .6), ou de type beta-galactosidase (EC.no 3.2.1 .23), ou de type nitrate oxydoréductase-NADPH (EC.no 1 .6.6.2.), ou de type xanthine-oxydase (E.C. no 1 .1 .3.22) ou de type lactoperoxydase (E.C. no 1 .1 1 .1 .7.).  Said first enzymatic catalysis generator entering the arrangement of the device preferably comprises synthetic membranes carrying immobilized enzymes, for example glucose-oxidase type (EC.no 1 .3.4), or catalase type (EC. No. 1 .1 1 .1 .6), or beta-galactosidase type (EC.no 3.2.1 .23), or nitrate oxidoreductase-NADPH type (EC.no.1.6.6.2.), or type xanthine oxidase (EC No. 1 .1 .3.22) or lactoperoxidase type (EC No. 1 .1 1 .1 .7.).

En outre ledit premier générateur entrant dans l'agencement du dispositif comporte et fournit, de manière unitaire ou sous formes associées, un ou plusieurs composés fournisseurs d'oxygène associés tels que par exemple et de façon non limitative:  Furthermore, said first generator entering the arrangement of the device comprises and furnishes, unitarily or in associated forms, one or more associated oxygen supplier compounds such as, for example, and without limitation:

- le glucose, le lactose, la xanthine,  glucose, lactose, xanthine,

- le peroxyde d'hydrogène, le peroxyde de magnésium , le percarbonate de sodium,  hydrogen peroxide, magnesium peroxide, sodium percarbonate,

- l'acide per acétique, l'ozone.  - Peracetic acid, ozone.

Ledit deuxième générateur de champs magnétiques produit soit des champs magnétiques constants d'intensités choisies entre 0,2 à 2 Tesla soit des champs magnétiques puisés d'intensités variables de 0,2 à 50 Tesla, avec des fréquences de pulsation de 0,2 à 500 kHz.  Said second magnetic field generator produces either constant magnetic fields of intensities chosen between 0.2 to 2 Tesla or pulsed magnetic fields of variable intensities of 0.2 to 50 Tesla, with pulse frequencies of 0.2 to 500 kHz.

La mise en œuvre dudit générateur de catalyse enzymatique comporte aussi l'introduction dans l'enceinte d'un ou plusieurs substrats associés tels que, par exemple et de façon non l im itative, du th iocyanate de sod ium (NaSCN ) ou de potassium (KSCN), ou des solutions diversement associées d'antiseptiques chimiques (hypochlorites, permanganate, sulfites, nitrites, ... .) et d'antimicrobiens biologiques (lysozyme, nisine, ...) Le générateur de catalyse enzymatique selon l'invention se caractérise par le fait que sa mise en œuvre produit des radicaux libres, seuls ou mélangés, tels que par exemple et de façon non limitative : The implementation of said enzymatic catalysis generator also comprises the introduction into the chamber of one or more associated substrates such as, for example and non-exclusively, sodium iodide (NaSCN) or potassium thiocyanate (KSCN), or variously associated solutions of chemical antiseptics (hypochlorites, permanganate, sulphites, nitrites, ...) and biological antimicrobials (lysozyme, nisin, ...) The enzymatic catalysis generator according to the invention is characterized by the fact that its implementation produces free radicals, alone or mixed, such as for example and without limitation:

- L'anion super oxyde 02 et trioxyde 03,  The superoxide anion 02 and trioxide 03,

- Le ra d i ca l hydroxyle OH, le radical hydroperoxyle HO2, le peroxyde d'hydrogène H2O2,  Hydroxyl radical OH, hydroperoxyl radical HO2, hydrogen peroxide H2O2,

- L'oxyde n itrique NO, le trioxyde d in itré N203, le d ioxyde n itré N02, le peroxynitrite ONOO, l'hydroperoxynitrite ONHO2, - L'oxythiocyanate OSCN, le superoxythiocyanate O2SCN, le trioxythiocyanate O3SCN,  - Nitric oxide NO, nitrite trioxide N203, nitroxide N02, peroxynitrite ONOO, hydroperoxynitrite ONHO2, - oxythiocyanate OSCN, superoxythiocyanate O2SCN, trioxythiocyanate O3SCN,

- Le dioxyde de soufre SO2, le trioxyde de soufre SO3 et son acide HSO3, Sulfur dioxide SO2, sulfur trioxide SO3 and its acid HSO3,

- L'acide hypochloreux HOCI, - Hypochlorous acid HOCI,

Ce générateur de catalyse enzymatique selon l'invention permet de produire, à un coût acceptable par l'industrie, un flux continu de radicaux libres et de substrats chimiques oxygénés aux compositions adaptées à des applications spécifiques.  This enzymatic catalysis generator according to the invention makes it possible to produce, at an acceptable cost by the industry, a continuous stream of free radicals and oxygenated chemical substrates with compositions adapted to specific applications.

b) Le générateur de champs électromagnétiques  b) The generator of electromagnetic fields

Deux technologies physiques sont largement expérimentées dans diverses filières agro-alimentaires en vue d'obtenir une stérilisation microbienne des aliments : les Champs Electriques Puisés (CE. P.), et les Champs Magnétiques Constants (C.M.C) ou Puisés (C.M.P.).  Two physical technologies are extensively tested in various agro-food chains in order to obtain microbial sterilization of food: the Electric Fields Pulsed (CE P.), and the Constant Magnetic Fields (C.M.C) or Pulsed (C.M.P.).

- Technologie des Champs Electriques Puisés (C.E.P.)  - Pulsed Electric Field Technology (C.E.P.)

Ce procédé technologique repose sur l'application d'impulsions électriques courtes (de l'ordre de la microseconde), avec une amplitude élevée de champ électrique (supérieure à 10 kV cm-1 ), à des échantillons alimentaires placés entre deux électrodes. Les C.E.P permettent d'obtenir des inactivations très variables de micro-organismes traités. Généralement il est possible de détruire partiellement les micro-organismes à la surface des aliments avec des diminutions de l'ordre de 3 à 5 log . dans des populations bactériennes. La sensibilité des micro-organismes aux CE. P. varient avec leur genre. Les bactéries à Gram positif sont moins sensibles que les bactéries à Gram négatif.  This technological process relies on the application of short electric pulses (of the order of a microsecond), with a high amplitude of electric field (greater than 10 kV cm-1), to food samples placed between two electrodes. C.E.P make it possible to obtain highly variable inactivations of treated microorganisms. Generally it is possible to partially destroy microorganisms on the surface of food with decreases of the order of 3 to 5 log. in bacterial populations. The sensitivity of microorganisms to EC. P. vary with their gender. Gram-positive bacteria are less sensitive than Gram-negative bacteria.

Les spores bactériennes semblent plus résistantes que les formes végétatives. Bacterial spores appear to be more resistant than vegetative forms.

Plusieurs paramètres tels que intensité du champ électrique, durée du traitement, nature et fréquence des impulsions et température sont susceptibles de faire varier l 'efficacité d 'u n tra itement par l es C . E . P . Le taux d' inactivation aug mente généralement si l'intensité du champ électrique augmente. Le traitement par les champs électriques puisés entraîne une élévation de température qui augmente les mécanismes d'inactivation bactérienne, mais qui peut aussi, au-delà de certaines limites, altérer certaines des caractéristiques des produits. Several parameters such as electric field intensity, treatment duration, nature and frequency of pulses and temperature are likely to vary the efficiency of a treatment by C. E. P. The inactivation rate generally increases as the intensity of the electric field increases. Treatment by pulsed electric fields causes a rise in temperature that increases the mechanisms of bacterial inactivation, but may also, beyond certain limits, alter some of the characteristics of the products.

Pure Puise Technologies (filiale de Maxwell Lab., San Diego, Californie) a déposé plusieurs demandes de brevet concernant le traitement de différentes denrées alimentaires liquides (lait, œufs liquides, jus de fruit) par champs électriques puisés.  Pure Puise Technologies (a subsidiary of Maxwell Lab., San Diego, California) has filed several patent applications for the treatment of various liquid foodstuffs (milk, liquid eggs, fruit juice) by pulsed electric fields.

- Technologie des Champs Magnétiques Constants (CMC) et des Champs Magnétiques Puisés (CM. P.) : cette technologie diffère par nature et mode d'action des champs électriques puisés.  - Constant Magnetic Field (CMC) and Pulsed Magnetic Field (CM) technology: this technology differs in nature and mode of action from pulsed electric fields.

Parmi les différentes formes de champs magnétiques, les champs magnétiques pu i sés (C M . P . ) à h aute densité de flux, laissent prévoir des perspectives d'applications intéressantes, notamment dans la décontamination des aliments.  Among the various forms of magnetic fields, the magnetic fields (CMP) with a flux density, suggest interesting applications, especially in the decontamination of food.

HOFMANN en 1985 a constaté que des CM. P. de haute intensité (de 5 à 50 T, et une fréquence de pulsation comprise entre 5 et 500 kHz, permettent d'obtenir des réductions d'au moins 2 log. des populations microbiennes étudiées dans différents aliments (lait, yaourt, pain).  HOFMANN in 1985 found that CM. P. of high intensity (from 5 to 50 T, and a pulse frequency between 5 and 500 kHz, allow to obtain reductions of at least 2 log of microbial populations studied in different foods (milk, yoghurt, bread ).

Les effets des champs magnétiques sur les micro-organismes sont aussi divers que les contextes expérimentaux à partir desquels ils ont été décrits. L'énergie libérée par les CM. P. entraîne des ruptures de liaisons des molécules constitutives de hauts poids mol écu l a i res (AD N ) , a bouti ssa nt à l ' i n h i b it ion et à l a mort cel l u l a i re (HOFMANN - 1 985). L'appl ication des C M . P . su r u ne popu l ation de spores d e Pénicillium, entraîne des modifications de l'aspect des colonies, mais des populations de Listeria, Escherichia et de Bacillus ne présentent aucune modification après le même traitement (CAUBET - 1999).  The effects of magnetic fields on microorganisms are as diverse as the experimental contexts from which they have been described. The energy released by the CMs. P. leads to breaks in the bonds of the molecules constituting high molecular weights (AD N), at the start of cell death and death (HOFMANN - 1 985). The application of C Ms. P. Penicillium spore population growth results in changes in colony appearance, but Listeria, Escherichia and Bacillus populations show no change after the same treatment (CAUBET - 1999).

Le document N° WO 85/02094 (G. HOFMANN) décrit l'utilisation de champs magnétiques puisés de 5 à 50 Tesla, d'une fréquence de pulsation de 5 à 500 kHz, qui réduisent de manière significative (1 ,4 à 3,6 log.) le nombre de micro-organismes inoculés dans des aliments. La durée d'exposition totale est comprise entre 25 s et 1 0 ms. Chaque impulsion est constituée de 1 0 oscillations. Au delà, l'intensité du champ est réd u ite de man ière trop importante (-10 % après chaque oscillation). L'augmentation de température constatée est de 5°C, et les qualités organoleptiques des aliments sont inchangées.  No. WO 85/02094 (G. HOFMANN) describes the use of pulsed magnetic fields of 5 to 50 Tesla, with a pulse frequency of 5 to 500 kHz, which significantly reduce (1, 4 to 3 , 6 log.) The number of microorganisms inoculated into food. The total exposure time is between 25 s and 10 ms. Each pulse consists of 10 oscillations. Beyond this, the intensity of the field is reduced too much (-10% after each oscillation). The observed temperature increase is 5 ° C, and the organoleptic qualities of the food are unchanged.

- Le nouveau dispositif de décontamination et de stérilisation selon l'invention se caractérise par le fa it q ue la com b ina ison du générateur enzymatique avec le générateur de champs magnétiques permet de produire des flux liquides ou gazeux d'éléments chimiques de transition (molécules ionisées , radicaux libres oxygénés et substrats oxydés,) dotés de puissantes activités synergiques biocides contre les virus, les bactéries, les spores, les fungi et les protozoaires. The new decontamination and sterilization device according to the invention is characterized by the fact that the com bination of the enzymatic generator with the magnetic field generator makes it possible to produce liquid or gaseous flows. transitional chemical elements (ionized molecules, oxygenated free radicals and oxidized substrates) with powerful synergistic biocidal activities against viruses, bacteria, spores, fungi and protozoa.

La mise en œuvre du dispositif biomagnétique selon l'invention permet de développer un nouveau procédé de décontamination et de stérilisation des produits alimentaires ou agricoles, des fluides ou des matériels industriels, comprenant les étapes suivantes consistant à :  The implementation of the biomagnetic device according to the invention makes it possible to develop a new process for the decontamination and sterilization of food or agricultural products, fluids or industrial equipment, comprising the following steps:

a) - produire, par catalyse enzymatique spécifique, une pluralité de molécules ionisées et/ou de radicaux chimiques libres de transition en flux liquides ou gazeux continus,  a) - producing, by specific enzymatic catalysis, a plurality of ionized molecules and / or free transition chemical radicals in continuous liquid or gaseous flows,

b) - amplifier, par des champs électromagnétiques fixes ou continus, les réactivités chimiques et biologiques spécifiques des éléments chimiques de transition, c) - appliquer lesdits éléments de transition, aux réactivités chimiques amplifiées et synergiques, pour :  b) - amplifying, by fixed or continuous electromagnetic fields, the specific chemical and biological reactivities of transition chemical elements, c) - applying said transition elements, with amplified and synergistic chemical reactivities, for:

- traiter des fluides industriels (eaux usées, effluents liquides, fumées, boues de décantation,...),  - treat industrial fluids (wastewater, liquid effluents, fumes, sludge, ...),

- aseptiser des produits alimentaires (eaux de boisson, vins, lait et produits laitiers, jus de fruits,) ou agricole (fruits, légumes, feuilles et tisanes, champignons, céréales et graines, carcasses et produits d'abattoirs,...),  - sanitize food products (drinking water, wine, milk and dairy products, fruit juice,) or agricultural products (fruits, vegetables, leaves and herbal teas, mushrooms, cereals and seeds, carcasses and slaughterhouse products, etc.) ,

- produire des solutions antiseptiques de lavage pour les décontaminations de surface (matériels, machines, outils, récipients, locaux industriels et hospitaliers,...). - produce antiseptic washing solutions for surface decontamination (equipment, machines, tools, containers, industrial and hospital premises, ...).

Description des formes de réalisation préférées de l'invention Description of the Preferred Embodiments of the Invention

Selon une forme de réalisation préférée mais non limitative de l'invention, le dispositif comprend une enceinte close pourvue d'au moins un générateur de catalyse enzymatique et d'au moins un générateur de champ magnétique permanent, et au travers de laquelle peuvent transiter divers produits minéraux et/ou organiques en solutions liquides.  According to a preferred but non-limiting embodiment of the invention, the device comprises a closed chamber provided with at least one enzymatic catalysis generator and at least one permanent magnetic field generator, and through which various mineral and / or organic products in liquid solutions.

En référence à la figure 1 , le générateur enzymatique est agencé selon le format d'un module plan de microfiltration comportant une entrée 1 et une sortie 5 et est constitué d'un empilement successif et alterné de plaques de support 2 aptes à supporter des membranes, et de membranes 3, ces plaques 2 et ces membranes 3 étant serrées entre les deux plateaux terminaux d'un filtre presse. Les faces des plaques de support 2 comportent des rainures facilitant la turbulence des fluides et la collecte du filtrat. Les membranes 3 fixées sur les plaques de support 2 du dispositif selon l'invention peuvent être, de façon préférée mais non exclusive, des membranes de microfiltration, en nylon hydrophile préalablement activées par un greffage covalent d'enzymes. Par ailleurs, les plaques de support 2 sont préférentiellement réalisées en matériau synthétique. With reference to FIG. 1, the enzymatic generator is arranged according to the format of a microfiltration plane module comprising an inlet 1 and an outlet 5 and consists of a successive and alternating stack of support plates 2 able to support membranes. , and membranes 3, these plates 2 and these membranes 3 being clamped between the two end plates of a filter press. The faces of the support plates 2 comprise grooves facilitating the turbulence of the fluids and the collection of the filtrate. The membranes 3 fixed on the support plates 2 of the device according to the invention may be, preferably but not exclusively, hydrophilic nylon microfiltration membranes previously activated by a covalent grafting of enzymes. Furthermore, the support plates 2 are preferably made of synthetic material.

En référence à la figure 2, le générateur de champ magnétique comprend des aimants permanents de deux Tesia sous forme de plaques 6 disposées de manière axiale dans une cartouche synthétique 7 comportant une sortie 8, et une entrée 9 reliée à la sortie 5 du générateur catalytique.  With reference to FIG. 2, the magnetic field generator comprises permanent magnets of two Tesia in the form of plates 6 arranged axially in a synthetic cartridge 7 having an outlet 8, and an inlet 9 connected to the output 5 of the catalytic generator. .

Les différents aliments (laits, jus de fruits, vins), riches en eau, en composés chimiques naturels fournisseurs d'oxygène (glucose, lactose, xanthine, etc.) et en substrats oxydables endogènes (thiocyanate SCN"), et m is en contact avec l a membrane active induisent une activation catalytique de radicaux libres oxygénés tels que l'anion super oxyde O2 et trioxyde O3, le radical hydroxyle OH et hydroperoxyle HO2, oxythiocyanate OSCN, le super-oxythiocyanate O2SCN, le trioxythiocyanate O3SCN, qui participent à une aseptisation « froide » et continue au sein des liquides alimentaires au contact. L'introduction de diverses compositions chimiques riches en molécules oxygénées et en substrats enzymatiques spécifiques, conduit à la production continue de radicaux chimiques libres oxygénés et de substrats oxydés dont la réactivité et le potentiel oxydatif vis-à-vis d'autres substrats minéraux et/ou organiques sont ensuite amplifiés et démultipliés par passage dans le générateur de champs magnétiques. The various foods (milks, fruit juices, wines), rich in water, in natural chemical compounds suppliers of oxygen (glucose, lactose, xanthine, etc.) and in endogenous oxidizable substrates (thiocyanate SCN " ), and m is in contact with the active membrane induces a catalytic activation of oxygen free radicals such as the O2 superoxide oxide and O3 trioxide, the hydroxyl radical OH and hydroperoxyl HO2, OSCN oxythiocyanate, the O2SCN super-oxythiocyanate, the O3SCN trioxythiocyanate, which participate in a "Cold" and continuous sterilization in food liquids on contact The introduction of various chemical compositions rich in oxygen molecules and specific enzyme substrates leads to the continuous production of oxygenated free radicals and oxidized substrates, the reactivity and oxidative potential vis-à-vis other mineral and / or organic substrates are then amplified and multiplied by passing through the generator of magnetic fields.

Le dispositif objet de l'invention permet d'obtenir notamment un flux sortant concentré et continu de radicaux ch imiques libres à fort pouvoir oxydatif dotés d'activités biocides élevées vis-à-vis des microorganismes (protozoaires, bactéries, virus, fungi et moisissures) et utilisables pour la décontamination stérilisante de divers outils et de surfaces industrielles.  The device which is the subject of the invention makes it possible to obtain in particular a concentrated and continuous outflow of free radicals with high oxidative power and high biocidal activities with respect to microorganisms (protozoa, bacteria, viruses, fungi and molds). ) and usable for the sterilizing decontamination of various tools and industrial surfaces.

1 ) Application au lait et produits laitiers  1) Application to milk and dairy products

Selon une forme de réalisation de l'invention, les parois intérieures du générateur de catalyse enzymatique (Figure 1 ) sont recouvertes d'au moins une membrane 3 en nylon porteuse d'enzymes immobilisées en mélange, de type beta-galactosidase, glucose-oxydase et lactoperoxydase. Le mélange enzymatique retenu génère, à partir du lactose, du peroxyde d'hydrogène (H2O2) selon la réaction suivante :  According to one embodiment of the invention, the inner walls of the enzymatic catalysis generator (FIG. 1) are covered with at least one nylon membrane 3 carrying immobilized enzymes in a mixture, of beta-galactosidase, glucose oxidase type. and lactoperoxidase. The enzymatic mixture retained generates, from lactose, hydrogen peroxide (H2O2) according to the following reaction:

Lactose + Galactosidase -> Glucose + Galactose  Lactose + Galactosidase -> Glucose + Galactose

Glucose + Gucose oxydase -> D.gluconolactone + H2O2 Chaque membrane en nylon porteuse de galactosidase, de glucose-oxydase et de peroxydases greffées, est intercalée entre deux plaques (2) (cf. Figurel ). Les membranes sont définitivement fixées sur les plaques par rapprochement et pression des plaques terminales du filtre presse. L'introduction d'un volume donné de lait de vache, préchauffé à 10 degrés C, active le système enzymatique « Galactosidase + Glucose oxydase» par le lactose endogène du lait et entraîne l'oxydation catalytique du thiocyanate de sodium (NaSCN) et de potassium (KSCN) présents naturellement dans le lait. La production d'oxythiocyanate (OSCN") antimicrobien suractivé pendant son transit (20 - 60 secondes) dans le générateur associé à Champ Magnétique Constant (CMC à 2 Tesla) permet de pratiquer une pasteurisation complète et définitive, à température ambiante, du lait reçu dans la cuve de stockage. Glucose + Gucose oxidase -> D.gluconolactone + H2O2 Each nylon membrane carrying galactosidase, glucose oxidase and grafted peroxidase is inserted between two plates (2) (see Figurel). The membranes are permanently fixed on the plates by bringing together and pressing the end plates of the filter press. The introduction of a given volume of cow's milk, preheated to 10 degrees C, activates the enzymatic system "Galactosidase + Glucose oxidase" by endogenous milk lactose and leads to the catalytic oxidation of sodium thiocyanate (NaSCN) and potassium (KSCN) naturally present in the milk. The production of oxythiocyanate (OSCN " ) antimicrobial overactivated during its transit (20 - 60 seconds) in the generator associated with Constant Magnetic Field (CMC at 2 Tesla) makes it possible to perform a complete and final pasteurization, at room temperature, the milk received in the storage tank.

Ce mode de réalisation de l'invention et son application permettent d'obtenir une conservation prolongée du lait de 12 jours en moyenne à 10°C. Le dispositif ainsi constitué peut être utilisé à répétition, sur plusieurs lots successifs de lait, pendant plusieurs semaines. Il est aisément régénérable par renouvellement des membranes actives ce qui en fait un dispositif efficace et peu coûteux pour traiter et aseptiser des aliments liquides tels que laits et produits laitiers, jus de fruits et eaux de boissons.  This embodiment of the invention and its application make it possible to obtain a prolonged storage of the milk of 12 days on average at 10 ° C. The device thus constituted can be used repeatedly over several successive batches of milk for several weeks. It is easily regenerable by renewal of active membranes which makes it an effective and inexpensive device for treating and sanitizing liquid foods such as milks and dairy products, fruit juices and drinking water.

Une variante possible du mode de traitement décrit ci-dessus consiste à utiliser d es rad i ca u x l i b res d e th iocya n ate g én érés pa r cata l yse e nzym ati q u e (lactoperoxydase, glucose oxydase, xanthine oxydase,..) à partir de composés fourn isseurs de peroxyde d'oxygène (glucose, percarbonate de sod ium, ...) et additionnés de nisine puis suractivés ensuite par les champs magnétiques générés par le dispositif selon l'invention.  A possible variant of the treatment mode described above is to use radionuclides of the above-mentioned ingredients (lactoperoxidase, glucose oxidase, xanthine oxidase, etc.). from compounds supplying oxygen peroxide (glucose, sodium percarbonate, etc.) and added with nisin and then overactivated by the magnetic fields generated by the device according to the invention.

2) Application aux vins  2) Application to wines

Selon une forme de réalisation de l'invention, le dispositif comprend une enceinte close dans laquelle sont agencés au moins un générateur de sulfites et de radicaux libres, associé à au moins générateur de champ électrique puisé (CE. P.), le champ électrique généré par ledit au moins un générateur de champ électrique puisé étant de très forte intensité (de l'ordre de 35 kV/cm), sous forme d'impulsions de très courtes durées (de l'ordre de la microseconde).  According to one embodiment of the invention, the device comprises a closed chamber in which at least one generator of sulphites and free radicals, associated with at least one pulsed electric field generator (CE), is located. generated by said at least one pulsed electric field generator being of very high intensity (of the order of 35 kV / cm), in the form of pulses of very short durations (of the order of one microsecond).

Les champs électriques puisés utilisés seuls dans le traitement des vins contaminés par des levures de type Brettanomyces conduisent à des réductions significatives des populations de levures et à une stabilisation microbiologique temporaire des vins sur quelques mois. Par contre les résultats obtenus avec le dispositif combiné selon l'invention (CE. P. associés aux sulfites) démontrent une destruction complète de la microflore du vin, avec une conservation définitive du vin traité et une réduction associée des doses de sulfites nécessaires, sans incidences qualitatives défavorables. The pulsed electric fields used alone in the treatment of wines contaminated with Brettanomyces yeasts lead to significant reductions in yeast populations and a temporary microbiological stabilization of the wines over a few months. On the other hand, the results obtained with the combined device according to the invention (CE, associated with sulphites) demonstrate a complete destruction of the microflora of the wine, with a final conservation of the treated wine and an associated reduction of the necessary sulphite doses, without adverse qualitative effects.

Le dispositif et le procédé selon l'invention, basés sur l'utilisation de radicaux l ibres et d' ions associés à un champ électrique puisé permettent d'obten ir u ne pasteurisation à froid de divers liquides alimentaires. Une série d'impulsions de très courte durée (m icrosecondes) d'u n champ électrique intense ainsi qu'un léger traitement thermique (+50 °C) complémentaire détru isent par lyse irréversible la totalité des microflores présentes dans les liquides alimentaires.  The device and method according to the invention, based on the use of ionic radicals and ions associated with a pulsed electric field make it possible to obtain a cold pasteurization of various liquid foodstuffs. A series of very short pulses (microseconds) of an intense electric field as well as a slight heat treatment (+ 50 ° C) complementary destroyed by irreversible lysis all microflora present in food liquids.

Aucune modification chimique notoire au niveau des molécules neutres ou ioniques n'est constatée, l'activité enzymatique subsiste et la composition vitaminique du produit est conservée. Toutefois, et contrairement au CEP seul, la technique du CEP associée au radicaux libres permet de détruire les spores.  No significant chemical changes in neutral or ionic molecules are observed, the enzymatic activity remains and the vitamin composition of the product is retained. However, and unlike the CEP alone, the CEP technique associated with free radicals can destroy the spores.

3) Application aux fruits, légumes et carcasses  3) Application to fruits, vegetables and carcasses

Selon une forme de réalisation de l'invention, le dispositif comprend une enceinte close dans laquelle sont agencés au moins un générateur de catalyse enzymatique associé à au moins un générateur de champ magnétique puisé (CM. P.) à électroaimants, d'intensité variable de 5 à 50 Tesla, avec une fréquence de pulsation de 5 à 500 kHz, ladite enceinte étant configurée pour que divers fluides, solutions et produits chargés de rad icaux l ibres transitent au travers d'elle. Le dispositif selon l'invention permet d'obtenir la stérilisation complète d'une suspension expérimentale  According to one embodiment of the invention, the device comprises a closed chamber in which at least one enzymatic catalysis generator is associated with at least one pulsed magnetic field generator (CM, P.) with electromagnets of variable intensity. from 5 to 50 Tesla, with a pulse frequency of 5 to 500 kHz, said enclosure being configured for a variety of fluids, solutions and products charged with free radicals to pass therethrough. The device according to the invention makes it possible to obtain complete sterilization of an experimental suspension

o  o

titrant 10 Escherichia coli contre une réduction de 5 log. pour la même suspension bactérienne traitée par CMP seul . titrating Escherichia coli against a reduction of 5 log. for the same bacterial suspension treated with CMP alone.

Ainsi, d'une manière préférentielle, non exclusive, les flux de radicaux oxygénés activés par CMP obtenus selon ce mode de réalisation sont appliqués au lavage et à la désinfection des fruits et des légumes frais (dont la 4eme gamme), des tisanes, des graines, des champignons ainsi qu'à la décontamination sanitaire des surfaces de carcasses et des produits carnés d'abattoirs. Thus, preferentially, not exclusive, the flow of oxygen radicals by activated CMP obtained according to this embodiment are applied to the washing and disinfecting fruits and vegetables (including the 4 th range), herbal tea, seeds, fungi and sanitary decontamination of carcass surfaces and slaughter meat products.

A titre d'exemple non limitatif, le lavage et la décontamination de salades de 4eme gamme effectués à raison de 1 douche des végétaux pendant 5 minutes à 10°C, avec 5 vol u mes d' u n e sol ution aq ueuse à 2 % de radicaux oxydés (percarbonate+ thiocyanate) activés par CMP pour 1 volume de végétaux, permettent d'obtenir des réductions respectives de 5 et 7 log. de la population des contaminants bactériens résidants (Pseudomonas 105 CFU/ml) ou expérimentaux (Listeria 10,7 CFU/ml) contre 3 log. en moyenne pour les salades traitées par CMP ou par lavages à l'eau chlorée. De même, une solution constituée de radicaux libres oxydatifs (H2O2+ thiocyanate) produits par catalyse enzymatique et suractivée par CM. P. est avantageusement utilisée en nébulisations pour assurer la fraîcheur des fruits et légumes après récolte, lutter contre le développement des bactéries et des moisissures de surface et augmenter ainsi la durée de conservation de ces aliments au cours de leur commercialisation. By way of non-limiting example, the washing and decontamination of 4 th range salads made at 1 shower plant for 5 minutes at 10 ° C with 5 vol u my a ground ution aq ueuse 2% oxidized radicals (percarbonate + thiocyanate) activated by CMP for 1 volume of plants, make it possible to obtain respective reductions of 5 and 7 log. of the population of resident (Pseudomonas 105 CFU / ml) or experimental bacterial contaminants (Listeria 10.7 CFU / ml) against 3 log. on average for salads treated with CMP or washed with chlorinated water. Similarly, a solution consisting of oxidative free radicals (H2O2 + thiocyanate) produced by enzymatic catalysis and overactivated by CM. P. is advantageously used in nebulisations to ensure the freshness of fruit and vegetables after harvest, fight against the development of bacteria and surface mold and thus increase the shelf life of these foods during their marketing.

A titre de deuxième exemple, la décontamination microbienne complète des surfaces de carcasses de poulets en abattoir est obtenue par pulvérisations avec une solution de radicaux libres oxydés (H2O2+nitrates) additionnée de lysozyme et suractivée par CMP. Par contre l'exposition des carcasses à un puissant traitement CEP à 1000 pulsations pendant 200 secondes, avec une lumière UV puisée à la dose totale de 5 J/cm2 ne réduit que de 2 à 2,4 log. la viabilité de Salmonella et de Listeria déposées expérimentalement en surface. As a second example, complete microbial decontamination of carcass surfaces of chickens in slaughterhouses is obtained by spraying with a solution of oxidized free radicals (H2O2 + nitrates) supplemented with lysozyme and overactivated by CMP. On the other hand, the exposure of the carcasses to a powerful CEP treatment at 1000 pulsations for 200 seconds, with a UV light pulsed at the total dose of 5 J / cm 2 reduces only 2 to 2.4 log. the viability of Salmonella and Listeria deposited experimentally on the surface.

A titre de troisième exemple d'application, des solutions de radicaux libres soufrés (thiocyanate, ion sulfite, oxyde de soufre, dioxyde de soufre, trioxyde de soufre et son acide HSO3,) obtenus par catalyse et suractivés par CM. P. peuvent être utilisées en pulvérisations sur les feuilles de vignes et de pommes de terre, sur les graines et semences de légumes et sur les fruits pour lutter contre les bactéries et les moisissures de surfaces et traiter les diverses maladies cryptogamiques saisonnières (oïdium, mildiou, etc.).  As a third example of application, solutions of sulfur free radicals (thiocyanate, sulfite ion, sulfur oxide, sulfur dioxide, sulfur trioxide and its acid HSO3,) obtained by catalysis and overactivated by CM. P. can be used for spraying on the leaves of vines and potatoes, on seeds and vegetable seeds and on fruits to fight against bacteria and molds on the surface and to treat the various seasonal fungal diseases (powdery mildew, mildew , etc.).

Les CM. P. sont capables d'inactiver partiellement certains micro-organismes dans les aliments. Les CM. P. combinées aux molécules ionisées et aux radicaux libres selon l'invention présentent plusieurs avantages technologiques : efficacité stérilisante, faible augmentation de température, peu d'altérations organoleptiques, possibilité de traitement au travers de l'emballage.  CMs. P. are able to partially inactivate certain microorganisms in food. CMs. P. combined with the ionized molecules and free radicals according to the invention have several technological advantages: sterilizing efficacy, low temperature increase, few organoleptic alterations, possibility of treatment through the packaging.

Le générateur électromagnétique entrant dans l'agencement du dispositif selon l'invention, peut produire soit un champ magnétique constant CMC (aimants en plaques ou en cartouches), soit un champ électrique puisé (CEP) variable (bobines solénoïdes d'électro-aimants, etc.).  The electromagnetic generator entering the arrangement of the device according to the invention can produce either a constant magnetic field CMC (magnets in plates or cartridges), or a pulsed electric field (CEP) variable (solenoid coils of electromagnets, etc.).

A la différence des appareils actuels générateurs de CE. P. ou de C.M.C. dont les performances antimicrobiennes stérilisantes restent variables, partielles, et aléatoires, le dispositif biophysique selon l'invention permet d'obtenir un flux sortant concentré, hyperactif et continu de molécules ionisées et de radicaux chimiques libres à fort pouvoir oxydatif et doté d'activités stérilisantes complètes vis-à-vis d'un large spectre de nnicroorganisnnes (protozoaires, bactéries ,virus, fungi et moisissures) et utilisables notamment pour la décontamination des produits alimentaires (laits et produits laitiers, viandes, fruits et légumes, boissons, ..) Unlike current CE generators. P. or CMC whose sterilizing antimicrobial performance remains variable, partial and random, the biophysical device according to the invention makes it possible to obtain a concentrated, hyperactive and continuous outflow of ionized molecules and free radicals with high oxidative power and with complete sterilizing activities for a wide range of spectrum of microorganisms (protozoa, bacteria, viruses, fungi and molds) and used in particular for the decontamination of food products (milk and milk products, meat, fruits and vegetables, drinks, ..)

4) Application aux eaux usées et boues d'épuration  4) Application to wastewater and sewage sludge

Une variante du dispositif selon l'invention et notamment du générateur enzymatique de radicaux libres est également indiquée de manière non limitative ci- après. Elle consiste à utiliser des membranes synthétiques porteuses d'un mélange d'enzymes constitué de peroxydase végétale de raifort (H.R.P. E.C. n° 1 .1 1 .1 .7,) de nitrate-réductase (E.C. n° 1 .9.6.1 ) et d'oxyde nitrique synthétase (E.C. n° 1 .14.13.39). Le module plan comporte une série proximale de plaques de support de membranes porteuses de nitrate réductases greffées, une série médiane de plaques de support de membranes porteuses d'oxyde nitrique synthétases greffées, et une série terminale de plaques de support de membranes porteuses de peroxydases greffées.  A variant of the device according to the invention and in particular of the enzymatic generator of free radicals is also indicated in a nonlimiting manner hereinafter. It consists in using synthetic membranes carrying an enzyme mixture consisting of horseradish plant peroxidase (HRPEC No. 1 .1 .1 .1 .7), nitrate reductase (EC No. 1 .9.6.1) and nitric oxide synthetase (EC No. 1, 14.13.39). The planar module comprises a proximal series of grafted nitrate reductase membrane support plates, a median series of grafted nitric oxide synthetase membrane support plates, and a terminal series of grafted peroxidase membrane support plates. .

Le module plan est al imenté de façon continue par une pompe injectant, en entrée de l'appareil, sous une pression de 0,2 bar, une solution spécifique de substrats, de formulation suivante :  The planar module is continuously fed by a pump injecting, at the inlet of the apparatus, under a pressure of 0.2 bar, a specific solution of substrates, of the following formulation:

Nitrite de potassium (KNO2) 1 g  Potassium Nitrite (KNO2) 1 g

Permanganate de potassium (KMnO4) 5 g Potassium permanganate (KMnO 4 ) 5 g

Acide peracétique (CH4CO3) 1 g Peracetic acid (CH 4 CO 3 ) 1 g

Eau q.s.p. 1000 ml  Water q.s. 1000 ml

Le flux sortant du module , soumis à un CMP à électroaimants , d'intensité variable de 5 à 50 Tesia, avec une fréquence de pulsation de 5 à 500 kHz, est constitué d'eau, de peroxyde d'hydrogène H2O2 et de divers radicaux azotés oxydés tels que l'ion nitrite (NO2"), l'oxyde nitrique NO", le trioxyde dinitré (N2O3), le dioxyde nitré (NO2), le peroxynitrite (ONOO), l'hydroperoxynitrite (ONHO2), l'oxypermanganate MnO5) . Le m éla nge d e ces d ifférents rad icaux l i b res présente d es activités antimicrobiennes instantanées et élevées contre des populations de microorganismes divers tels que des virus (herpès, pox, grippes, rétrovirus, entérovirus, hépatite...), des bactéries (staphylocoques, streptocoques, listérias, colibacilles, pseudomonas, lésionnelle, bacilles, spores...), des fungi (champignons et moisissures), des protozoaires (amibes, cryptosporidies, etc.). The flux coming out of the module, subjected to an electromagnet CMP, of variable intensity from 5 to 50 Tesia, with a pulse frequency of 5 to 500 kHz, consists of water, hydrogen peroxide H2O2 and various radicals. oxidized nitrogen such as nitrite ion (NO2 " ), nitric oxide NO " , dinitrated trioxide (N2O3), nitrated dioxide (NO2), peroxynitrite (ONOO), hydroperoxynitrite (ONHO2), oxypermanganate MnO 5 ). The release of these free radical elements presents instant and high anti-microbial activities against populations of various microorganisms such as viruses (herpes, pox, influenza, retrovirus, enterovirus, hepatitis, etc.), bacteria ( staphylococci, streptococci, listeria, E. coli, pseudomonas, lesions, bacilli, spores ...), fungi (fungi and molds), protozoa (amoebae, cryptosporidia, etc.).

Le flux sortant induit aussi une réaction oxydative des micropolluants organiques et métalliques et un blanchiment des substrats organiques contenus dans les effluents liquides et dans les boues de décantation des eaux usées. Le flux sortant peut aussi être appliqué par aspersion sur des déchets organiques solides graisseux de stations d'épuration dont il provoque la dégradation par oxydation accélérée. The outflow also induces an oxidative reaction of the organic and metallic micropollutants and a bleaching of the organic substrates contained in the liquid effluents and in the sewage sludge. The outflow can also be applied by sprinkling on fatty organic solid waste from purification plants which it causes degradation by accelerated oxidation.

De même le dispositif ci-dessus est avantageusement utilisé pour oxyder les composés aromatiques volatils et les composés minéraux présents dans les fumées et les gaz industriels. Ce type d'application consiste à injecter et à faire diffuser et barboter les fumées et les gaz pollués dans une chambre au travers d'une solution aqueuse de radicaux oxygénés. L'oxydation accélérée conduit à la dégradation et à la diminution partielle ou totale des composés aromatiques et des minéraux présents.  Similarly, the above device is advantageously used to oxidize volatile aromatic compounds and inorganic compounds present in fumes and industrial gases. This type of application consists of injecting and diffusing and bubbling the polluted fumes and gases into a chamber through an aqueous solution of oxygen radicals. Accelerated oxidation leads to the degradation and partial or total decrease of aromatic compounds and minerals present.

De même, le dispositif selon l'invention utilisé pour le traitement d'eaux naturelles polluées par des pesticides agricoles tels que l'atrazine et la simazine, permet d'obtenir une oxydation radicalaire efficace de ces polluants ainsi que leur diminution notable dans l'eau. Les résultats obtenus indiquent qu'un seul traitement habituel des eaux à l'ozone (3 minutes à 4 mg/L) permet de réduire la teneur initiale d'atrazine de 50 %. L'utilisation du dispositif selon l'invention conduit à une réduction de 90 % de l'atrazine pour une dose d'ozone égale à 1 mg/L et pour un rapport H2O2/O3 = 0,4 g/g.  Similarly, the device according to the invention used for the treatment of natural waters polluted by agricultural pesticides such as atrazine and simazine, makes it possible to obtain an effective radical oxidation of these pollutants as well as their significant decrease in water. The results obtained indicate that a single treatment of water with ozone (3 minutes at 4 mg / L) reduces the initial atrazine content by 50%. The use of the device according to the invention leads to a 90% reduction of atrazine for an ozone dose equal to 1 mg / L and for a H2O2 / O3 ratio = 0.4 g / g.

L'appareil ainsi obtenu est destiné aux traitements des eaux brutes ou à la régénération et à la décontamination des eaux usées. Pour ce faire, le dispositif selon l'invention est utilisé en circuit relié à des installations préexistantes d'une chaîne de traitement des eaux.  The apparatus thus obtained is intended for the treatment of raw water or the regeneration and decontamination of wastewater. To do this, the device according to the invention is used in circuit connected to pre-existing installations of a water treatment chain.

L'association complémentaire du dispositif selon l'invention à ces installations conduit à une production accélérée de radicaux libres oxygénés et à une oxydation catalytique des micropolluants organiques et métalliques. Le flux d'eau sortant de l'appareil peut être relié à un dispositif au charbon actif qui fixe et retient les composés organiques résiduels et les oxydes métalliques.  The complementary combination of the device according to the invention with these installations leads to accelerated production of oxygen free radicals and catalytic oxidation of organic and metallic micropollutants. The flow of water out of the unit can be connected to an activated carbon device that fixes and retains residual organic compounds and metal oxides.

Conclusions  conclusions

Le générateur d'éléments chimiques de transition( molécules ionisées et radicaux chimiques libres) , associé au générateur de champs électromagnétiques dans le dispositif selon l'invention permet de produire de manière pratique, à partir de différentes compositions chimiques déterminées, un flux continu et hyperactif de radicaux l ibres oxygénés et de substrats oxydés, en phase vapeur ou l iqu ide, utilisables pour l'aseptisation de différents liquides (laits, vins, jus de fruit, ovo produits, eaux, etc.), et pour le nettoyage et la décontamination de produits agricoles, de surfaces et de matériels industriels ainsi que pour la détoxification et l'assainissement des fluides pollués (eaux et airs) et pour le traitement destructif et le recyclage des boues d'épuration et des déchets organiques. The generator of transition chemical elements (ionized molecules and free chemical radicals), associated with the generator of electromagnetic fields in the device according to the invention makes it possible to produce in a practical manner, from various specific chemical compositions, a continuous and hyperactive flow. oxygenated radicals and oxidized substrates, in the vapor or liquid phase, which can be used for the aseptization of different liquids (milk, wine, fruit juice, ovo products, water, etc.), and for the cleaning and decontamination of agricultural products, surfaces and industrial equipment as well as for the detoxification and remediation of polluted fluids (water and air) and for the destructive treatment and recycling of sewage sludge and organic waste.

L'invention a été décrite ci-dessus en référence à des formes de réalisation données à titre de purs exemples. Il va de soi qu'elle s'étend à toutes les formes de réalisations couvertes par les revendications ci-annexées. En particulier, tout type de générateur de molécules ionisées et/ou de radicaux chimiques libres et tout type de générateur de champs électromagnétiques peuvent être utilisés, dans la mesure où :  The invention has been described above with reference to embodiments given as pure examples. It goes without saying that it extends to all forms of achievements covered by the appended claims. In particular, any type of generator of ionized molecules and / or free chemical radicals and any type of electromagnetic field generator can be used, insofar as:

- ces générateurs sont utilisés de manière combinée, notamment de manière simultanée ou séquentielle, et  these generators are used in a combined manner, in particular simultaneously or sequentially, and

- l'intensité des champs magnétiques est choisie de manière à amplifier les réactivités chimiques et biologiques spécifiques des molécules et/ou radicaux générés par le générateur de molécules ionisées et/ou de radicaux chimiques libres.  the intensity of the magnetic fields is chosen so as to amplify the specific chemical and biological reactivities of the molecules and / or radicals generated by the generator of ionized molecules and / or free chemical radicals.

Claims

REVENDICATIONS 1 . Dispositif de décontamination et de stérilisation pour des produits alimentaires ou agricoles, des fluides ou des matériels industriels, caractérisé en ce q u ' i l comprend : - un premier générateur de catalyse enzymatique agencé selon le format d'un module plan de microfiltration comportant une entrée (1 ) et une sortie (5) et est constitué d'un empilement successif et alterné de plaques de support (2) aptes à su pporter des membranes, et de membranes (3), ces plaques (2) et ces membranes (3) étant serrées entre les deux plateaux terminaux d'un filtre presse, les faces des plaques de support (2) comportant des rainures facilitant la turbulence des fluides et la collecte du filtrat.  1. Device for decontamination and sterilization for food or agricultural products, fluids or industrial equipment, characterized in that it comprises: a first enzymatic catalysis generator arranged according to the format of a microfiltration module module having an inlet ( 1) and an outlet (5) and consists of a successive and alternating stack of support plates (2) able to bear membranes, and membranes (3), these plates (2) and these membranes (3) being clamped between the two end plates of a press filter, the faces of the support plates (2) having grooves facilitating the turbulence of the fluids and the collection of the filtrate. - un deuxième générateur de champs électromagnétiques, comprenant au moins un aimant soit sous forme de plaques ou de cartouches productrices de champs magnétiques constants, soit un électro aimant solénoïde producteur de champs magnétiques puisés, lesdits premier et deuxième générateurs étant configurés pour produire de manière combinée, notamment de façon simultanée ou séquentielle, des flux liquides ou gazeux de molécules ionisées de transition et/ou de radicaux chimiques libres. a second electromagnetic field generator, comprising at least one magnet in the form of plates or cartridges generating constant magnetic fields, or a solenoid electromagnet producing pulsed magnetic fields, said first and second generators being configured to produce in a combined manner , in particular simultaneously or sequentially, liquid or gaseous flows of transition ionized molecules and / or free chemical radicals. 2. Dispositif de décontamination et de stérilisation selon la revendication 1 , caractérisé en ce que ledit premier générateur catalytique contient des membranes synthétiques (3) porteuses d'enzymes immobilisées du groupe des oxydoréductases, notamment de type glucose-oxyd a se ( EC . n o l . 1 .3.4 ) , d e type cata l a s e (EC . no l .1 1 . 1 .6) , de type beta-galactosidase EC.no3.2.1 .23), de type nitrate oxydoréductase-NAD P H . ( EC . no1 .6.6.2.), de type xanthine-oxydase (E.C. no1 .1 .3.22) et de type lactoperoxydase (E.C.nol .1 1 .1 .7.). 2. A decontamination and sterilization device according to claim 1, characterized in that said first catalytic generator contains synthetic membranes (3) carrying immobilized enzymes of the group of oxidoreductases, in particular of glucose-oxidase type (EC). 1 .3.4), of catatase type (EC No. 1-1.16), of beta-galactosidase type EC.no3.2.1.23), of nitrate oxidoreductase-NAD PH type. (EC No. 1.6.6.2), xanthine oxidase (E.C. No. 1..3.22) and lactoperoxidase (E.C.nol.1.1.7). 3. Dispositif de décontamination et de stérilisation selon la revendication 2, caractérisé en ce que les membranes (3) sont des membranes synthétiques porteuses d'un mélange d'enzymes constitué de peroxydases, de nitrate-réductases et d'oxyde nitrique synthétases, ledit module plan comportant une série proximale de plaques de support de membranes porteuses de nitrate réductases greffées, une série médiane de plaques de support de membranes porteuses d'oxyde nitrique synthétases greffées, et une série terminale de plaques de support de membranes porteuses de peroxydases greffées. 3. Decontamination and sterilization device according to claim 2, characterized in that the membranes (3) are synthetic membranes carrying an enzyme mixture consisting of peroxidases, nitrate reductases and nitric oxide synthetases, said planar module comprising a proximal series of grafted nitrate reductase-bearing membrane support plates, a median series of support plates for nitric oxide-bearing membranes grafted synthetases; and a terminal series of grafted peroxidase membrane support plates. 4. Dispositif de décontamination et de stérilisation selon les revendications 2 ou 3 caractérisé en ce en ce qu'il comporte des moyens d'introduction dans le générateur de catalyse enzymatique, en phase liquide ou gazeuse, d'un ou plusieurs composés fournisseurs d'oxygène associés tels que par exemple et de façon non limitative : 4. Device for decontamination and sterilization according to claims 2 or 3, characterized in that it comprises means for introducing into the enzymatic catalysis generator, in the liquid or gaseous phase, one or more compounds which supply oxygen associated such as for example and without limitation: - le glucose, le lactose, la xanthine, le peroxyde d'hydrogène, le peroxyde de magnésium, le permanganate de potassium, l'acide per acétique, l'ozone. glucose, lactose, xanthine, hydrogen peroxide, magnesium peroxide, potassium permanganate, peracetic acid, ozone. 5. Dispositif de décontamination et de stérilisation selon les revendications 2, 3, ou 4 caractérisé en ce qu'il comporte des moyens d"introduction dans l'enceinte d'un ou plusieurs substrats enzymatiques associés tels que par exemple et de façon non limitative; du thiocyanate de sodium (NaSCN) ou de potassium (KSCN), du bisulfite de sod ium (NaHS03), de l'hydro sulfite de sod ium (Na2S204) et du métabisulfite de sod ium (Na.2S205), des nitrites de sodium (NaN02) ou de potassium (KN02), de l'hypochlorite de sodium (NaOCI),  5. decontamination device and sterilization according to claims 2, 3 or 4 characterized in that it comprises means for introduction into the chamber of one or more associated enzyme substrates such as for example and without limitation sodium thiocyanate (NaSCN) or potassium (KSCN), sodium bisulfite (NaHSO 3), sodium hydrosulfite (Na 2 S 2 O 4) and sodium metabisulfite (Na 2 S 2 O 5), nitrites of sodium (NaNO2) or potassium (KNO2), sodium hypochlorite (NaOCI), 6. Dispositif de décontamination et de stérilisation selon les revendications 2, 3, 4, ou 5 caractérisé par le fait que sa mise en œuvre produit des radicaux libres seuls ou mélangés tels que par exemple et de façon non limitative : 6. Device for decontamination and sterilization according to claims 2, 3, 4, or 5 characterized in that its implementation produces free radicals alone or mixed such as for example and without limitation: - L'anion super oxyde 02 et trioxyde 03, - Le rad ica l h yd roxyl e O H , l e rad ica l h yd roperoxyl e H O2 , l e peroxyd e d'hydrogène H2O2,  Superoxide O 2 anion and trioxide O 3, - Radicoidal hydrogen and hydrogen radical, H 2 O 2, hydrogen peroxidized H 2 O 2, - L'oxyd e n itriq ue N O , l e trioxyde d in itré N 203, l e d ioxyde n itré N 02 , l e peroxynitrite ONOO, l'hydroperoxynitrite ONHO2, - L'oxythiocyanate OSCN, le superoxythiocyanate O2SCN, le trioxythiocyanate O3SCN, - Le dioxyde de soufre SO2, le trioxyde de soufre SO3 et son acide HSO3, - The oxidizing oxide NO, the trioxide d in itra N 203, the oxide nitre N 02, the peroxynitrite ONOO, the hydroperoxynitrite ONHO2, - the oxythiocyanate OSCN, the superoxythiocyanate O2SCN, the trioxythiocyanate O3SCN, - the dioxide of SO2 sulfur, SO3 sulfur trioxide and its HSO3 acid, - L'acide hypochloreux HOCI, - Hypochlorous acid HOCI, 7. Dispositif de décontamination et de stérilisation selon la revendication 1 , caractérisé en ce que ledit deuxième générateur de champs magnétiques produit soit des champs magnétiques constants d'intensités choisies entre 0,2 à 2 Tesia soit des champs magnétiques puisés d'intensités variables de 0,2 à 50 Tesia, avec des fréquences de pulsation de 0,2 à 500 kHz. 7. A decontamination and sterilization device according to claim 1, characterized in that said second magnetic field generator produces either constant magnetic fields of intensities chosen between 0.2 to 2 Tesia or pulsed magnetic fields of variable intensity. 0.2 to 50 Tesia, with pulse rates of 0.2 to 500 kHz. 8. Dispositif de décontamination et de stérilisation selon les revendications 1 , 2, 3, 4, 5, 6 et 7 caractérisé par le fait que la combinaison du générateur enzymatique avec le générateur de champs magnétiques permet de produire des flux liquides ou gazeux d'éléments chimiques de transition (molécules ionisées , radicaux libres oxygénés et substrats oxydés,) dotés de puissantes activités synergiques biocides contre les virus, les bactéries, les spores, les fungi et les protozoaires. 8. Device for decontamination and sterilization according to claims 1, 2, 3, 4, 5, 6 and 7 characterized in that the combination of the enzyme generator with the magnetic field generator produces liquid or gaseous flows of transitional chemical elements (ionized molecules, oxygenated free radicals and oxidized substrates) with powerful synergistic biocidal activities against viruses, bacteria, spores, fungi and protozoa. 9. Procédé de décontamination et de stérilisation des produits alimentaires ou agricoles, des fluides ou des matériels industriels, comprenant les étapes suivantes consistant à :  9. A method for decontaminating and sterilizing food or agricultural products, fluids or industrial equipment, comprising the following steps: a) - produire, par catalyse enzymatique spécifique, une pluralité de molécules ionisées et/ou de radicaux chimiques libres de transition en flux liquides ou gazeux continus,  a) - producing, by specific enzymatic catalysis, a plurality of ionized molecules and / or free transition chemical radicals in continuous liquid or gaseous flows, b) - amplifier les réactivités chimiques et biologiques spécifiques des molécules en transit par des champs électromagnétiques fixes ou continus,  b) - amplify the specific chemical and biological reactivities of the molecules in transit by fixed or continuous electromagnetic fields, c) - appliquer lesdites molécules ionisées et/ou lesdits radicaux de transition aux réactivités chimiques amplifiées et synergiques pour :  c) - applying said ionized molecules and / or said transition radicals to amplified and synergistic chemical reactivities for: - traiter des fluides industriels (eaux usées, effluents liquides, fumées, boues de décantation,...),  - treat industrial fluids (wastewater, liquid effluents, fumes, sludge, ...), - aseptiser des produits alimentaires (eaux de boisson, vins, lait et produits laitiers, jus de fruits,) ou agricole (fruits, légumes, feuilles et tisanes, champignons, céréales et graines, carcasses et produits d'abattoirs,...),  - sanitize food products (drinking water, wine, milk and dairy products, fruit juice,) or agricultural products (fruits, vegetables, leaves and herbal teas, mushrooms, cereals and seeds, carcasses and slaughterhouse products, etc.) , - produire des solutions antiseptiques de lavage pour les décontaminations de surface (matériels, machines, outils, récipients, locaux industriels et hospitaliers,...).  - produce antiseptic washing solutions for surface decontamination (equipment, machines, tools, containers, industrial and hospital premises, ...).
PCT/IB2012/050646 2011-02-11 2012-02-13 Decontamination and sterilization device and process, in particular for food or agricultural products, fluids or industrial materials WO2012107914A1 (en)

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CN107467481A (en) * 2017-09-30 2017-12-15 付军伟 Energy-saving high-frequency impulse magnetic field sterilizing equipment and its process for sterilizing
CN107494722A (en) * 2017-07-17 2017-12-22 湖南省粮油产品质量监测中心 A kind of preserving rice method of high working ratio pulse magnetic field treatment

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US5389369A (en) 1991-02-21 1995-02-14 Exoxemis, Inc. Halo peroxidase containing compositions for killing yeast and sporular microorganisms
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CN107467481A (en) * 2017-09-30 2017-12-15 付军伟 Energy-saving high-frequency impulse magnetic field sterilizing equipment and its process for sterilizing

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