WO2012020174A1 - Process and device for treating contaminated materiel - Google Patents

Abstract

Process and device for treating contaminated materiel, said materiel being thermally sensitive and/or thermally stable and/or of complex geometries, which are capable of synergistically using the variation in the causticity of a composition formed by carbon dioxide (CO₂) and caustic soda (sodium hydroxide (NaOH)) and the continuous regeneration of said composition by continuously separating the soluble and insoluble contaminants extracted by said composition, using filtration membranes, so as simultaneously to carry out operations of cleaning and inactivating all known types of infectious contaminants, including the most resistant ones, i.e. prions, without damaging the materiel.

Description

 METHOD AND DEVICE FOR PROCESSING CONTAMINATED MATERIAL DESCRIPTION

TECHNICAL AREA

 The present invention relates to a method and a device for treating contaminated materials, in particular contaminated medical devices.

 "Treatment method" means a cleaning process, a disinfection process, a prion inactivation process, a terminal sterilization process, a rinsing process, and a drying process, as described in more detail below. .

 In particular, a treatment process is understood to mean an entire sterilization process successively incorporating the stages of cleaning, disinfection and / or inactivation of the prions and endotoxins, terminal sterilization; said sterilization process further having intermediate rinsing and drying steps.

Contaminants are dirt or debris (debris of blood, stool, tissue, respiratory secretions, body fluids, other organic and inorganic matter, etc.) on the equipment as a result of an intervention, a manufacturing process or a use; on the other hand we mean by contaminants germs also called Conventional Transmissable Agents (TCAs) contained in these soils or from other sources, these are: yeasts, fungi, protozoa, bacteria in vegetative form, bacteria organized in the form of biofilm, bacterial spores, viruses, mycobacteria, algae. In addition, contaminants are proteins called prions that can be infectious like traditional microorganisms; which is really unusual, hence the name of Unconventional Communicable Agents (NCTA). These NCTAs are capable of transmitting Creutzfeldt-Jakob Disease (CJD) or its variant (vCJD), which is transmissible spongiform encephalopathy (TSE), also known as prion disease. Finally, the term "contaminants" refers to the pyrogenic components that are sources of significant fever and exist mainly on the walls of gram-negative bacteria and certain blue or green algae: these are the endotoxins. STATE OF THE PRIOR ART

 In medical, dental, veterinary etc., when treating contaminated material, it is often necessary to respond primarily to two requirements that are themselves difficult to compatible: obtaining the sterile state and maintaining integrity physical of the processed material.

 Obtaining the sterile state required is difficult because it is the result of a complex process that is to say a chain of successive actions that will allow a progressive reduction of the infectious load until said sterile condition required. If one of the steps is not correctly executed, the end result will be compromised; which would lead to infections in the hospital setting called nosocomial infections because they were caught by a subject who did not have these infections before he was in hospital. Nosocomial infections are recognized as major public health problems by their frequency, cost and severity. The risk of getting an infection in the hospital is 7-30%. These nosocomial infections are often contracted when performing certain acts for diagnostic, preventive or curative purposes requiring the use of reusable medical devices which unfortunately the sterile condition was not guaranteed due to faulty treatment.

 Despite the establishment, in health facilities, of a quality system based on normative references to improve the execution of the steps of cleaning, disinfection, inactivation of prions and / or endotoxins, terminal sterilization, rinsing and intermediate drying; the risks of nosocomial infections and damage to the physical integrity of the treated material persist due to the part of failures due to a lack of reproducibility related to the human factor and secondly because of the limitations and defects of the processes and current devices for treating contaminated materials.

The cleaning stage is decisive because it determines the quality of the following disinfection and / or sterilization procedures: existing disinfectants and sterilants are effective only on previously cleaned surfaces. After surgery to avoid corrosion of the material and drying of dirt and secretions that may promote the adhesion of microorganisms to surfaces of complex geometries and the subsequent formation of biofilm (coating or film of colonies of microorganisms that covers the surfaces of the material ), the cleaning must be done as early as possible, which is not often the case. So, bacteria or other Microorganisms secrete an adhesive and protective matrix that allows them to attach to many types of surfaces and colonize them to form biofilms. Thanks to this extracellular matrix composed of polymeric substances, biofilm bacteria are more resistant than bacteria in suspension to commonly used detergents and disinfectants. The cleaning is still and especially inefficient for several medical devices with complex geometries with areas (interstices, crevices, crevices, cracks, joints, blind holes, occluded ends, cavities, serrations, grooves, hidden microporosities etc.) incompatible with the circulation. cleaning fluid / disinfectant and thus promoting the accumulation of contaminants and the subsequent development of biofilm. This inability to penetrate complex geometries is due to the fact that aqueous solutions, in this case water, have a high surface tension. Endoscopes are a typical example of complex geometry medical devices and are increasingly used for internal exploration, biopsy and micro-invasive surgery, among others. Endoscopes have valves, long channels that are very difficult to clean manually, resulting in a result that is not always satisfactory or reproducible (incomplete brushing and / or swabbing, insufficient brushing and / or swabbing time, used brush and / or swab, inefficient detergent ). In addition some channels are very thin (internal diameter of 1 to 1.2 mm) not allowing manual cleaning by swabbing. To solve this problem, endoscope washer-disinfectors with an automatic irrigation system using connectors for cleaning the fine channels, have been proposed. But endoscope washer-disinfectors with connector systems can not effectively clean the internal lumen of the endoscope channels, especially in the presence of biofilm in the complex geometries of these channels, as evidenced by several literature documents such as that, among others, [Pajkos A, Vickery K, Cossart Y, Is biofilm accumulation on a tubing endoscope a contributor to the failure of clearing and decontamination? Journal of Hospital Infection (2004) 58, 224-229 ~ K. Marion, J. Freney, G. James, E. Bergeron, Renaud FNR, JW Costeron, Using an efficient biofilm detaching agent: an essential step for the improvement of endoscopy reprocessing protocols, Journal of Hospital Infection (2006) 64, 136-142]. On the other hand, it creates pockets of air inside the channels thus causing protected areas against the cleaning agent and / or disinfectant. Disinfection does not eliminate all germs, but only certain germs according to the known risk of an intervention. Depending on the destination of the equipment and the resistance of infectious agents to disinfection, health professionals evaluate the risk of infection on a growing scale: low risk, median risk, high risk, "prion" risk. Next, the infectious risk is evaluated as low, median, high, or very high (risk "prion"); a corresponding level of treatment is required: low-level disinfection (activity spectrum: bactericidal), intermediate-level disinfection (activity spectrum: bactericidal, fungicidal, virucidal, tuberculocidal), high-level disinfection, respectively (spectrum of activity: bactericidal, fungicidal, virucidal, tuberculocidal, mycobactericidal, sporicidal), and finally the inactivation of prions. However, the expected activity spectra of disinfectants are not often obtained for several reasons. On the one hand, the detergent or more generally the organic or inorganic materials poorly removed during the cleaning, inactivate or react with the disinfectant product; the existence of a biofilm also protects microorganisms against the action of disinfectants. Sometimes an endoscope can be manually cleaned properly but disinfected inappropriately. Indeed, a disinfectant used below its minimum concentration of effectiveness can not ensure a high level of disinfection and can pose a significant risk of nosocomial infection. Minimum concentration of effectiveness means the concentration from which the disinfectant begins to have a significant effect on the infectious contaminant. On the other hand, since the advent of prion risk, aldehyde disinfectants such as glutaraldehyde are increasingly replaced by peracetic acid, because aldehydes fix prions; however, recent studies reveal in [G. Kampf, R. Blob, H. Martiny, Surface fixation of dried blood by glutaraldehyde and peracetic acid, Journal of Hospital Infection (2004) 57, 139-143], that peracetic acid would also fix prions. In addition, the complex geometry of materials such as endoscopes generate areas that are difficult to access by aqueous disinfectants with high surface tension, which results in nosocomial infections. Finally, the lack of effective self-disinfection washer-disinfectors, leads to the formation of biofilm inside washer-disinfectors; which generates an additional source of contamination.

Prion inactivation (NCTA) is a current issue in hospitals. Prion diseases or transmissible spongiform encephalopathies (TSE) are deadly degenerative diseases of the central nervous system. There is no today screening test in humans or treatment of these diseases, and the outcome is always fatal. Indeed, various experimental studies highlight the exceptional resistance of unconventional transmissible agents (NCTAs) to the known physical and chemical inactivation processes. As a result, no routine sterilization or disinfection mode (saturated water vapor, dry heat, gamma irradiation, ethylene oxide, low temperature plasma gas, etc.) is sufficiently effective to inactivate NCTAs. The World Health Organization (WHO) recommends procedures that combine chemical and physical effects; For example, in the event of contact with the risky tissues, the heat-resistant material is treated by immersion in 1M sodium hydroxide or 2% sodium hypochlorite (bleach) for 1 hour followed by steam sterilization. ° C for 18 minutes; and the thermosensitive material is treated by immersion in 2M sodium hydroxide for 1 hour followed by a low temperature sterilization or disinfection.

 But these recommendations have many disadvantages and constraints:

 - corrosive conditions for the equipment (too long immersion time);

 - the exposure of hospital staff not only to the risks of contamination but also to dangerous solvents that must be further prepared as and before each use.

 On the other hand, these WHO recommendations for the inactivation of prions do not take into account complex geometries that are difficult to access; because aqueous solutions can not reach anfractuosities because of their high surface tension. However, very recently, a new risk of prion transmission by endoscopes (example type of instruments with complex geometry) has been identified.

In fact, for Creutzfeldt-Jakob Disease (CJD) and vCJD, the tissues at risk are: the central nervous system, the eye and the optic nerve, the organized lymphoid formations with germinal centers at the spleen, lymph nodes, tonsils, appendix, Peyer's plate, and equivalent formations of the large intestine, rectum, and aero-digestive junction. Because of this, flexible endoscopy is an act possibly contaminating the variant Creutzfeldt-Jakob Disease (vCJD) because of the passage of the aero-digestive junction, the poorly known dissemination of lymphoid formations, the difficulty of knowing if the act is at risk or not (contact with ulceration or involuntary break-in, treatment of patients at risk but without any particular characteristic). All Flexible endoscopes that can not withstand steam sterilization are concerned: gastroscopy, colonoscopy (and biopsy), ENT, bronchoscopy, laryngoscopy, urology, etc.

 In addition, the inactivation of prions is not done systematically; it is done only when the treated patient is suspected of having a prion disease. This situation may result in a healthy carrier not being identified resulting in a significant risk of infection. It therefore seems important to have a process that by default inactivates prions whatever the patient.

 Rinsing removes residues of detergent or disinfectant. The problem with rinsing is that it is often a source of recontamination and / or corrosion of the disinfected material when the rinsing water is not sufficiently sterile or demineralized. On the other hand, when the intermediate rinsing (s) is (are) defective this generates the problem of incompatibility between the detergent (s) and the disinfectant (s). Finally, if the final rinsing is defective, it can persist on the material of toxic residual detergents or disinfectants. These toxic residual agents often cause biocompatibility problems (non-compatibility with biological tissues leads to rejection problems) even after terminal sterilization. These toxic agents are all the more difficult to remove when it comes to medical devices with complex and thermosensitive geometries.

 Drying is often defective because of areas of water retention especially when it comes to heat-sensitive instruments that are difficult to dry and complex like flexible endoscopes; and this often leads to the proliferation of hydrophilic microorganisms. In addition, the external hot air can be a source of recontamination of the disinfected material due to lack of sterility. [Lawrence F. Muscarella, Inconsistencies in endoscope-reprocessing and infection-control guidelines: The importance of endoscopic drying, American Journal of Gastroenterology (2006) 101, 2147-2154], largely describes the risks associated with poor drying. With regard to the physical integrity of the equipment, traditional drying methods have the major disadvantage of deteriorating fragile materials during the liquid-gas phase transition.

Terminal sterilization can kill all types of conventional transmissible agents (ATC) and if possible maintain the sterile condition in a package until use. The sterility state is considered to be reached when the theoretical probability that a viable microorganism is present on a device is equal or less than 1/10 ⁶ : this is the sterility assurance level. According to standards NF EN ISO 9001 and NF EN ISO 9002 as well as the standards NF EN 46001, NF EN 46002, ISO 1138 and ISO 14937 sterilization is part of special processes for which the results can not be fully verified by a control final product made retrospectively; hence the obligation to achieve a level of sterility insurance. As a result, obtaining a high level of disinfection is not sufficient to say that a process is a terminal sterilization process. It is necessary that this process, as a precautionary principle, can kill on its own, apart from the cleaning and disinfection steps, the totality of an initial charge of 10 ⁶ spores up to a probability of existence of living microorganism equal to 10 ^'6 ; said spores being the most resistant forms of bacteria. Knowing the duration (D) necessary to inactivate 90% of an initial charge of 10 ⁶ spores, the duration of the terminal sterilization process must be at least 12 times this duration D to be able to reach the level of assurance of sterility of 10 ^{". 6} is a reduction of 12 Logs As soon as the duration of the terminal sterilization process is determined, it is routinely validated that a probability of existence of living microorganism equal to ^10-6 is reached by a reduction of at least 6 Log an initial load of 10 ⁶ spores present on biological indicators that did not undergo the previous cleaning and disinfection steps. A reduction greater than or equal to 6 Log on biological indicators of initial charge of 10 ⁶ is not necessarily a sterilization and can be only a high-level disinfection if the treatment time required to obtain a probability of existence of microorganism . living equal to 10 ^"6 is not reached We can not use any type of spores to validate a sterilization process; it requires specific and wrapped biological indicators; the shell providing an additional constraint. Thus, several processes which by abuse of language are called terminal sterilization processes are only disinfection processes, and at the very end, high level disinfection processes.

 The usual terminal sterilization methods are all limited in their application.

Steam sterilization, while being the standard in hospital sterilization, is incompatible with temperature-sensitive instruments such as flexible endoscopes. Steam sterilization saturated water also requires a long drying time and several repeated vacuum operations to eliminate any presence of air, because the air decreases the thermal effect and especially the wetting and hydrolyzing power of the saturated water vapor; hence a strong loss of the sterilizing power of saturated water vapor. Despite the repeated vacuum operations, however, we often face problems of poor diffusion of water vapor because of the presence of hidden residual air in the complex geometries of rigid endoscopes, for example. It is also sometimes formed supersaturated water vapor, which is a vapor too wet; this results in excessive wetting leading to defective drying. In addition, it is necessary that the water used is demineralized and highly purified by reverse osmosis or it is formed after drying various colorations, corrosive salt deposits such as chlorides, rust deposits, scale deposits and deposits. water rings.

 Ethylene oxide, a sterilizing agent that is compatible with thermosensitive instruments, is toxic, flammable, carcinogenic and requires, after a treatment time of at least 2 hours, long hours (12 to 24 hours) of degassing and desorption; which is not practical for the rapid reprocessing of endoscopes in hospitals. Ethylene oxide is also ineffective on prions.

Hydrogen Peroxide (H ₂ O ₂ ) Plasma Sterilization is a recent sterilization process for thermosensitive materials that requires less treatment time (75 minutes to 3 hours) than ethylene oxide sterilization; but it is incompatible with paper packaging (hydrogen peroxide vapors are strongly adsorbed by cellulose-containing materials), is inefficient for long (310 mm to 2 m) or narrow channels (1 to 1 diameters) , 2 mm) endoscopes for example, is inactive on prions and requires a very high initial vacuum about a hundred times more than in a steam sterilizer. On the other hand, because of the short life span of the plasma chemical species, it is impossible to create a plasma state in a large volume; the volume of the standard sterilization chamber is therefore limited to 70 liters.

 Gamma sterilization, while effective, destroys the mechanical properties of polymeric materials and can not be practiced in hospitals because it requires not very convenient infrastructure.

Sterilization can also be done cold by soaking in a chemical product and is performed on clean, critical or semi-critical thermosensitive material. It does not require conditioning to maintain the sterile condition; it nevertheless requires long hours of soaking (10 hours for glutaraldehyde 3.5% to 25 ° C, 5 hours for peracetic acid 7% at 25 ° C, to hope a reduction of an initial charge of 10 ⁶ spores up to a probability of existence of live microorganism equal to 10 ^"6 ) and the management of the quality of the rinsing water not to recontaminate the treated material However there is no guarantee of the process that is to say there is no means to control the effectiveness of the sterilization For example, liquid sterilization is entirely dependent on the operator and therefore not always reproducible and under these conditions the operator is exposed to dangerous solvents and the material is quickly corroded.

 It should also be noted that all of the various methods for terminating sterilization mentioned above are very limited as regards the ability to sterilize inaccessible places (small gaps, crevices, cracks, blind holes, cavities and other hidden porosities) of endoscopes, for example, and fail. in the presence of biofilm or organic or inorganic residues.

To remedy the problems of thermosensitive materials and complex geometries difficult to access, it has been proposed the treatment of contaminated material with dense fluids under pressure or dense fluids. Dense fluids under pressure or dense fluids are fluids which under pressure and depending on the temperature are in the gaseous, solid, liquid or supercritical state. The supercritical state is obtained beyond a critical point characterized by a critical temperature, and a critical pressure. Supercritical fluids behave like a gas-liquid hybrid and thus have a very low viscosity and a very low surface tension, a high diffusivity and a modulable density. The very low surface tensions and viscosity of dense fluids in the liquid or supercritical state allow them to penetrate into hard-to-reach places (interstices, crevices, crevices, cracks, joints, blind holes, occluded ends, cavities, serrations, grooves, hidden microporosities etc.). The very high diffusivity results in a large mass transfer. Among the dense fluids in the liquid or supercritical state, the best known and used is carbon dioxide (C0 ₂ ). Indeed, when the carbon dioxide (C0 ₂ ) produced by industries is released into the atmosphere; as a greenhouse gas it poses problems on a global scale; but when it is captured rather than rejected, it is used inter alia in its liquid state, or supercritical as a non-toxic and ecological solvent (non-emission of Volatile Organic Compounds (VOC), non-pollution of the water table, non-destruction of the ozone layer, carbon dioxide (C0 ₂ ) is easily recyclable). In addition, carbon dioxide (C (¼) as solvent is non-toxic, chemically inert, odorless, colorless, highly pure, tasteless, non-flammable, abundant and cheap, has low critical temperature and pressure, has a Modulable solvent power, does not leave residual solvent and does not require a drying step.

Since 1987, one of the first studies concerning attempts to sterilize microorganisms by gaseous, liquid or supercritical carbon dioxide (C0 ₂ ) has been known; it is the document of Masamichi KAMIHIRA, et al., "Sterilization of Microorganisms with Supercritical Carbon Dioxide", Agricultural and Biological Chemistry Vol.51, No.2 (1987) pp.407-412. The authors of this study used gaseous, liquid or supercritical carbon dioxide (C0 ₂ ) and came to the conclusion that although liquid or supercritical carbon dioxide (C0 ₂ ) can inactivate viruses quickly and effectively and the vegetative forms of bacteria it is only in the supercritical state that the carbon dioxide (CO ₂ ) had a sporicidal effect which nevertheless remains insufficient. In fact, carbon dioxide (CO ₂ ) alone in the supercritical state hardly inactivates the most resistant forms of bacteria, ie spores, without recourse to very high temperatures and pressures, and therefore to large energy consumption and for a very long treatment time greater than 24 hours. The authors of this study also used supercritical carbon dioxide (C0 ₂ ) with additives such as water and other chemical additives, in this case disinfectants / sterilizers, and came to the conclusion that the effect Supercritical carbon dioxide (C0 ₂ ) sterilant is further optimized by addition of disinfectants / sterilizers such as ethanol at 2% by weight of the composition or acetic acid at 0.5% by weight. weight of the composition. But despite the addition of disinfectants / sterilizers, it takes about 3.6 hours to inactivate 90% of the initial charge or 43.2 hours to reach a probability of living microorganism equal to 10 ^"6 , a The challenge for those skilled in the field of supercritical carbon dioxide (C0 ₂ ) sterilization is therefore to find additives capable of acting in synergy with carbon dioxide (C0 ₂ ). supercritical to effectively and quickly sterilize the contaminated material up to a probability of existence of live microorganism equal to 10 ^"6 , a reduction of 12 Log. To ensure the safety of the patient on whom the treated material will be used, these additives and / or their decomposition products must be on the other hand, to be non-toxic if not easily extractable, biocompatible and, moreover, these additives must preserve the physical integrity of the material treated.

However, currently the only additives known from US-A-5213619, US-A-200703432 and WO-A-200708618 make it difficult to achieve for a generally long time (4 hours) a reduction of 6 Logs on biological indicators with the supercritical carbon dioxide (C0 ₂ ) and this generally on unpackaged material; however, the packaging adds an additional constraint and it would require a reduction of 12 Log corresponding to a probability of living microorganism equal to or greater than 10 ^-6 to pretend to have sterilized the material.These additives are for the most part oxidants such as as hydrogen peroxide, peracetic acid, trifluoroacetic acid which are especially highly corrosive to material having brass, copper, aluminum, carbon steel, polyurethane, nylon etc. components, so the longer the treatment time the more the corrosion risks increase, but no means in the prior art are provided to remedy this problem, and strong oxidizers such as peroxides tend to bind the bacteria to the surfaces of the material rather than the in addition, the trifluoroacetic acid is scarce and its toxicological effect is little known.It should also be recalled that according to the document G. Kampf, R. Blob, H. Martiny, "Surface fixation of dried blood by glutaraldehyde and peracetic acid" Journal of Hospital Infection (2004) 57, 139-143, that peracetic acid would also fix prions; which is a major drawback. On the other hand, using hydrogen peroxide which is the least corrosive oxidative additive among those mentioned above, it usually takes at least 4 hours to inactivate 10 ⁶ spores with hydrogen peroxide (¾ (¼)) as a supercritical carbon dioxide (C0 ₂ ) additive, ie at least 8 hours to reach a lifetime probability of living microorganism equal to 10 ^-6 , this time is shorter than the total time required for the oxide sterilization ethylene but still remains too long for rapid reprocessing of contaminated material such as endoscopes in hospitals.

On the other hand, like other existing sterilization systems these supercritical carbon dioxide (C0 ₂ ) sterilization processes require prior cleaning of medical devices by conventional devices and technologies to remove as much dirt and grime as possible. coarse contaminants; supercritical carbon dioxide (C0 ₂ ) being used only for the sterilization of macroscopically clean material but having residual contaminants at the scale microscopic. However, traditional cleaning systems used in health care facilities do not eliminate biofilms and strongly adhered proteins, especially in inaccessible places and sometimes even in accessible places; macroscopically clean and dry material may therefore have strongly adhered biofilms and proteins difficult to remove by liquid or supercritical carbon dioxide (C0 ₂ ).

Indeed, in general, the dense fluids under pressure such as liquid or supercritical carbon dioxide (C0 ₂ ), although easily penetrating the complex geometries, solubilize on the one hand, very difficultly macromolecular contaminants and other Very difficult solubilize polar contaminants when they themselves are apolar, or very difficult solubilize nonpolar contaminants when they are themselves polar. For example, compounds of high molecular weight such as amino acids, proteins, polymers, viscous oils and especially polar compounds are indeed very slightly soluble in carbon dioxide (C0 ₂ ) liquid or supercritical. Thus dense fluids such as liquid or supercritical carbon dioxide (CO ₂ ) do not alone make it possible to eliminate biofilms and strongly adhered proteins.

The cleaning effect of liquid or supercritical carbon dioxide (C0 ₂ ) is also not improved by the addition of disinfectants / sterilizers. In fact, on the one hand, aldehyde-type disinfectants such as glutaraldehyde tend to attach proteins (prions) to the surfaces of the material rather than detaching them; highly potent oxidizing disinfectants / sterilants such as peracetic acid also tend to attach prions as well as bacteria to the material rather than detaching them. On the other hand said liquid or supercritical (C0 ₂ ) assistant disinfectants / sterilants have no abrasive character to detach biofilms and strongly adhered proteins.

The inactivation of the prions is also not carried out by the aforementioned supercritical carbon dioxide (CO ₂ ) processes with or without the aforementioned disinfectants / sterilants. Indeed, these proteinaceous contaminants have a supercritical carbon dioxide (C0 ₂ ) resistant amyloid structure and said disinfectants / sterilants to be deactivated.

In the aforementioned supercritical carbon dioxide (CO ₂ ) processes the additive can be filtered to remove insoluble contaminants but soluble contaminants. in the additive are difficult to separate during the course of the treatment cycle; it follows a gradual decrease in the effectiveness of cosolvent or additive hence a lack of reproducibility of the effectiveness of the treatment.

 On the other hand, the problem of redeposition of contaminants on the material treated during the depressurization remains without effective solution in the prior art.

 There is therefore, in the prior art, no method of sterilization of thermosensitive instruments which is not only able to quickly and efficiently treat difficult to reach locations of complex geometries but also to inactivate prions by default while preserving the physical integrity of the equipment.

 The fact that the cleaning, disinfection, inactivation of prions and / or endotoxins and terminal sterilization operations are separated in time and space increases the total treatment time of the contaminated material, the exposure risks of infectious agents and the risks of nosocomial infections by transporting said infectious agents to healthy environments.

 Generally, after the cleaning / disinfection operations, the operator visually checks the cleanliness and condition of the equipment before any packaging and terminal sterilization operations. It follows that when the equipment is poorly disinfected, the operator risks being contaminated.

 If the cleaning, disinfection, sterilization and inactivation of prions and / or endotoxins were carried out simultaneously, the risk of failure and the time required to complete the sterilization process would be reduced. In addition we would gain in reproducibility and at the same time protect the operator against infections and dangerous solvents.

 There are methods for performing sequentially in the same enclosure cleaning, disinfection, sterilization; but no known method of the prior art performs simultaneously cleaning, disinfection, sterilization, inactivation of prions and / or endotoxin, continuous separation of soluble and insoluble contaminants and continuous regeneration of processing agents, while preserving the physical integrity of the material being processed.

SUMMARY OF THE INVENTION

The present invention is not only intended to overcome the disadvantages, limitations and defects mentioned above of the prior art but also to meet current needs in the areas of cleaning, disinfection, prion inactivation and sterilization.

 An object of the present invention is therefore to provide a method and a device for treating contaminated material that can not only remove biofilms, proteins in general, and in particular prions and / or endotoxins, which can to strongly adhere to surfaces in general and in particular to those which are difficult to reach instruments with complex geometry; but also to disinfect, sterilize, inactivate the prions and / or endotoxins on said surfaces, while preserving the physical integrity of the material whether it is thermally sensitive and / or thermostable and / or complex geometries.

 Another object of the present invention is to provide a method and a device for treating contaminated equipment making it possible to simplify the flow diagram of reprocessing actions of medical devices.

 Another object of the present invention is to provide a method and a device for treating contaminated material for effectively performing a self-disinfection to prevent the subsequent formation of biofilms, a source of cross contamination.

 Another object of the present invention is to provide a method and a device for treating contaminated equipment making it possible to compensate for, reduce or even effectively eliminate, in a satisfactory manner, the requirements in force, the risks of failure or the lack of reproducibility. performance related to the human factor during the sterilization process.

 Another object of the present invention is to provide a method and a device for treating contaminated equipment to minimize the risk of contamination and operator accidents in this case during the inactivation of prions.

 Another object of the present invention is to provide a method and a device for treating contaminated equipment to eliminate the risk of recontamination related to the rinsing and drying steps.

Another object of the present invention is to provide a method and a device for treating contaminated equipment to overcome the risk of incompatibility between the detergent and the disinfectant following a bad rinse. To achieve the objects assigned to the invention, the Applicant combines two seemingly incompatible products: carbon dioxide (CO ₂ ) and sodium hydroxide solution (sodium hydroxide (NaOH)) caustic. Indeed, it is known that the sodium hydroxide solution (Sodium hydroxide (NaOH)) loses its cleaning and disinfecting properties in the presence of carbon dioxide (C0 ₂ ) by loss of causticity due to neutralization by anti-basic effect said carbon dioxide (C0 ₂ ). There is therefore a flagrant incompatibility between sodium hydroxide solution (sodium hydroxide (NaOH)) and carbon dioxide (C0 ₂ ), as does the incompatibility between detergents and disinfectants.

However, it is known as mentioned above in the present description, that the carbon dioxide (C0 ₂ ) in the dense state has a cleansing action, bacteriostatic, virucidal and bactericidal effective on vegetative forms etc. but the carbon dioxide (C0 ₂ ) in the dense state hardly has a sporicidal action and does not allow to inactivate the prions and endotoxins. On the other hand, carbon dioxide (C0 ₂ ) in the dense state although able to solubilize hydrophobic micro-contaminants in the most complex geometries is unable to remove biofilms and strongly adhered proteins. The macromolecular particles and the proteins are indeed very slightly soluble in liquid or supercritical carbon dioxide (C0 ₂ ).

 It is also known that caustic soda (sodium hydroxide (NaOH)) inactivates prions and endotoxins, caustic soda (sodium hydroxide (NaOH)) is a good cleaning agent for easily accessible but inefficient external surfaces on complex geometries and that caustic soda is a good bacteriostatic agent but a bad sterilizing agent. Indeed it is known that spores of bacteria apparently killed by sodium hydroxide (sodium hydroxide (NaOH)) caustic can be regenerated with lysozyme. But it is also known that sodium hydroxide (Sodium Hydroxide (NaOH)) is very corrosive and eventually corrodes after a long period of continuous contact, even very corrosion resistant material such as stainless steel. Thus, the caustic nature of soda (sodium hydroxide (NaOH)) limits its use to low or very low concentrations in common cleaning and disinfection applications where the role of sodium hydroxide (sodium hydroxide (NaOH)) caustic is often reduced to pH control.

On the other hand, it is also known, as described in the document Aline Dumas et al, The Influence of Processes for the Purification of Human Bone Allografts on the Matrix Surface and Cytocompatibility, Biomaterials 27 (2006) 4204-4211, that sodium hydroxide (Sodium Hydroxide (NaOH)) caustic destroys the physical integrity and collagen fibers of bone substitutes.

The Applicant has found, after much research and experiments, quite surprisingly and against all expectations, that by pressurizing a composition formed by carbon dioxide (C0 ₂ ) and sodium hydroxide solution (sodium hydroxide (NaOH)), at successive cycles of decarbonation (removal of CO ₂ ) and carbonation (addition of CO ₂ ), said composition could acquire both cleaning and inactivation properties of all known types of contaminants infectious including the most resistant that is to say the prions, with much better performance than those of the prior art. In other words, by subjecting said composition to successive decarbonation / carbonation cycles, it acts as a hybrid cleaning-sterilizing agent.

 In addition, the Applicant has found that through successive cycles of decarbonation / carbonation there is no longer any limitation as to the capacity of the contaminated material to withstand solutions of high concentration of sodium hydroxide (sodium hydroxide (NaOH)) caustic because it is now possible for said sodium hydroxide solution (sodium hydroxide (NaOH)) to be contacted with the contaminated material for a period of time insufficient to corrode it. In other words, "caustic flashes" are produced by decarbonation. Thus, it is possible to use high concentrations of caustic soda (NaOH), for example of the order of 20M, without requiring corrosion inhibitors.

 The Applicant, furthermore, has devised a new filtration membrane system for effecting the separation of the soluble and insoluble contaminants extracted by said composition and the regeneration thereof in its original state; as a result, the degree of removal and inactivation of contaminants increases over time. The new filtration membrane system also allows in situ decolouration of the filtration membranes.

Thus, the objects assigned to the invention are achieved by a method for treating thermosensitive and / or thermostable contaminated material and / or complex geometries, capable of using synergistically the modulation of the causticity of a composition formed by the carbon dioxide (C0 ₂ ) and sodium hydroxide (sodium hydroxide (NaOH)) and the continuous regeneration of said composition by continuous separation of the soluble and insoluble contaminants extracted therefrom with the aid of filtration membranes, for simultaneously performing the cleaning and inactivation operations of all known types of infectious contaminants including the most resistant, that is to say the prions, without damaging the equipment; said method being characterized in that it comprises steps of:

 a) introducing contaminated material into a treatment chamber;

b) forming in situ a composition having a caustic power which can be modulated from carbon dioxide (CO ₂ ) and sodium hydroxide solution (sodium hydroxide (NaOH)); and

c) contacting the contaminated material with the composition obtained and simultaneously cleaning the contaminated material and the inactivation of infectious contaminants by modulating the causticity of said composition by subjecting it to successive cycles of decarbonation / carbonation; decarbonation (removal of carbon dioxide (C0 ₂ )) to make it caustic; carbonation (addition of carbon dioxide (CO ₂ )) to make it non-caustic and to form microparticles or nanoparticles of bicarbonate and sodium carbonate which are mild detergents and abrasives; and

 d) simultaneously with steps b) and c) subjecting said composition to mechanical agitation;

 e) recirculating, preferably continuously all or part of the composition containing the extracted contaminants, without depressurizing, preferably, but not exclusively, the treatment chamber; and

 f) not only continuously and selectively separating the soluble and insoluble contaminants extracted by the composition through a battery of easy loading / unloading filtration membranes and capable of being embedded in a separation chamber (230), said membranes filtration system (284, 285, 286, 287) for successively or selectively microfiltration, ultrafiltration, nanofiltration, reverse osmosis and regenerate the composition in its original state; but also continuously inactivate the remaining infectious contaminants extracted by the composition, making the composition this time caustic by decarbonation; and;

 g) reintroduce into the treatment chamber a desired fraction or all of the composition renewed and purified to treat the material; and

h) repeat steps c) to g) at least once; i) rinsing and neutralizing the bicarbonate and carbonate microparticles and nanoparticles by only recirculating the carbonated water with carbon dioxide (C0 ₂ ); said carbonated water being further sterile by reverse osmosis filtration in the separation chamber (230);

 j) drying the treated material with carbon dioxide

(C0 ₂ );

 k) release the treated material from the treatment chamber.

In step d) the stirring means include but are not limited to the use of stirrer magnetically coupled to an electric motor or connected directly to an electric motor, the use of rotating drum magnetically coupled to an engine electric or connected directly to an electric motor by a shaft passing through the wall of the autoclave, the use of jets, the use of agitation by recirculation of the fluid, the use of agitation by heating the fluid, the use of agitation by formation of bubbles in the fluid, the use of ultrasound.

According to embodiments of the method of the invention:

When the thermosensitive and / or thermostable contaminated material and / or complex geometries is not yet cleaned, the method according to the invention performs a treatment corresponding to a cleaning with simultaneous inactivation of infectious contaminants and performs after step k) a self-disinfection of the whole installation using saturated steam followed by a final drying using carbon dioxide (C0 ₂ ) in the supercritical state.

 When the thermosensitive contaminated material is cleaned and disinfected and is packaged or not, the method according to the invention carries out a treatment corresponding to a terminal sterilization of the thermosensitive material with default inactivation of the prions.

 When the thermostable contaminated material is cleaned and disinfected and is packaged or not, the method according to the invention carries out a treatment corresponding to a terminal sterilization of the thermostable material with default inactivation of the prions.

Thus, a contaminated material treatment process is used to simultaneously clean, inactivate any type of infectious contaminants, continuously separate soluble and insoluble contaminants and continuously regenerate the treatment agents. Consequently, the time required to carry out the cleaning, high-level disinfection and terminal sterilization, inactivation of prions and / or endotoxins is significantly reduced because, on the one hand, these operations are no longer separated in time. and space but are done simultaneously and secondly, the intermediate rinsing and drying operations are faster and more efficient.

 In addition, the method of treating contaminated material according to the invention, allows for the terminal sterilization of contaminated material thermosensitive and / or thermostable and / or complex geometries.

In addition, to treat the contaminated material, the process according to the invention uses only two products: carbon dioxide (CO ₂ ) and and sodium hydroxide solution (sodium hydroxide (NaOH)) caustic.

 Moreover these two products are abundant, cheap, and are non-toxic.

 Moreover; these two products can be obtained from a single product: a solution of sodium bicarbonate, preferably this sodium bicarbonate solution is a mineral water of natural source rich in bicarbonate such as commercial mineral water St- Yorre very rich in sodium bicarbonate (4368mg / l).

 Of course, other natural mineral waters rich in bicarbonate of other known commercial brands may be used in the context of the present invention.

 In addition, natural mineral waters rich in bicarbonate can be used in the raw state in the context of the present invention.

 Indeed, the method according to the invention can advantageously incorporate on-site production stages of these two products consisting of:

 introducing a solution of sodium bicarbonate (NaHC (¾)) into the separation chamber in which is embedded a battery of filtration membranes successively comprising a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a membrane of reverse osmosis;

subjecting the sodium bicarbonate solution (NaHCOa) to acoustic emissions and / or heating said solution to temperatures above 60 ° C to release carbon dioxide (CO ₂ ) and form sodium carbonate (Na ₂ CO ₃₎ );

recovering the carbon dioxide (CO ₂ ) using one or more gas-liquid separation membranes and a compressor; and sending the carbon dioxide (C0 ₂ ) into the treatment chamber or storing it; - Add slaked lime Ca (OH) ₂ to sodium carbonate (Na ₂ CO ₃ ) to produce the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic Ca ²⁺ calcium ions being stopped later by the membrane nanofiltration capable of stopping divalent ions, sodium hydroxide solution (sodium hydroxide (NaOH)) being recovered after nanofiltration.

On the other hand, carbon dioxide (C0 ₂ ) can be produced from ambient air or fumes; thanks to a compressor, the air or fumes are (are) sucked up and put in contact with the caustic soda solution (Sodium hydroxide (NaOH)) using one or more membranes of gas-liquid contact with said carbon dioxide (C0 ₂ ); this makes it possible to selectively capture the carbon dioxide (C0 ₂ ) contained in the air or the fumes.

Generally, the costs of transporting, handling, storing carbon dioxide (C0 ₂ ) excessively increase the total operating cost of a dense carbon dioxide (C0 ₂ ) treatment process. On the other hand, the greater the amount of carbon dioxide (CO ₂ ) required to carry out the treatment, the greater the volume of the chamber required to store the carbon dioxide (CO ₂ ) is bulky and requires significant handling, which makes carbon dioxide cleaning systems (C0 ₂ ) difficult to move. Moreover, in the case of a shortage of carbon dioxide (C0 ₂ ), it is necessary to wait a relatively long time to be delivered.

By means of the process according to the invention these above-mentioned problems are overcome, while on the spot manufacturer, as mentioned above, the carbon dioxide (C0 ₂ ) is manufactured. In addition, the process according to the invention not only synergistically combines the advantages of carbon dioxide (C0 ₂ ) in the dense state, sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and filtration membranes but also to remedy their respective limitations.

Indeed, during carbonation cycles the advantages of carbon dioxide (C0 ₂ ) in the dense state are optimized and during the decarbonation cycles the advantages of the caustic soda solution (sodium hydroxide (NaOH)) are optimized.

On the other hand, the Applicant has found that successive cycles of decarbonation / carbonation significantly reduce the time, pressure and temperature necessary to achieve the sterilization of thermosensitive materials at room temperature. using carbon dioxide (C0 ₂ ) in the dense state. Therefore, the process according to the invention considerably reduces the treatment time, simultaneously performing the cleaning and sterilization of the contaminated material.

In addition, the microparticles and nanoparticles of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ), formed during the reaction between the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic and the dioxide of carbon (C0 ₂ ) in the dense state, are non-corrosive surfactant compounds having a detergent action. On the other hand, they are soft abrasives that under the effect of agitation and pressure will play the role of a brush or swab in places usually inaccessible much more reproducible and more efficient than when manual cleaning. This allows scouring even the complex geometries of a contaminated material such as an endoscope and thus remove biofilms and dried proteins in said complex geometries.

In a particularly advantageous manner, the reaction between the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and the carbon dioxide (CO ₂ ) in the dense state, preferably in the supercritical state, is a reaction. exothermic. The Applicant has unexpectedly found that this temperature may be around 50 ° C. Thus, we can achieve significant energy savings by passing the usual heating means. The energy released can also be recovered by heat exchangers placed appropriately in any place where there is energy exchange, for example in the treatment chamber and in the separation chamber.

Filtration membranes, in addition, can regenerate the carbon dioxide (C0 ₂ ) in the dense state and caustic soda (sodium hydroxide (NaOH)) solution by continuously separating soluble and insoluble contaminants.

The pressure necessary for the operation of the filtration membranes is provided by the carbon dioxide (C0 ₂ ) in the dense state.

The filtration membranes are de-fouled with sodium hydroxide solution (sodium hydroxide (NaOH)) and by reverse filtration with carbon dioxide (C0 ₂ ) in the dense state.

Advantageously but not necessarily, the process according to the invention can be optimized, in particular as a function of the material, the level of contamination and / or the desired duration of treatment, by the addition of other compounds to the two basic products. of the process according to the invention that are the caustic soda solution (sodium hydroxide (NaOH)) and carbon dioxide (C0 ₂ ).

In addition, said sodium hydroxide solution (caustic sodium hydroxide (NaOH)) may be replaced or combined with a strong hydroxyl-containing base (OH) and have as diluent alcohol such as ethanol or hydrogen peroxide. (H ₂ O ₂ ).

Thus, whatever the treatment, according to the desired purpose, during step b) o can replace the sodium hydroxide solution (Sodium hydroxide (NaOH)) with caustic hydroxyl (OH) or capable of forming bicarbonate or carbonate in the presence of carbon dioxide (C0 ₂ ). The caustic products include, but are not limited to, sodium hypochlorite (NaClO), potassium hydroxide or potassium hydroxide (KOH).

Advantageously, carbon dioxide (C0 ₂ ) will be used to optimize the effectiveness of sodium hypochlorite (NaCIO) by controlling its pH during the inactivation of prions.

 Whatever the treatment, during step b) the soda solution can be coupled

(Sodium hydroxide (NaOH)) caustic with hydroxyl (OH) group-containing caustics or capable of forming bicarbonate or carbonate in the presence of carbon dioxide (C0 ₂ ). Said caustics including, but not limited to, Ammonium hydroxide (NH ₄ OH), Ammonium tetramethyl hydroxide (N (CH ₃ ) ₄ OH), Lithium Hydroxide (LiOH) , Calcium Hydroxide (Ca (OH) ₂ ), Magnesium Hydroxide (Mg (OH) ₂ ), Barium Hydroxide (Ba (OH) ₂ ), Cesium Hydroxide (CsOH), Strontium Hydroxide (Sr (OH) ₂ ), Rubidium Hydroxide (RbOH), Copper Hydroxide (Cu (OH) ₂ ) or a mixture thereof.

 Whatever the treatment, in step b) sodium hydroxide (sodium hydroxide (NaOH)) can be combined with the sodium carbonates and bicarbonates or the carbonates and bicarbonates of the abovementioned hydroxyl group products.

 Whatever the treatment, in step b) hydroxyl group (OH) caustic products can be obtained from their respective carbonate and / or bicarbonate. When the treatment is cleaning with simultaneous inactivation of infectious contaminants:

In steps c) to h), antimicrobial essential oils can be added in limited quantities to optimize the continuous inactivation of infectious contaminants. Advantageously, said antimicrobial essential oils are extracted on the spot with the aid of carbon dioxide (C0 ₂ ) in the dense state, starting, preferably, but not exclusively, from natural plant or animal sources introduced, preferably but not exclusively in the separation chamber.

In addition, the antimicrobial essential oils can be advantageously extracted, preferably, but not exclusively, in the separation chamber, using the carbon dioxide (C0 ₂ ) in the dense state, from the contaminants themselves. for example, contaminants resulting from the cleaning of contaminated materials such as debris of blood, organic matter, tissue, respiratory secretions, body fluids, contents released by the microorganisms exploded etc.

 Examples of antimicrobial essential oils that may be used include, but are not limited to, thymol, carvacrol, eugenol, menthol, geraniol, verbenone, eucalyptol, carvone, cedrol hinokitiol, berberine, citral, limonene, volatile fatty acids, etc.

- In steps c) to h) may be added, in limited quantities, anionic or nonionic surfactants or surfactants, detergents, oils, enzymes such as thermostable alkaline proteases, hydrogen peroxide (hydrogen peroxide) , sodium hypochlorite (bleach) which primarily promote the cleaning action of the composition formed by the caustic soda solution (sodium hydroxide (NaOH)) and the carbon dioxide (C0 ₂ ) at the dense state. These additives are then removed from the composition formed by the caustic soda solution (sodium hydroxide (NaOH)) and the carbon dioxide (CO ₂ ) in the dense state, thanks to the filtration membranes.

 - In step f), in addition to decarbonation, the inactivation of infectious contaminants in the separation chamber can also be done by adding disinfectant or sterilizing agents such as peracetic acid, hydrogen peroxide and so on. ; said disinfecting or sterilizing agents being subsequently removed after their action thanks to the filtration membranes.

- During steps c) to h) preferably towards the end of treatment, disinfectant / sterilizing additives can be added to the composition with anti-aggregating agents, chelating agents, surfactants to optimize the inactivation of the microorganisms, detachment and / or inactivation of prions and / or endotoxins. Examples of additives that are suitable for this situation include, but are not limited to, alcohols such as 60% to 95% ethanol, hydrogen peroxide, chlorine dioxide, hypochlorite. sodium, ethylene oxide, sodium dodecyl sulfate SDS (5%), formaldehyde, glutaraldehyde, ammonia, B-propiolactone, phenol, phenol derivatives, iodophors, sodium metaperiodate , urea, antimicrobial essential oils and mixtures thereof.

 - In step c) to h), can be added proteinase K which hydrolyzes the residual forms of prions become sensitive to proteinase K after treatment with sodium hydroxide (sodium hydroxide (NaOH)) caustic. In this step, chelating agents may also be added to extract copper Cu and zinc Zn ions that are in the active site of the prion protein to optimize its inactivation.

When the treatment is terminal sterilization of thermosensitive material with default inactivation of prions:

In steps b) to h), antimicrobial essential oils can be added to the composition in limited quantities to optimize the inactivation of infectious contaminants. Advantageously, said antimicrobial essential oils are extracted on site using carbon dioxide (C0 ₂ ) in the dense state, starting, preferably, but not exclusively, from natural plant or animal sources introduced, preferably but not exclusively in the separation chamber. Examples of antimicrobial essential oils that can be used include, but are not limited to, thymol, carvacrol, peugentol, menthol, geraniol, verbenone, eucalyptol, carvone, cedrol, hinokitiol, berberine, citral, limonene, volatile fatty acids etc.

- In step b) can be added to the composition, in a limited quantity, under vacuum and / or by ultrasonic spray nozzles, disinfectant / sterilizing additives with anti-aggregating agents, chelants, surfactants to optimize inactivation microorganisms and possible endotoxins and prions; said disinfectant / sterilant additives being added and treated in the same way as the sodium hydroxide solution (Sodium Hydroxide (NaOH)). Examples of additives suitable for this situation include, but are not limited to, alcohols such as 60% to 95% ethanol, hydrogen peroxide, chlorine dioxide, sodium hypochlorite, chlorine ethylene oxide, sodium dodecyl sulfate SDS (5%), formaldehyde, glutaraldehyde, ammonia, β-propiolactone, phenol, phenol derivatives, iodophors, sodium metaperiodate, urea, with oils essential antimicrobial agents, and mixtures thereof which primarily promote the action of inactivation of infectious contaminants, of the composition formed by the sodium hydroxide solution (sodium hydroxide (NaOH)) and the carbon dioxide (C0 ₂ ) in the state supercritical.

 Between step i) of rinsing and step j) of drying, it is advantageous to introduce additional steps consisting of:

adding to the carbon dioxide (CO ₂ ) in the supercritical state, disinfecting / sterilizing agents, preferably, but not exclusively, under vacuum and / or spray atomized form with the aid of ultrasonic spray nozzle; said disinfecting / sterilizing agents being at least at a minimum concentration of effectiveness and in sufficient quantity to thoroughly impregnate all external and internal surfaces of the contaminated materials; said disinfecting / sterilizing agents being added and treated in the same manner as the sodium hydroxide solution (Sodium Hydroxide (NaOH)) previously added.

 - perform successive cycles of decompression / compression or depressurization / pressurization;

 vacuum removal, said disinfecting / sterilizing agents from the treatment chamber;

 - rinse with carbonated water or ethanol.

Examples of additives that lend themselves well to this situation include, but are not limited to, acetic acid, peracetic acid, alcohols such as 60% to 95% ethanol, hydrogen peroxide which promote mainly the action of inactivation of infectious contaminants of carbon dioxide (C0 ₂ ) in the supercritical state. When the treatment is cleaning with simultaneous inactivation of infectious contaminants or when the treatment is terminal sterilization of thermosensitive material with default inactivation of prions:

 - In step i) rinsing, can be added acetic acid, peracetic acid or other acids such as hydrochloric acid (HCl) to optimize the neutralization of microparticles and nanoparticles of bicarbonate and carbonate .

- During the supercritical drying step j), co-solvents or drying aids can be added to promote the removal of water or liquid products; examples of cosolvents that may be used include, but are not limited to, alcohols, acetone, hydrofluorocarbons (HFCs) [preferably pentafluoroethane] (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoropropane (HFC245fa), difluoromethane (HFC-32), monofluoromethane, trifluoromethane (HFC-23), hydrofluoroethers (HFE), fluorosurfactants and mixtures thereof. The said drying aids are themselves subsequently removed by liquid carbon dioxide (CO ₂ ) and trapped in the separation chamber when all the water retained on the surface of the treated material is removed.

- On the other hand, in the presence of material having components sensitive to hydrogen peroxide (hydrogen peroxide (H ₂ O ₂ )), or to chlorine dioxide, such as, for example, brass, copper, aluminum, carbon steel, polyurethane, nylon etc. ; corrosion inhibitors are added before or during the addition of hydrogen peroxide (hydrogen peroxide (H ₂ O ₂ )), or chlorine dioxide. Examples of corrosion inhibitors that may be used include, but are not limited to, benzole groups, preferably azoles, preferably imidazoles, axoles, thiozoles, mercaptobenzothiozoles, indoles, pyrazoles, benzoates, borates, chromates, dichromates, molybdates, vanadates, phosphates, tungstates, silicates and mixtures thereof.

- In steps b) to j), optionally, to optimize the process according to the invention, other fluids in the liquid state and / or supercritical can be used, in limited quantities, in combination with carbon dioxide (C0 ₂ ) supercritical. Examples of fluids include, without limitation, hydrofluorocarbons (HFCs) [preferably pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoropropane (HFC245fa), difluoromethane (HFC-32), monofluoromethane, trifluoromethane (HFC-23), hydrofluoroethers (HFE), sulfur hexafluoride, nitrous oxide, nitrous oxide, methane, ethane, propane , butane, isobutane, pentane, propene, ethylene, methanol, ethanol, iso-propanol, butanol, helium, neon, argon, krypton, xenon , nitrogen (N ₂ ), hydrogen (H ₂ ), oxygen (0 ₂ ), ozone (O ₃ ), fluorine (F ₂ ), hydrogen chloride (HC1), antimicrobial essential oils and mixtures thereof.

During the unclogging of the filtration membranes, in addition to the products used above, it is of course possible to use other chemicals to de-foul the filtration membranes such as, but not exclusively, hydrochloric acid (HC1), the acid acetic acid, peracetic acid, hydrogen peroxide (H ₂ O ₂ ), nitric acid (HNO ₃ ), sodium hypochlorite (aCIO) etc. Contaminated materials that can be treated by the method according to the invention include contaminated medical devices which are on the one hand, single-use or reusable medical devices designed by industrialists and requiring to be cleaned and sterilized beforehand. be used in hospitals, clinics, laboratories; on the other hand, the bone tissues needing to be cleaned and sterilized before being used in hospitals, clinics etc. and intended for use in allografts, autografts, or xenografts; In addition, contaminated medical devices are medical devices and other sources of contamination such as clothing, watches, bracelets, rings for hospital staff or clinics, etc.

 Medical devices means surgical and ancillary instruments, apparatus, materials, products, articles or articles intended by the manufacturer for use in the medical, dental or veterinary field, in the performance of certain acts for for the purpose of diagnosis, prevention, control, therapeutic treatment or mitigation of a disease, mitigation or compensation for an injury or disability, study, replacement or modification of the anatomy or physiological process and intended either to be introduced into cavities or sterile tissues or into the vascular system regardless of the approach, either to be in contact with a mucosa, a skin damaged superficially, or intact skin

 Contaminated materials that can be processed by the process according to the invention also include materials intended to be brought into contact with food in the food industry, catering etc.

 Contaminated materials that can be processed by the process according to the invention also include materials, microelectronics and electronics, semiconductors, mechanical parts of various kinds.

 In general, contaminated materials that can be treated by the process according to the invention means any solid material that needs to be purified and / or disinfected and / or sterilized; said material may be constituted by materials such as natural or synthetic polymers, metals and / or alloys, glasses, ceramics, composites.

The objects assigned to the invention are also achieved by means of a device for implementing the contaminated material treatment process, characterized in that it comprises: a treatment chamber comprising:

 o means for receiving the contaminated materials;

 o means for introducing the treatment agent in the form of high speed jets on the contaminated equipment;

 o means to make the pressure rapidly hydrostatic around the contaminated material;

 o stirring means;

 o heating / cooling means such as heat exchangers for regulating the temperature;

 o acoustic emission means;

 o spraying means of the treatment agents in atomized form on the contaminated materials;

 one or more gas-liquid separation membranes connected to the treatment chamber;

 one or more gas-liquid contact membranes connected to the treatment chamber;

 at least one separation chamber which, during the implementation of the treatment method according to the invention, not only continuously separates the extracted soluble and insoluble contaminants and thus regenerates the treatment agent in its original state; ; but also to inactivate microorganisms, endotoxins and prions; said separation chamber being characterized in that it comprises:

 o inside and in a recessed manner, a battery of filtration membranes with easy loading / unloading, said filtration membranes making it possible successively or selectively, microfiltration, ultrafiltration, nanofiltration, reverse osmosis and regenerate the composition or treatment agent in its original state; means for continuously inactivating infectious contaminants extracted and for regenerating filtration membranes such as heating / cooling means and acoustic emission means;

 o means of regeneration of the filtration membranes;

 o recirculation means;

one or more gas-liquid contact membranes connected to the separation chamber; one or more gas-liquid separation membranes connected to the separation chamber;

 an aqueous or non-aqueous treatment agent delivery system comprising specific compartments for the recycled treatment agents;

 a system for supplying fluids in the dense state (liquid, supercritical) comprising specific compartments for the recycled fluids;

 a chamber for recovering inactivated and effluent-free contaminants in which is incorporated one or more filtration membranes, in this case a reverse osmosis membrane; and having on the outside a gas-liquid separation membrane associated therewith;

 one or more gas-liquid separation membranes connected to the inactivated contaminants recovery chamber;

 means for controlling the temperature and the pressure;

 an automatic control system making it possible to select the desired treatment.

Advantageously, the fact that the filtration membranes are inside the separation chamber described above, makes it possible to unclog in situ without disassembling their structure. The filtration membranes are in the form of a flat disc when they are all embedded in the separation chamber.

It should be noted that it is quite possible for the filtration membranes to be outside the separation chamber described above; but the disadvantage is that on the one hand each of the filtration membranes must be embedded in its own chamber and it is impossible to unclog the filtration membranes under these conditions without disassembling. In this case the filtration membranes may have flat disk shapes, tubular shapes, spiral shapes, hollow fiber shapes, rotary disk shapes, or any other form that may be determined by those skilled in the art.

The invention furthermore relates to the use of said device for carrying out the process according to the invention for carrying out conventional cleaning, disinfection, liquid sterilization, steam sterilization and sterilization processes. ethylene oxide, cleaning / disinfection by a dense fluid under pressure. SUMMARY DESCRIPTION OF THE FIGURES

The invention will be better understood and other features and advantages thereof will appear more clearly on reading the following description made with reference to the accompanying drawings which show, by way of non-limiting examples, embodiments of the invention. 'invention.

- Figure 1 shows schematically an embodiment of the device for implementing the method of the invention.

 - Figure 2 shows schematically an embodiment of the separation chamber of the device.

 - Figure 3 shows, schematically, an example of the constituents of the filter bank of the separation chamber of the device.

 FIG. 4 schematically represents an exemplary arrangement of the constituents of the filter bank of FIG. 3.

 - Figure 5 shows, schematically, another example of arrangement of the constituents of the filter bank of Figure 3.

DETAILED DESCRIPTION OF THE INVENTION

The device (100) according to the invention will be described, by way of non-limiting example, in a preferred application relating to a device adapted for the treatment of contaminated medical devices in this case the endoscopes. It is understood that the device (100) and its components represented by the drawings are given for illustrative and non-limiting purposes and that various variations are possible from them, concerning, for example, the geometry, the size various components of the device (100). Furthermore, it is understood that other devices or installations known from the prior art may be suitable for the implementation of certain aspects of the process according to the invention, and in particular the conventional devices for cleaning with dense fluids. under pressure, with or without rotary drum. With reference to FIG. 1, the device (100) comprises an enclosure (101) that can be pressurized, preferably in a vertical position, constituting the treatment chamber (101) for the contaminated materials. The enclosure (101) has a cylindrical shape according to Figure 1 and has a circular door (106) opening and closing, preferably automatic and fast. According to variants, the enclosure (101) may be of parallelepipedal shape with a rectangular side door opening and closing, preferably automatic and fast. The volume of the treatment chamber (101) is variable depending on the application and will be, for example 10 liters to 10 m ³ .

 According to the invention, the enclosure (101) is an autoclave having a high sealing at closure. The materials constituting the treatment chamber (101) are all those compatible with the contact with dense fluids at pressures that may be greater than 300 bars and the surfactant solvents / cosolvents and additives, used at different temperatures depending on the conditions of the treatment. 'invention. These materials can generally withstand temperatures that may be greater than 200 ° C. Stainless steel is generally used as the material constituting the process chamber (101).

 Advantageously, according to the invention, the autoclave or treatment chamber (101) can be manufactured with a metal inner envelope reinforced by a composite reinforcement. This coupling has the advantage of limiting the weight and cost of the device while maintaining compatibility with the pressure / temperature / solvent conditions described in the invention. The metal inner envelope is composed of all materials compatible with the contact with dense fluids under pressures that may be greater than 300 bars and the solvents / cosolvents used at different temperatures according to the conditions of the invention, for example the stainless steel. The reinforcing composites used in the metal casing are made with high-strength fibers, for example carbon or aramid fibers bonded by a polymeric resin, for example an epoxy resin.

According to the invention, the device (100) further comprises a system (107) removable by the handling means (107a) and for performing an easy loading unloading of the material to be treated. The system (107) includes cylindrical baskets (102) for receiving the contaminated material, in this case endoscopes; said cylindrical baskets (102) are suspended from a hollow shaft (107b) having nozzles for dispensing jet-like (109) cleaning and / or disinfecting and / or sterilizing agents on the contaminated materials. The hollow axis (107b) also has horizontal spray arms (not shown) above and below each cylindrical basket (102). The hollow shaft (107b) has, in addition, on its surface connecting means (not shown) for the irrigation of internal channels with complex geometries flexible endoscopes for example.

 According to one embodiment of the invention, the device (100) further comprises an agitator (104) which is either a direct magnetic coupling with integrated motorization

(103), directly driven by an electric motor (103); said agitator (104) having a hollow shaft acting as a stirring shaft and fluid injection. On the other hand, the hollow shaft of the stirrer (104) passes through the wall of the autoclave (101) with a non-rotating seal, that is to say the hollow shaft is rigidly fixed to the wall by screw as described in CA1081755A1, thus avoiding the problems of leakage or wear posed by the rotary joints of the prior art. According to the invention, the agitator

(104) is adapted to receive at its end (105) the cylindrical baskets (102) by mechanical coupling of the hollow shaft of the agitator (104) with the hollow shaft (107b) of the loading system (107). unloading the material to be processed. By way of example, the mechanical coupling can be done by simple interlocking or by screwing. On the other hand the agitator (104) is adapted to additionally receive on its rotating axis a cylindrical nozzle system (110) having nozzles on all its components: the upper circular base (HOd), the lower circular base (110c) and its spokes (110b), the other circular parts (110e) and the vertical axes (110a). The cylindrical nozzle system (110) is preferably rotatable by fluid inlet under pressure. Said nozzles are intended to dispense, in the form of jets (109), the cleaning and / or disinfecting and / or sterilizing agent, in this case the composition formed by the carbon dioxide in the dense state and the sodium hydroxide solution (Hydroxide of sodium (NaOH)) not only on the contaminated materials contained in the cylindrical baskets (102) but also on the walls of the treatment chamber (101) in the form of jets (109a) in order to simultaneously treat the contaminated materials and self-disinfecting the treatment chamber (101). Dispersion in the form of jets in the vicinity of the contaminated equipment makes it possible to increase the contact time of the cleaning and / or disinfecting and / or sterilizing agent with the contaminated material before its loss of solubility in carbon dioxide (C0 ₂ ) in the dense state.

It should be noted that the nozzles of the cylindrical nozzle system (110) and those of the hollow shaft (107b) of the system (107) are arranged to rapidly produce a hydrostatic pressure around the contaminated equipment. Thus, we avoid a difference too much pressure on the surfaces of the contaminated equipment and therefore fragile materials that are very sensitive to pressure are protected.

 Under the effect of the agitator (104) the cylindrical baskets (102) are subjected to a rotational movement that can reach if necessary 1500 revolutions / minute. Thus the cylindrical baskets (102), including their contents, behave like the blades of the impeller of the agitator (104) but uniformly stir the entire volume of the treatment chamber (101) contrary to said blades of the which generally can only agitate the reagent medium in the treatment chamber (101). It follows a total homogenization of the reactive medium in the treatment chamber (101) and a better contact between the cleaning agent and / or disinfectant and / or sterilizing and contaminated materials. The cleaning, disinfection and sterilization of complex geometries are thus performed with higher performance than those of the prior art.

 The device (100) further includes one or more ultrasonic spray nozzles (108) for fractionating the additives into very small volatile droplets (109b).

The unloading loading system (107), the ultrasonic spray nozzles (108), the cylindrical nozzle system (110), the cylindrical baskets (102) and the agitator (104) are made of materials that can withstand the operating conditions of the invention; said materials being preferably of stainless steel or PTFE (Teflon ^®).

 The treatment chamber (101) further comprises means for heating or acoustic emissions (not shown).

The device (100) according to the invention further comprises one or more gas-liquid contact membranes (230a, 206), one or more gas-liquid separation membranes (230b, 230c, 403a, 303); said gas-liquid contact membranes for rapid diffusion of gases into liquids on a microscopic scale; said gas-liquid separation membranes for extremely rapid degassing of liquids on a microscopic scale. Said diaphragms contact or gas-liquid separation (230a, 230b, 230c, 206, 403a, 303) are tubular hollow fiber membranes such as those described in US-A 5,490,884 or those of Liqui-Cel ^®. Said contact or gas-liquid separation membranes (230a, 230b, 230c, 206, 403a, 303) are, of course, embedded in rooms or autoclaves adapted and resistant to the pressures and temperatures used in the process according to the invention.

 The device (100) according to the invention further comprises a continuous separation chamber (230) for the contaminants extracted from the materials contaminated by the treatment agents; said separation and recycling chamber (230) having means for filtration (28), filter regeneration, recirculation (400) and physical inactivation means of the filtered contaminants that are the heating means (241) and the acoustic emission means (242). This has the advantage of avoiding the redeposition of contaminants and isolating infectious contaminants in a room where we can use drastic conditions to inactivate them permanently without the risk of damaging the treated material that is in the shelter in the room. treatment (101). On the other hand, the filtration means make it possible to regenerate the treatment agents.

 Several types of pumps known in the state of the art and able to withstand high pressures, temperatures, alkalinity, acidities can be used as a recirculation pump (400) in the context of this invention; preferably they are piston or diaphragm pumps, more preferably they are pumps such as those described in US6986647B2 and WO-A-2006041600.

 The details on the separation chamber (230), on the filtration means (28), on the recirculation means (400) are illustrated in FIGS. 3, 4, 5.

With reference to FIG. 2, the separation chamber (230) has the same characteristics as the treatment chamber (101) as previously described; but having, preferably, but not exclusively, a smaller volume; by way of nonlimiting example, a volume that can be half, or third, or a quarter of that of the treatment chamber (101). The separation chamber (230) is preferably made of stainless steel. The separation chamber (230) may preferably have a cylindrical shape and be in a vertical or horizontal position, preferably in a horizontal position as illustrated. The separating chamber (230) has one or two automatic and fast opening / closing doors (238), inter alia for loading, unloading, or replacing the filter bank (28) as further illustrated in FIG. 4, 5. The separation chamber (230) is divided into two parts (235) and (239) by the filter bank (28), the portion (239) being the cleanest compartment. The portion (235) of the separation chamber (230) receives aqueous or non-aqueous treatment agents such as solvents / co-solvents or additives the delivery system (200) of aqueous or non-aqueous treatment agents via the channels (5, 5a, 10a) controlled respectively by the valves (203, 202, 112 to 117). The portion (235) of the separation chamber (230) also receives the treatment fluids containing the contaminants extracted from the treatment chamber (101) through the pipe (10) controlled by the valves (111 and 111a). . The filter bank (28) filters the original contaminant-laden fluid (236) into ultra-pure fluid (237). The filter bank (28) also filters aqueous or non-aqueous treatment agents such as solvents / cosolvents or additives from the aqueous or non-aqueous treatment agent supply system (200); If necessary, for example, ultra-pure solvents / cosolvents or additives (237) which have no undesired or selectively filtered substances are obtained.

One or more hydrophobic gas-liquid separation membranes (403a) are connected to the separation chamber (230) and allow to separate the dense fluid in this case carbon dioxide (C0 ₂ ) in the dense state of any product aqueous or non-aqueous. The valve (403) of the pipe (9) allows to escape the dense fluid under pressure, for example during recirculation or depressurization operations. As illustrated in FIG. 2, the separation between the parts (235) and (239) is not very pronounced; the filter bank (28) being directly in contact with the contaminated fluid (236) and kept stable by the shims (240).

 The filter bank (28) comprises at least one microfiltration membrane (284), at least one ultrafiltration membrane (285), at least one nanofiltration membrane (286) and at least one reverse osmosis membrane (287) ; said filtration membranes being preferably, but not exclusively, easy to discharge or recharge; said filtration membranes (284, 285, 286, 287) for successively or selectively microfiltration, ultrafiltration, nanofiltration, reverse osmosis and regenerate the composition or treatment agent in its original state. It should be noted that the microfiltration membrane may be preceded by an ordinary filter (not shown) for prior filtration.

The microfiltration membrane (284) has pores of size between 0.1 and 10 μηι. It helps to stop undissolved contaminants such as bacteria and particles in suspension and passes molecular weight macromolecules 10,000 to 500,000 Daltons, viruses, prions, endotoxins, multivalent ions, monovalent ions, sugars, acids, dissociated acids and water.

 The ultrafiltration membrane (285) has pores of size between 0.01 and 0.05 μπι. It stops undissolved contaminants such as molecular weight molecules 10,000 to 500,000 Daltons, bacteria, viruses, prions, endotoxins and particles in suspension; and passes multivalent ions, monovalent ions, sugars, acids, dissociated acids and water.

 The nanofiltration membrane (286) has pores of size between 0.001 and 0.01 μηι. It allows to stop dissolved and undissolved contaminants such as molecular weight molecules 10,000 to 500,000 Daltons, bacteria, viruses, prions, endotoxins, multivalent ions, sugars, dissociated acids and suspended particles ; and passes monovalent ions, acids and water.

 The reverse osmosis membrane (287) has pores between 0.5 and 1.5 nm in size. It allows to stop dissolved and undissolved contaminants such as molecules of molecular weight 10,000 to 500,000 Daltons, bacteria, viruses, prions, endotoxins, multivalent ions, monovalent ions, acids, dissociated acids and suspended particles; and lets pass only the water.

In other words, the ions responsible for the hardness of the water such as calcium ions Ca ²⁺ , and magnesium Mg ²⁺ etc. are stopped by the nanofiltration membrane (286) and the ions resulting from the dissociation of sodium hydroxide (Na ⁺ and OH ^' ) are stopped by the reverse osmosis membrane (287).

With reference to Figures 3, 4 and 5; the filter bank (28) comprises metal grids (281, 283, 288) for separating and / or stabilizing and / or supporting the filter membranes (284, 285, 286, 287). The metal grids (281, 283, 288) have larger diameter pores (at least greater than 1 μπι) than the filtration membranes (284, 285, 286, 287); thus making it possible to recover the filtrates or to inject via the valves (112 to 117) (see FIG. - Circulate some filtration membranes and preferentially use others. The preferential injection by the valves (112 to 117) makes it possible not only to prevent certain products from reacting with others already fixed on the filtering membranes but also to save time during recirculation; for example during the rinsing phase with pure water and when there is almost no more contaminant, we will realize preferentially reverse osmosis and we will do without microfiltration, ultrafiltration and nanofiltration. The grid (288) makes it possible to wedge the filtering membranes and the other intermediate grids in the grid (281) which is intended to wrap the assembly together to form a block according to the arrangement illustrated in FIG. is used in Figure 2. The grids (281, 283, 288) have on their surfaces seals (not shown) inflatable or full-thrust and preferably of toric shape and materials resistant to high pressure conditions and temperatures, alkalinity or acidity prevailing in the separation chamber (230); said materials can be for example PTFE (Teflon ^®) or a rich composite PTFE (Teflon ^®). These seals make it possible to increase the seal between the wall of the separation chamber (230) and the grid (281) on the one hand and on the other hand the seal between the grid (281) and the grids (283), 288). Thus the fluid can not move from one space to another without being filtered by a filter membrane (284, 285, 286, 287).

 In variants, a metal grid (288) will be used instead of shims (240).

 In this case, preferably, but not exclusively, the grids (281, 283, 288) have hollow portions allowing the introduction of physical means such as heat exchangers (241) and acoustic emission means (242) between them. filtration membranes (284, 285, 286, 287) or in parts (235 and 239).

 FIG. 5 represents another example of arrangement of the constituents of the filter bank. In this case a sleeve (290) is used to facilitate the introduction of the filter bank (28) into the separation chamber (230). The sleeve (290) is attached to the filter bank (28) by a suitable connector means (289) and has a length adapted to wedge the filter bank (28) into the separation chamber (230).

The filtration membranes (284, 285, 286, 287) are preferably constituted by materials that can withstand the drastic conditions (temperature increase, ultrasound, strong bases, strong acids, disinfecting agents, sterilizing agents such as water vapor). which can reign in the separation chamber (230). Preferably these materials are stainless steels, ceramics (oxides of zirconium, titanium, alumina), PTFE (Teflon ^® ) etc.

The aqueous or non-aqueous treatment agent supply system (200) comprises a plurality of compartments for containing non-aqueous treatment agents. recycled and recycled. The aqueous or non-aqueous treatment agents are intended to be used preferably as additives to the dense fluid under pressure, in this case carbon dioxide (C0 ₂ ) in the dense state. The device (100) further comprises a recovery chamber (300) contaminants or waste without effluents. Said recovery chamber (300) of contaminants or waste without effluent is an autoclave of the same nature as the autoclaves (100 and 230) and further comprises one or more filtration membranes, preferably, but not exclusively, an osmosis membrane (287) wedged by grids (288) themselves within a grid (281).

 The pipes in which the composition of the invention circulates preferably, but not exclusively, have an internal diameter large enough to prevent any obstruction; this inner diameter is preferably, but not exclusively, between 1.6 and 12 mm.

The device (100) further comprises a system (500) for adding, storing and recycling the dense fluid under pressure, in this case carbon dioxide (C0 ₂ ).

 The system (500) includes a recovery tank system (501) having compartments specific to each recycled fluid.

 The system (500) further comprises a storage tank system (500a) having compartments specific to each new and not yet recycled fluid.

With reference to FIG. 1, the recovery tanks (501) may have a thermostatically controlled double jacket (not shown) in which a cooling fluid circulates in order to keep the dense fluid under pressure in this state, in this case carbon dioxide, in the liquid state. (C0 ₂ ).

Before being introduced into the treatment chamber (101), the dense fluid under pressure in this case the liquid carbon dioxide (CO ₂ ) coming from one of the specific compartments of the tanks (501, 500a) controlled by the valves (502, 503) is first filtered with one or more filtration membranes (504) in series or in parallel, preferably nanofiltration or reverse osmosis membranes to obtain a dense fluid under pressure occurrence of carbon dioxide (C0 ₂ ) ultra pure liquid and pharmaceutical grade. Thanks to a compressor (505), the dense fluid under pressure, in this case carbon dioxide (C0 ₂ ) is subjected to pressures greater than its critical pressure (73 bar) and is introduced via of the valve (506) in a supercritical exchanger (507) which is for example an enclosure having a thermostatically controlled double jacket (not shown) in which circulates a heat transfer fluid for heating the dense fluid under pressure to carbon dioxide (C0 ₂ ) above its critical temperature (31 ° C).

 The device according to the invention may advantageously comprise a central unit (not shown) for controlling the automatic execution of the method according to the invention by means of pressure and temperature sensors and / or regulating devices, control probes of the fluid level in the treatment chamber (101) for example. For this purpose, the valves described are preferably automatic pneumatic valves; as well as the pumps (201, 232, 400), the compressors (205, 505, 509), the heating / cooling means (241 and others not shown), the acoustic emission means (241 and others not shown) , the stirrer (104), the ultrasonic nozzles (108) are preferably controllable by a central unit.

Referring to Figures 1 and 2, will be described, preferred embodiments of the contaminated material treatment method according to the invention, implemented in the device (100) according to the invention.

 Step a): introduction of the contaminated material into the treatment chamber (101: In a first step, the contaminated materials are introduced into the treatment chamber (101), if necessary fixed by means known per se in the cylindrical baskets (102) .

^■ When the treatment is cleaning with simultaneous inactivation of infectious contaminants:

 Any type of material can be introduced into the treatment chamber (101), whether it is thermally sensitive, thermostable, or complex geometries.

Advantageously, for materials with complex geometries such as flexible endoscopes, the internal channels are connected to connection means, such as quick connectors (not shown) located on the outer surface of the hollow shaft (107b), so that to allow their direct irrigation especially with sodium hydroxide solution (Sodium Hydroxide (NaOH)), which naturally diffuse with difficulty in the internal channels because it is not volatile but much more easily in case of total immersion of the materials contaminated by the said soda solution (Sodium hydroxide (NaOH)) caustic. Indeed, in the case where small volumes of treatment chamber (101), the total immersion of the contaminated materials in the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic will be preferred; but when large volumes of treatment chamber (101) are used on a large scale, too large quantities of sodium hydroxide solution (sodium hydroxide (NaOH)) are required to fully immerse the contaminated materials, which is economically uninteresting and technically requires an excessively long time to saturate later this significant amount of sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic carbonation with carbon dioxide (C0 ₂ ). Thus, according to the invention, thanks to the quick couplings located on the outer surface of the hollow shaft (107b) of the system (107), several endoscopes can be processed simultaneously in a large volume of treatment chamber (101) without necessarily using large amounts of sodium hydroxide solution (sodium hydroxide (NaOH)) caustic.

^■ When the treatment is a terminal sterilization of the thermosensitive material with default inactivation of the prions:

The packaging of the thermosensitive material is in conventional packaging commonly used for ethylene oxide sterilization or for plasma sterilization of hydrogen peroxide; it is for example a trade mark Tyvek ^® or Mylar ^® .

 ■ When the treatment is a terminal sterilization of thermostable material with default inactivation of prions:

 The material is packaged in conventional packaging commonly used for steam sterilization and well known to those skilled in the art. Steps b) and c): in situ formation of the modular caustic composition and decarbonation carbonation cycles:

The sodium hydroxide solution (sodium hydroxide (NaOH)) and supercritical carbon dioxide (C0 ₂ ) are added simultaneously and / or successively.

When it is desired to neutralize rapidly the sodium hydroxide solution (caustic sodium hydroxide (NaOH)), it is added in atomized form by means of an ultrasonic spray nozzle (108) allowing it to be split into very fine volatile droplets in the treatment chamber (101) previously filled with carbon dioxide (CO ₂ ) in the dense state, preferably in the supercritical state. Thus, in the treatment chamber (101) microparticle powders and nanoparticles of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ), according to the SAS technique (Supercritical Anti Solvent) known from generation of powders. In this case, ethanol will advantageously be used as a solvent for the sodium hydroxide solution (caustic sodium hydroxide (NaOH)).

^■ When the treatment is cleaning with simultaneous inactivation of infectious contaminants:

 Preferably, the sodium hydroxide solution (sodium hydroxide (NaOH)) is added first.

 The soda solution (sodium hydroxide (NaOH)) caustic can be introduced directly into the treatment chamber (101) using a high pressure pump (201) and through the pipe (4) controlled by the valve (204); said sodium hydroxide solution (caustic sodium hydroxide (NaOH)) being preferably, but not exclusively, at temperatures between 20 and 60 ° C. In this case, preferably, the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) is introduced in atomized form by one or more ultrasonic spray nozzles (108) for fractionating the sodium hydroxide solution (sodium hydroxide (NaOH)). )) in very fine volatile droplets (109b) capable of efficiently diffusing into the complex geometries of the external surfaces of the contaminated materials. Apart from the ultrasonic and / or megason spraying nozzles (108), other types of nozzles or means for atomizing aqueous solutions, known to those skilled in the art, may also be used.

In addition, the sodium hydroxide solution (Sodium Hydroxide (NaOH)) can be introduced by means of a high pressure pump (201) indirectly into the treatment chamber (101) via the controlled pipe (5). by the valve (203) when it is desired to filter it in the separation chamber (230), otherwise via the pipes (5a and 10a) controlled respectively by the valves (204) and (112 to 117) and then by the chamber separating (230) between the nanofiltration (286) and reverse osmosis membranes (287). Using the recirculation pump (400), the sodium hydroxide solution (Sodium Hydroxide (NaOH)) then enters the pipe (2) controlled by the valve (402) via the pipes (7b, 7) controlled by the valves (405, 413). The pipe (2) is connected to the agitator (104) which has at least one inlet for introducing fluid through the hollow stirring shaft. In the case where the sodium hydroxide solution (Sodium hydroxide (NaOH)) caustic is filtered in the separation chamber (230) by the filter bank (28) will stop at the nanofiltration membrane (286) which passes only water and monovalent ions as the components of the sodium hydroxide (Na ⁺ and OH ^" ).

 Alternatively, the caustic soda solution (sodium hydroxide (NaOH)) can also be added in solid form. In the solid state, the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) is introduced directly into the treatment chamber (101) at the same time as the contaminated materials, in the form of a fine powder or inside a water-soluble envelope; then water is added in sufficient quantity to form the sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic.

 In variants, another diluent (hydrogen peroxide, alcohol, etc.) may be used in combination or instead of water.

 Alternatively, the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) can also be added in the form of a solid, fine powder in order to form in the treatment chamber (101) an aerosol of sodium hydroxide (sodium hydroxide (NaOH)) caustic to the using air or neutral gases and under conditions of relative humidity, preferably, but not exclusively, between 5 and 95%.

 Said sodium hydroxide aerosol (Sodium hydroxide (NaOH)) may alternatively be formed from a fine solid sodium (Na) powder with the aid of air or neutral gases and under conditions of relative humidity. preferably, but not exclusively, between 5 and 95%.

 Said sodium hydroxide solution (Sodium Hydroxide (NaOH)) added must have at least a minimum concentration of effectiveness and must be in sufficient quantity to impregnate all the external and internal surfaces of the contaminated materials contained in the treatment chamber (101). ).

 By minimum concentration of effectiveness is meant the concentration from which sodium hydroxide (Sodium hydroxide (NaOH)) becomes caustic for an infectious contaminant. This minimum concentration of efficacy varies according to the infectious contaminant considered; for example it is higher for NCTAs (Unconventional Transmission Agent) than for TCAs (Unconventional Transmission Agent). And among ATC, this minimum concentration of efficiency is higher for spores than for vegetative forms of bacteria.

Thus, sodium hydroxide solution (sodium hydroxide (NaOH)) caustic will be added at concentrations between 0.01 M and 20M; preferably, but not exclusively, concentrations between 2M and 10M; at temperatures, preferably, but not exclusively, between 20 and 60 ° C and at pressures, preferably, but not exclusively, greater than 0 bar and less than or equal to 700 bar. It is understood that sodium hydroxide (Sodium hydroxide (NaOH)) is added at very high pressures of the order of 700 bars, when beforehand it has been reached by progressive increase a pressure of the same order of magnitude in the chamber treatment (101).

 The sufficient quantity of sodium hydroxide solution (Sodium Hydroxide (NaOH)) to impregnate all the external and internal surfaces of the contaminated materials contained in the treatment chamber (101) is a function of the quantity and the total surface area of contaminated material. to be treated as well as the level of soiling or soiling.

 Preferably, but not exclusively, the sodium hydroxide solution (sodium hydroxide (NaOH)), once added as jets (109, 109a, 109b, 109c) on the contaminated materials, is immediately removed from the treatment chamber ( 101) through the pipe (10) and recirculated with the pump (400) after being regenerated by the filtration membranes (284, 285, 286, 287) of the separation chamber (230). This allows the sodium hydroxide solution (Sodium Hydroxide (NaOH)) to be renewed as it reacts with the contaminated materials and to consume small amounts of sodium hydroxide solution (sodium hydroxide (NaOH)) caustic.

Depending on the rate of evacuation of the sodium hydroxide solution (sodium hydroxide (NaOH)) from the treatment chamber (101) and the recirculation rate of the sodium hydroxide solution (caustic sodium hydroxide (NaOH)), it can occupy constantly, preferably, but not exclusively, 0.001% to 30% of the total volume of the treatment chamber (101); more preferably the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic constantly occupies 0.001% to 5% of the total volume of the treatment chamber (101). It should be noted that caustic soda (sodium hydroxide (NaOH)) solution is added for a time not sufficient to corrode the contaminated material but sufficient to corrode infectious contaminants. Preferably, but not exclusively, depending on the material to be treated, the concentration of sodium hydroxide solution (caustic sodium hydroxide (NaOH)) will be reduced to a low level. corrosive to the material but nevertheless corrosive to infectious contaminants to increase the contact time with said sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic without corroding the treated material. Of course, when supercritical carbon dioxide (C0 ₂ ) is added, the caustic concentration of sodium hydroxide solution (Sodium Hydroxide (NaOH)) will be safely increased to optimize the inactivation of infectious contaminants.

In variants, to protect fragile materials or materials with fragile components and sensitive to high pressures, sodium hydroxide solution (caustic sodium hydroxide (NaOH)) can be added so as to completely immerse the contaminated materials, or even fill the entire treatment chamber (101) for protecting the material against the effect of pressure when adding carbon dioxide (C0 ₂ ) to the supercritical state.

 In this first phase of adding sodium hydroxide solution (sodium hydroxide (NaOH)), advantageously, neutral gases may be added to reduce the surface tension of the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and thus optimize its contact with the complex geometries of the contaminated materials.

 Carbonation cycle:

Then, the carbon dioxide (C0 ₂ ) in the dense state, preferably in the supercritical state, is added so as to modulate the causticity of the sodium hydroxide solution (sodium hydroxide (NaOH)) and reduce the tension of surface of the aqueous portion of said sodium hydroxide solution (Sodium Hydroxide (NaOH)).

If we want to quickly obtain the non-caustic state is favored the contact between the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and carbon dioxide (C0 ₂ ). Indeed, thanks to one or more gas-liquid contact membranes (230a) for the diffusion of gases in liquids on a microscopic scale, an extremely fast carbonation is performed compared to carbonation by simple pressurization: with reference to FIG. 2, the valve (506b) being closed, the carbon dioxide (C0 ₂ ) in the dense state, preferably in the supercritical state is introduced into the gas-liquid contact membrane (230a) through the pipe (la) controlled by the valve (506c) to come into contact with the sodium hydroxide solution (caustic sodium hydroxide (NaOH)); then it goes out through the pipe (lb) controlled by the valve (506d) and joins the main pipe (1). Carbonated sodium hydroxide (sodium hydroxide (NaOH)) enters the treatment chamber (101) not only indirectly via the narrow channels of the endoscopes connected by means of hollow shaft connections (107b), bypassing the complex internal geometries of said endoscopes; but also, directly, by sprinkling in the form of jets (109 and 109a) on the external surfaces of the contaminated equipment and the walls of the treatment chamber (101).

Carbon dioxide (C0 ₂ ), in addition, allows the carbonation by being added directly to the contaminated materials in the form of jets (109c) through the pipes (1 and the).

If we do not want to quickly reach the non-caustic state we disadvantage the contact between the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and the carbon dioxide (CO ₂ ), we carry out a carbonation by simple pressurization in the form of jets (109, 109a, 109c) on the external surfaces of the contaminated materials and the walls of the treatment chamber (101).

Thus, the partial or complete non-corrosive state is obtained by carbonation of the caustic soda solution (sodium hydroxide (NaOH)) with carbon dioxide (C0 ₂ ) in the dense state, preferably in the state supercritical.

According to the invention, the carbon dioxide (CO ₂ ) can be added at pressures preferably, but not exclusively, between 1 and 700 bar; more preferably, but not exclusively, at supercritical pressures between 73 and 700 bar, more preferably between 73 and 300 bar and at levels preferably but not exclusively between 20 kg / h and 400 kg h.

The supercritical carbon dioxide (C0 ₂ ) is introduced at a temperature preferably between 31 ° C and 60 ° C, in all cases above 31 ° C.

The temperature is then maintained, preferably between 40 and 60 ° C in the treatment chamber (101). This range of temperatures makes it possible to treat the thermosensitive materials without degrading them. If the temperature rises above 60 ° C, to return to temperatures between 40 and 60 ° C, carbon dioxide (C0 ₂ ) in the dry ice state, in the state of snow in the liquid state can be introduced in sufficient quantity to bring the temperature between 40 and 60 ° C.

 The equilibrium pressure to be reached in the treatment chamber (101) after carbonation is preferably between 73 and 300 bar.

In addition to the possibility of directly introducing the carbon dioxide (C0 ₂ ) in the supercritical state, said supercritical state can be obtained indirectly in several ways: the carbon dioxide (CO ₂ ) can be introduced initially in the gaseous state and then the pressure can be increased by heating progressively until reaching the supercritical state;

the carbon dioxide (CO ₂ ) can be introduced initially in the liquid state at temperatures of between -56.6 ° C. and 30 ° C. and, on heating, the supercritical state is reached;

the carbon dioxide (CO ₂ ) can be introduced initially in the solid state at a temperature of -78.5 ° C. and on heating the supercritical state is reached;

The fact of adding carbon dioxide (C0 ₂ ) in the dense state, preferably in the supercritical state simultaneously in the form of jets (109c, 109, 109a) makes it possible to have a quasi-hydrostatic pressure at the fragile materials and eliminate the risk of deterioration may be due to a pressure difference too high at the fragile materials.

 To protect fragile materials or materials with fragile components and sensitive to high pressures, proceed as follows after first adding sodium hydroxide solution (sodium hydroxide (NaOH)) caustic so as to completely immerse the contaminated material or fill the whole treatment chamber (101):

then adding the carbon dioxide (C0 ₂ ) in the supercritical state until the desired pressure, preferably but not exclusively, of 73 to 300 bar is obtained in the treatment chamber (101) without, however, expanding the sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic;

 - while maintaining the constant pressure obtained in the treatment chamber (101), decreasing the opening of the valves (111 and 111a) the proportion of caustic soda solution (sodium hydroxide (NaOH)) in the treatment chamber (101); ) until the normal amount of sodium hydroxide solution (Sodium Hydroxide (NaOH)) is sufficient to impregnate all the external and internal surfaces of the contaminated materials contained in the treatment chamber (101).

When contacted, carbon dioxide (C0 ₂ ) and sodium hydroxide solution (Sodium Hydroxide (NaOH)) react together to form in the internal and external surfaces of contaminated materials microparticles and nanoparticles of sodium bicarbonate. sodium (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) according to the reactions:

NaOH + COl - NaHC ^Q ₃ 2NaOH + CO2 -> Na ₂ CO ₃ + H ₂ O

Thus, after complete carbonation, in situ, a non-corrosive composition consisting of microparticles and nanoparticles of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) and carbon dioxide (CO ₂ ) are formed. dense state, preferably in the supercritical state.

 Decarbonation cycle:

The decarbonation of the composition formed by reaction between the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and the carbon dioxide (C0 ₂ ) makes it possible to give the sodium hydroxide its caustic power for a sufficient time to corrode the macromolecular encrusted contaminants. and biofilms, for optimizing the saponification of fats, for effecting protein hydrolysis, detachment, destabilization and / or degradation and / or inactivation of prions and / or endotoxins and embrittlement of the external envelope of proteins. spores; but nevertheless insufficient time to corrode the material.

The decarbonation can be obtained quickly by decompression or depressurization of the treatment chamber (101). But generally, the decompression or depressurization of the treatment chamber (101) under pressure results in a non-selective output of all treatment agents. In other words, the carbon dioxide (CO ₂ ) is simultaneously evacuated with the sodium hydroxide (sodium hydroxide (NaOH)) which one wants to control the causticity. However during decarbonation, only the evacuation of carbon dioxide (C0 ₂ ) is desired.

 Advantageously, this problem is solved by virtue of the present invention by using one or more hydrophobic gas-liquid separation membranes (230b) (FIG. 1) according to the following sequence.

The decarbonation is obtained by depressurization or decompression by opening the valves (111b, 111c, 111d) preferably located in the upper part of the treatment chamber (101); the mixture (NaOH) / (CO ₂ ) is divided into its two main components, sodium hydroxide solution (sodium hydroxide (NaOH)) and carbon dioxide (CO ₂ ) using the hydrophobic membrane ( 230b) that allows only the return of the sodium hydroxide solution (sodium hydroxide (NaOH)) decarbonated caustic and any hydrophilic compound in the treatment chamber (101). Thus, only the carbon dioxide (C0 ₂ ) is released from the treatment chamber (101). Advantageously, the carbon dioxide (C0 ₂ ) released from the treatment chamber (101) can enter a pipe (10b) to join the separation chamber (230) where once purified with the filtration membranes, can escape through the pipe (9) controlled by the valves (403 and 414). With the compressor (509) the purified carbon dioxide (CO ₂ ) is stored in its specific compartment in the tank system (501).

When carbon dioxide (CO ₂ ) is released, it can carry hydrophobic compounds that are useful for one aspect of the treatment, such as oils that are useful for saponification, especially in the case where the soil to be cleaned is important.

In accordance with the invention, there is provided a hydrophilic membrane (230c) for gas-liquid separation which contiguously follows the hydrophobic membrane (230b) for gas-liquid separation and which is capable of extracting carbon dioxide (C0 ₂ ) said useful hydrophobic compounds and return them to the treatment chamber (101). With the valve (11 ld) closed, access to said hydrophilic membrane (230c) for gas-liquid separation is controlled by the valve (111e) and the return of said useful hydrophobic compounds to the treatment chamber (101) is controlled by the check valve (111 f).

 Said hydrophilic membrane (230c) for gas-liquid separation is preferably ceramic or hydrophilic polymers.

The decarbonation obtained by depressurization or decompression of the treatment chamber (101) can be optimized by a moderate increase in temperature above 60 ° C, preferably between (60 and 70 ° C), or by the action of ultrasound or megasons, or by substitution of carbon dioxide (C0 ₂ ) by inert gases (nitrogen, helium, argon etc.) or a combination of these actions. Ultrasound is used at frequencies from 20 KHz to 1 MHz. Megasons are used at frequencies from 1 MHz to 100 MHz. Said inert gases come from a specific compartment in the system (500a) and enter the pipes (1) and (2) through the pipe (la).

Substituting carbon dioxide (C0 ₂ ) with inert gases also makes it possible not only to overcome the cooling problems resulting from rapid decompression but also to reduce the surface tension of the sodium hydroxide solution (sodium hydroxide (NaOH )) caustic.

During the decarbonation / carbonation cycles obtained by depressurization / pressurization or decompression / compression, the rate of depressurization / pressurization is preferably, but not exclusively, between 10 bar / hour and 4000 bar hour; the decompression / compression cycle rate is including, preferably, but not exclusively, between 1 cycle / hour and 200 cycles per hour; the pressure variation associated with the decompression / compression cycle is preferably, but not exclusively, between 1 bar and 700 bar.

The decarbonation can furthermore be obtained without depressurization, at constant supercritical pressure in the treatment chamber (101), by moderate increase of the temperature above 60 ° C, preferably between 60 and 70 ° C using heat exchangers (not shown) and / or using ultrasound and megasons using acoustic means (not shown). Under these conditions, the alkaline solutions of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) release carbon dioxide (CO ₂ ) and the sodium hydroxide (sodium hydroxide (NaOH)) returns to its original state. causticity.

 In addition, the decarbonation can be done during the recirculation (will be described later) of the entire composition.

 The time per unit cycle of decarbonation may be longer or shorter depending on the ability of the material to resist corrosion. As an indication, it can be between 1 millisecond to 10 minutes, or even greater than 10 minutes and preferably it can be between 1 minute and 5 minutes.

The time per unit carbonation cycle varies according to the rate of diffusion of carbon dioxide (C0 ₂ ) in sodium hydroxide (sodium hydroxide (NaOH)) caustic.

^■ When the treatment is a terminal sterilization of the thermosensitive material with default inactivation of the prions:

 The packaged material is placed in contact with the sodium hydroxide solution (sodium hydroxide (NaOH)), preferably, but not exclusively, in two ways:

o A vacuum is created whose level is included, preferably, but not exclusively, between the primary vacuum (1-10 ^{~ 3} bar) and the ultra-vacuum (10 ^{~ 10} -10 ^{~ 15} bar), and the solution is added caustic soda (sodium hydroxide (NaOH)) until its vapor pressure is reached, preferably, but not exclusively, between 18 and 200 torr and at temperatures, preferably, but not exclusively, between 20 and 60 ° C, more preferably between 40 and 60 ° C; said sodium hydroxide solution (sodium hydroxide (NaOH)) which can be further added in atomized form by means of an ultrasonic spray nozzle (108) for fractionating the aqueous solution of sodium hydroxide solution (hydroxide sodium (NaOH)) in very fine volatile droplets; said sodium hydroxide solution (caustic sodium hydroxide (NaOH)) being at least at a minimum concentration of effectiveness and in sufficient quantity to thoroughly impregnate all external and internal surfaces of the contaminated materials; the addition of sodium hydroxide solution (sodium hydroxide (NaOH)) vacuum caustic having the advantage of optimizing its diffusion in the complex geometries of the packaged material.

Without creating a vacuum, the sodium hydroxide solution (Sodium Hydroxide (NaOH)) in atomized form is added by means of spraying means such as an ultrasonic spray nozzle (108) for fractionating the aqueous solution solution. sodium hydroxide (sodium hydroxide (NaOH)) in very fine volatile droplets. Thus we obtain firstly, a better contact of the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic with the packaged material; on the other hand it avoids excessive wetting packaging; furthermore, contact of the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) with the packaged material before its reaction with carbon dioxide (C0 ₂ ) is promoted to form the bicarbonates and carbonates; said sodium hydroxide solution (caustic sodium hydroxide (NaOH)) being at least at a minimum concentration of efficiency and in a sufficient quantity to impregnate all the external and internal surfaces of the contaminated materials. This form of implementation of the method is better suited to materials that do not have complex geometries.

 It should be noted that the sodium hydroxide solution (sodium hydroxide (NaOH)) can also be added as described above when the treatment is cleaning with simultaneous inactivation of infectious contaminants.

Sodium hydroxide solution (Sodium Hydroxide (NaOH)) is added at concentrations between 0.01 M and 20M; preferably, but not exclusively, concentrations of between 2M and 10M; at temperatures, preferably, but not exclusively, between 20 and 60 ° C and at pressures, preferably but not exclusively, greater than 0 bar and less than or equal to 700 bar. It is understood that sodium hydroxide (sodium hydroxide (NaOH)) is added at very high pressures of the order of 700 bar, when beforehand it has been reached by gradually increasing a pressure of the same order of magnitude in the chamber treatment (101). Carbonation cycle:

Then, carbon dioxide (C0 ₂ ) can be added in the dense state under pressure, preferably in the supercritical state and at rates of between 20 kg / h and 400 kg / h, until pressures of preferably, but not exclusively, between 73 and 300 bar in the process chamber (101) and forming in situ a modulable caustic composition as previously described when the treatment is cleaning with simultaneous inactivation of infectious contaminants.

The supercritical carbon dioxide (C0 ₂ ) is introduced at a temperature preferably between 31 ° C and 60 ° C, in all cases above 31 ° C.

The temperature is then maintained, preferably between 40 and 60 ° C in the treatment chamber (101). This range of temperatures makes it possible to treat the thermosensitive materials without degrading them. If the temperature rises above 60 ° C, to return to temperatures between 40 and 60 ° C, carbon dioxide (C0 ₂ ) in the dry ice state, in the state of snow carbonic acid, in the liquid state can be introduced in sufficient quantity to bring the temperature between 40 and 60 ° C.

 During carbonation, rapid access to supercritical properties is preferred.

 Since the sodium hydroxide solution (sodium hydroxide (NaOH)) must be added in sufficient quantity to impregnate all the external and internal surfaces of the contaminated materials, it must not be excessively present in the treatment chamber ( 101) at the risk of compromising rapid access to supercritical properties.

 Thus, preferably, once all the external and internal surfaces of the contaminated materials have been impregnated with the sodium hydroxide solution (Sodium Hydroxide (NaOH)), it will be ensured that the valve (111) is eliminated. if necessary, excess sodium hydroxide solution (sodium hydroxide (NaOH)) caustic.

Preferably, but not exclusively, the sodium hydroxide solution (Sodium Hydroxide (NaOH)), once added as jets (109b) to the contaminated materials, is removed as soon as possible from the treatment chamber (101) by the pipe (10) and recirculated with the pump (400) after being regenerated by the filtration membranes (284, 285, 286, 287) of the separation chamber (230). This makes it possible to renew gradually the sodium hydroxide solution (Sodium hydroxide (NaOH)) caustic reacts with contaminated materials and consume small amounts of sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic.

 Depending on the rate of evacuation of the sodium hydroxide solution (sodium hydroxide (NaOH)) from the treatment chamber (101) and the recirculation rate of the sodium hydroxide solution (caustic sodium hydroxide (NaOH)), it can occupy constantly, preferably, but not exclusively, 0.001% to 30% of the total volume of the treatment chamber (101); more preferably the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic constantly occupies 0.001% to 5% of the total volume of the treatment chamber (101).

More preferably, to promote the action of supercritical carbon dioxide (C0 ₂ ) to be added later, the rate of evacuation of the sodium hydroxide solution (caustic Sodium hydroxide (NaOH)) from the treatment chamber (101 ) and its recirculation rate will be such that only a film of sodium hydroxide solution (sodium hydroxide (NaOH)) is produced on the surface of the packaging and the treated material. In addition, the contact surface between sodium hydroxide (caustic sodium hydroxide (NaOH)) and carbon dioxide (CO ₂ ) is thus increased, resulting in rapid carbonation.

 Decarbonation cycle:

The decarbonation of the composition formed by reaction between the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) and the carbon dioxide (C0 ₂ ) makes it possible to give the sodium hydroxide its caustic power for a sufficient time to achieve by default the cleaning of the contaminated material as well as the degradation of any encrusted macromolecular contaminants and biofilms, the saponification of possible fats, the hydrolysis of the proteins, the detachment, the destabilization and / or the degradation and / or the inactivation of possible prions and / or endotoxin and / or embrittlement of the outer envelope of the spores.

 During decarbonation, the rapid return to the caustic properties of caustic soda solution (sodium hydroxide (NaOH)) and its better contact with the complex geometries of the packaged material are sought.

Thus, the decarbonation will be preferably, but not exclusively, by decompression or depressurization of the treatment chamber (101) without evacuation of the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic whose causticity is to be controlled; this, thanks to one or more hydrophobic gas-liquid separation membranes (230b) (FIG. 1). Indeed, after suspension of recirculation (will be described later) of the composition and the continuous addition of supercritical carbon dioxide (C0 ₂ ), the decarbonation is obtained by depressurization or decompression by opening the valves (111b, 11c, 11ld) located preferably in the upper part of the treatment chamber (101); the mixture (NaOH) / (CO ₂ ) is divided into its two main components, sodium hydroxide solution (sodium hydroxide (NaOH)) and carbon dioxide (CO ₂ ), using the hydrophobic membrane of gas-liquid separation (230b) which only allows the return of the sodium hydroxide solution (sodium hydroxide (NaOH)) decarbonated caustic and any hydrophilic compound in the treatment chamber (101). Thus, only the carbon dioxide (C0 ₂ ) is released from the treatment chamber (101) and enters the pipe (10b) to reach the separation chamber (230) where once purified using the filtration membranes (284, 285, 286, 287), can escape through the pipe (9) controlled by the valves (403 and 414). With the compressor (509) the purified carbon dioxide (C0 ₂ ) is stored in its specific compartment in the tank system (501).

In addition, by means of the compressor (509) and / or the vacuum pump (232), the valves (1 l ia, 403) and / or (231, 231a, 304) being open, the outlet of the carbon dioxide ( C0 ₂ ) can be accelerated thereby reducing the pressure until the vapor pressure, under vacuum, of the sodium hydroxide (Sodium hydroxide (NaOH)) is reached; this becomes caustic again and also returns to its vapor state, hence better contact with the complex geometries of the packaged material. Although the soda is in the vapor state, it can not leave the treatment chamber (101) because the separation membrane (230b) of hydrophobic nature or very hydrophobic can not let the soda solution vapor (Hydroxide of sodium (NaOH)) which is hydrophilic in nature.

The decarbonation obtained by depressurization or decompression of the treatment chamber (101) may, in addition, be optimized by a moderate increase in temperature above 60 ° C, preferably between (60 and 70 ° C), or by action of ultrasound or megasons, or by substitution of carbon dioxide (C0 ₂ ) by inert gases (nitrogen, helium, argon etc.) or a combination of these actions. Ultrasound is used at frequencies from 20 KHz to 1 MHz. Megasons are used at frequencies from 1 MHz to 100 MHz. Said inert gases come from a specific compartment in the system (500a) and enter the pipes (1) and (2) through the pipe (la). The fact of substituting carbon dioxide (C0 ₂ ) with inert gases also makes it possible not only to overcome the cooling problems following rapid decompression but also to reduce the surface tension of the sodium hydroxide solution (sodium hydroxide). (NaOH)) caustic.

 During the decarbonation / carbonation cycles obtained by depressurization / pressurization or decompression / compression, the rate of depressurization / pressurization is between 10 bar hour and 4000 bar / hour; the decompression / compression cycle rate is from 1 cycle / hour to 200 cycles / hour; the pressure variation associated with the decompression / compression cycle is between 1 bar and 700 bar.

The decarbonation can furthermore be obtained without depressurization, at constant supercritical pressure in the treatment chamber (101), by moderate increase of the temperature above 60 ° C, preferably between 60 and 70 ° C using heat exchangers (not shown) and / or using ultrasound and megasons using acoustic means (not shown). Under these conditions, the alkaline solutions of sodium bicarbonate (NaHCC> 3) and sodium carbonate (Na ₂ CO ₃ ) release carbon dioxide (CO ₂ ) and sodium hydroxide (sodium hydroxide (NaOH)) its causticity.

 In addition, the decarbonation can be done during the recirculation (will be described later) of the entire composition.

 The time per unit cycle of decarbonation may be longer or shorter depending on the ability of the material to resist corrosion. As an indication, it can be between 1 millisecond to 10 minutes, or even greater than 10 minutes and preferably it can be between 1 minute and 5 minutes.

The time per unit carbonation cycle varies according to the rate of diffusion of carbon dioxide (C0 ₂ ) in sodium hydroxide (sodium hydroxide (NaOH)) caustic.

^■ When the treatment is a terminal sterilization of thermostable material with default inactivation of prions:

Soda (Sodium Hydroxide (NaOH)) is used in a state of saturated vapor with carbon dioxide (C0 ₂ ). In other words, sterilization with water vapor saturated with alkaline water is carried out while controlling the causticity of sodium hydroxide (sodium hydroxide (NaOH)) caustic. Carbon dioxide (C0 ₂ ) is added first, preferably in supercritical form in the form of jets (109c) through the pipes (1, 1c), in order to drive the air in the complex geometries which is less dense than carbon dioxide (C0 ₂ ). The valves (111 and 11 la) of the pipe (10) are open during the addition of carbon dioxide (C0 ₂ ) thus allowing the evacuated air to be evacuated.

The carbon dioxide (CO ₂ ), preferably in the supercritical state, is added at a rate of between 20 kg / h and 400 kg / h and at a temperature greater than or equal to 31 ° C. until pressures of preferably, but not exclusively, between 73 and 300 bars in the processing chamber (101); this pressure and temperature condition also makes it possible to initiate the inactivation of the microorganisms by the supercritical carbon dioxide (CO ₂ ) which diffuses inside them.

The air expelled by the carbon dioxide (C0 ₂ ) passes through the separation chamber (230) where the air / CO ₂ mixture is filtered and then through the pipe (9) controlled by the valve (403) to then be stored in a special tank of the tank system (501).

In another configuration, the air expelled by the carbon dioxide (C0 ₂ ) does not pass through the separation chamber (230) but through another pipe (not shown) provided with filters and then stored in a special tank of tank system (501).

The stored air / CO ₂ mixture may later be subjected to a particular treatment to separate them; said particular treatment may for example consist in adding the caustic soda to the air / CO ₂ mixture for trapping the CO ₂ and releasing the air, the C (½ being recovered later by the appropriate methods of decarbonation mentioned above; It also consists of liquefying the gas mixture and then separating them by means of the boiling point of each gas.

 Carbonation cycle:

After sufficient time to expel the air in the complex geometries of the packaged or unpackaged material, supercritical carbon dioxide (C0 ₂ ) is present in the process chamber (101).

Thus, we can not now do without several repeated vacuum operations generally necessary during sterilization with saturated water vapor, eliminating this time, with the aid of carbon dioxide (C0 ₂ ), completely in complex geometries, air which is a bad coolant decreasing the thermal effect and especially the wetting and hydrolysing power of saturated water vapor and therefore its sterilizing power; but also initiate the inactivation of microorganisms using supercritical carbon dioxide (C0 ₂ ).

After having preferably lowered the pressure of the carbon dioxide (CO ₂ ) to pressures of between 1 and 10 bar, the saturated sodium hydroxide (Sodium hydroxide (NaOH)) is then formed in the reaction chamber. separation (230) used in this case as a steam boiler.

 It should be noted that in the present invention there may be one or more additional separation chambers (230) for forming the saturated sodium hydroxide (sodium hydroxide (NaOH)) caustic at the same time as the evacuation of the air and thus begin the sterilization with saturated sodium hydroxide (Sodium Hydroxide (NaOH)) caustic as soon as said air evacuation is complete. The presence of at least two separation chambers (230) will make it possible to carry out sterilization with saturated sodium hydroxide (caustic sodium hydroxide (NaOH)) by displacement of the air by gravity or injection of saturated sodium hydroxide (Sodium hydroxide (NaOH)) caustic under pressure.

 After formation of the saturated sodium hydroxide (Sodium Hydroxide (NaOH)) in the separation chamber (230) by, preferably, but not exclusively, by the heating means (241), the treatment chamber (101) is filled. ) with the saturated sodium hydroxide (sodium hydroxide (NaOH)) caustic via the channels (7b, 7a, 7 and 2) controlled by the valves (405, 404, 413, 402) in the form of jets (109 , 109a).

In addition, the saturated sodium hydroxide (Sodium Hydroxide (NaOH)), before being introduced by the pump (400) into the treatment chamber (101) through the pipes (2) in the form of jets (109, 109a) may first be carbonated in the gas-liquid contact membranes (230a) with the dense carbon dioxide (CO ₂ ) from the line (1a).

It is also possible to add carbon dioxide (C0 ₂ ) directly into the treatment chamber (101) via the pipes (1 and 1c).

The sodium hydroxide (caustic sodium hydroxide (NaOH)) will be added at pressures preferably, but not exclusively, between 2 and 11 bar, at concentrations preferably, but not exclusively, between 1 and 20M, preferably still between 2 and 10M. The temperature is then maintained, preferably between 120 and 180 ° C in the treatment chamber (101). Thus, after complete carbonation, in situ, a non-corrosive composition consisting of microparticles and nanoparticles of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) and carbon dioxide (CO ₂ ) are formed. dense state, preferably in the supercritical state.

 Decarbonation cycle:

 As in the case of the previous treatment method of terminally sterilizing heat-sensitive material with default inactivation of prions, during decarbonation, the rapid return to the caustic properties of the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic and better contact of the latter with the complex geometries of the packaged material is sought.

 Thus, as in the case of the previous treatment method of terminally sterilizing heat-sensitive material with default inactivation of the prions, decarbonation will preferably, but not exclusively, be by decompression or depressurization of the treatment chamber (101). without evacuation of the sodium hydroxide solution (Sodium Hydroxide (NaOH)) which one wants to control the causticity.

Particularly, when the carbon dioxide (CO ₂ ) outlet is accelerated, the pressure decrease no longer reaches the vacuum range, but stops at pressures above 2 bar and the temperature is maintained above 120 ° C. in the treatment chamber. Thus, after total liberation of the carbon dioxide (CO ₂ ), the sodium hydroxide (sodium hydroxide (NaOH)) becomes caustic while remaining in the vapor state. Although the soda is in the vapor state, it can not leave the treatment chamber (101) because the separation membrane (230b) of hydrophobic nature or very hydrophobic can not let the soda solution vapor (Hydroxide of sodium (NaOH)) which is hydrophilic in nature.

 In addition, the decarbonation can be done during the recirculation (will be described later) of the entire composition.

During the decarbonation / carbonation cycles obtained by depressurization / pressurization or decompression / compression, the rate of depressurization / pressurization is preferably, but not exclusively, between 10 bar / hour and 100 bar / hour; the decompression / compression cycle rate is preferably, but not exclusively, from 1 cycle / hour to 10 cycles / hour; the pressure variation associated with the decompression / compression cycle is preferably, but not exclusively, between 1 bar and 10 bar. The unit of decarbonation time is a function of the concentration of caustic soda, the pressure and the temperature and the ability of the material to resist corrosion. Thus, in this case of treatment of thermostable materials, the unit of decarbonation time may be longer, since most thermostable materials are stainless steels. For example the unit of decarbonation time at a soda concentration of 2M can be between 30min and 1h. The real time decarbonation unit may be determined by those skilled in the art. Step d): mechanical stirring:

Whatever the treatment carried out, as soon as the sodium hydroxide solution (sodium hydroxide (NaOH)) and / or carbon dioxide (CO ₂ ) are added, preferably in the supercritical state, the stirrer is actuated. (104).

 Under the effect of the agitator (104) the cylindrical baskets (102) are subjected to a rotational movement that can reach if necessary 1500 revolutions / minute. Of course, the rotational movement can be periodically reversed. Thus the cylindrical baskets (102), including their contents, behave like the blades of the propeller of a stirrer and stir homogeneously the entire volume of the treatment chamber (101). This results in a complete homogenization of the reactive medium in the treatment chamber (101) and a better contact between the composition formed by sodium hydroxide (sodium hydroxide (NaOH)) caustic and carbon dioxide (C0) dense, preferably in the supercritical state with all surfaces of the contaminated materials. Said contact is all the more optimized thanks to the multidirectional moving jets (109) coming from the cylindrical nozzle system (110), the nozzle arms (not shown) and the axis nozzles (107b) carrying the cylindrical baskets (102). ).

The contacting of the internal and external surfaces of the contaminated materials with the composition of sodium bicarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ) and carbon dioxide (CO ₂ ) in the supercritical state, allows simultaneously perform the cleaning and inactivation of all known types of infectious contaminants such as yeasts, fungi, molds, protozoa, bacteria in vegetative form, bacteria in biofilm form, bacterial spores, viruses , mycobacteria, algae, endotoxins and prions. Steps e), f), g): recirculation, separation and inactivation of soluble and insoluble contaminants, reintroduction into the treatment chamber:

 ■ When the treatment is cleaning with simultaneous inactivation of infectious contaminants:

According to the invention, during the simultaneous phases of cleaning and inactivation of infectious contaminants, the composition consisting of alkaline solutions of sodium bicarbonate (NaHCCb) and sodium carbonate (Na ₂ CO 3), and carbon dioxide ( C0 ₂ ) in the dense state, preferably in the supercritical state, can be further recirculated preferably continuously by means of the recirculation pump (400).

 Separation of soluble and insoluble contaminants:

Generally, during the recirculation of the cleaning fluid, only the insoluble contaminants are separated; Soluble contaminants are separated only at the end of the reaction using other additional technologies (cyclone separators, activated carbon bed adsorption, etc.) requiring a lot of time and energy. If these conditions were applied in the present invention, the carbon dioxide (CO ₂ ) in the dense state preferably in the supercritical state and the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) would lose their physical properties. chemical after reacting with contaminants; and this would require a large consumption of these treatment agents and a fairly long treatment time.

Advantageously, thanks to the filtration membranes (284, 285, 286, 287) assembled in a single separation chamber (230) of the present invention, this problem is solved by simultaneously separating the soluble and insoluble contaminants extracted while continuously regenerating the treatment agents which are carbon dioxide (C0 ₂ ) in the dense state preferably in the supercritical state and the sodium hydroxide solution (Sodium hydroxide (NaOH)) and the filtration membranes (284, 285 , 286, 287) themselves.

With reference to FIG. 2, the contaminants extracted by the composition comprising sodium bicarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ) and carbon dioxide (CO ₂ ) in the dense state preferably, in the supercritical state, are evacuated to the separation chamber (230) through the pipe (10) controlled by the non-return valves (11 1, 111a). Thus, a contaminated fluid (236) is formed in the compartment (235) of the separation chamber (230). Under the effect of pressure, the fluid (236) is successively filtered by microfiltration membranes (284), ultrafiltration membranes (285), nanofiltration membranes (286), reverse osmosis membranes (287). The pressure difference around the filtration membranes (284, 285, 286, 287), in other words, obtaining a depression downstream of said filtration membranes (284, 285, 286, 287) is maintained. partly because of the creation of a high flow rate at the recirculation pump (400) which makes it possible to obtain a treatment agents outlet velocity greater than their rate of entry into the separation chamber (230), said input speed being controllable by the valves (111 and 111a) or by a metering pump (not shown) on the line (10); on the other hand, the depression downstream of the filtration membranes (284, 285, 286, 287) is advantageously maintained, in addition, by the compressor (509) which, via the pipe (9) controlled by the valve (403), continuously let carbon dioxide (C0 ₂ ) in the dense state preferably in the supercritical state, introduced into the separation chamber (230); the carbon dioxide (C0 ₂ ) in the dense state preferably in the supercritical state released is pure thanks to the filtration membranes (284, 285, 286, 287) and the gas-liquid separation membrane (403a) ; preferably, the hydrophobic membrane (403a) of gas-liquid separation is preferably made of PTFE (Teflon ^®) or polypropylene; said carbon dioxide (C0 ₂ ) in the dense state, preferably in the purified supercritical state, is then recirculated, without decompression, directly to the treatment chamber (101) via the pipes (9a then 2) or (9 and then 1), preferably through the pipes (9a and 2) respectively controlled by the valves (41 and 402). Moreover, the pressure difference around the filtration membranes (284, 285, 286, 287) can be controlled by downstream addition of the filtration membranes (284, 285, 286, 287) via the pipe (8). controlled by the valve (508), carbon dioxide (C0 ₂ ) in the dense state, preferably in the supercritical state and having a pressure below the pressure of carbon dioxide (C0 ₂ ) supercritical coming from the chamber treatment (101).

It should be noted that the upstream pressure of the filtration membranes (284, 285, 286, 287) is obtained by maintaining a constant pressure in the treatment chamber (101) by continuously adding carbon dioxide (C0 ₂ ) to the dense state, preferably in the supercritical state through the pipes (1a, 1, 2) so that the amount of carbon dioxide (CO ₂ ) in the dense state, preferably in the supercritical state, the treatment chamber (101) is largely greater than the amount of carbon dioxide (CO ₂ ) in the dense state, preferably in the outgoing supercritical state. Thus, by virtue of the upstream pressure of the filtration membranes (284, 285, 286, 287), all the infectious contaminants are successively stopped by the filtration membranes (284, 285, 286, 287); for example the bacteria are stopped by the microfiltration membrane (284), the viruses, prions, endotoxins are stopped by the ultrafiltration membrane (285); the other contaminants being stopped by the nanofiltration (286) and reverse osmosis membranes (287) as described above.

 Inactivation by passage in a pore of restricted diameter:

The pores of the filtration membranes (284, 285, 286, 287) have microscopic diameter diameters which allow, by frontal filtration, to force under pressure the infectious contaminants to pass in a space smaller than them; it follows a destruction of the membranes of the microorganisms or the tertiary or secondary structure of the prions and endotoxins; hence their inactivation.

 Inactivation by drastic conditions of temperature, acoustic emission and causticity in the separation chamber (230):

 It is also possible to subject the alkaline composition containing infectious contaminants extracted and still active under severe conditions to the separating chamber (230) to finally inactivate said infectious contaminants.

 The separation chamber (230) is provided with heating means such as heat exchangers (241) for heating the recirculated alkaline solutions at temperatures preferably between 60 ° C and 160 ° C, more preferably between 80 ° C and 140 ° C. The separation chamber (230) can also be provided with acoustic means (242) producing ultrasound and megasons making it possible to subject the recirculated alkaline solutions to acoustic emissions of high intensities; said high intensity ultrasound being used, preferably, but not exclusively, at frequencies from 200KHz to 1MHz and said high intensity megasons being used, preferably, but not exclusively, at frequencies from 10 MHz to 100 MHz.

These drastic conditions of temperature, acoustic emission and causticity make it possible to completely inactivate the microorganisms, the prions and endotoxins contained in the extracted contaminants without compromising the physical integrity of the treated materials which are sheltered in the environment. treatment chamber (101) where "soft" conditions of temperature, acoustic emission and causticity prevail. In addition, under these conditions of temperature and / or acoustic emission, the alkaline solutions of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) rapidly release carbon dioxide (C0 ₂ ) and Sodium hydroxide (sodium hydroxide (NaOH)) is reformed. The decarbonation of the composition is thus carried out during recirculation.

It is also possible to add in the part (235) of the separation chamber (230), by the system (200) and through the pipe (5) controlled by the valve (203), slaked lime Ca ( OH) ₂ to alkaline solutions to produce sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic; the calcium ions (Ca ²⁺ ) being later stopped by the nanofiltration membrane (286) capable of stopping the divalent ions.

In the separation chamber (230), the decarbonation can also be optimized by the combined use of the heating action, the action of ultrasound and megasons, the action of the slaked lime Ca (OH) ₂ .

Reintroduction into the treatment chamber (101):

Once purified, the carbon dioxide (CO ₂ ) previously released by the alkaline solutions of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) by increasing the temperature above 60 ° C and / or by submission to acoustic emissions, can escape through the pipe (9) controlled by the valve (403). Thanks to the compressor (509) the purified carbon dioxide (C0 ₂ ) is recycled to the treatment chamber (101) via the pipes (9a and 2) after its temperature is at least reduced below 60 ° C. thanks to the condenser (510).

It should be noted that if one is in the decarbonation phase, the purified carbon dioxide (C0 ₂ ) is recycled to a special compartment in the tank system (501).

 Soda (Sodium hydroxide (NaOH)) purified caustic between the nanofiltration membrane (286) and the reverse osmosis membrane (287) as well as the purified water (237) are recirculated by means of the recirculation pump ( 400) and opening the valves (405, 404, 413, 402) allowing the solutions to pass through the pipes (7b, 7a, 7, 2).

Solutions recirculated by the pump (400), before being introduced into the treatment chamber (101) via the pipes (2) in the form of jets (109, 109a), first pass through a heat exchanger (412) where they are cooled to at least a temperature below 60 ° C, then in the gas-liquid contact membranes (230a) where they are recarbonated with carbon dioxide (C0 ₂ ) supercritical from the pipe (the ).

In variants, the sodium hydroxide solution (sodium hydroxide (NaOH)) is not brought into contact with the carbon dioxide (C0 ₂ ) in the dense state, preferably in the supercritical state, in the membranes contact gas-liquid (230a) but in the treatment chamber (101) filled with carbon dioxide (C0 ₂ ) in the dense state preferably in the supercritical state. Thus, in the treatment chamber (101), powders of microparticles and nanoparticles of sodium bicarbonate (NaHCO ₃ ) and of sodium carbonate (a ₂ CO ₃ ) are produced, according to the known SAS technique (Supercritical Anti Solvent). powders.

^■ When the treatment is a terminal sterilization of the thermosensitive material with default inactivation of the prions:

 The composition can be recirculated, during carbonation, using the recirculation pump (400), preferably via the pipe (10a) controlled by the valves (112 to 117) and between the nanofiltration membrane (286) and the reverse osmosis membrane (287) to gain the pipeline (2) and then be rapidly carbonated using the gas-liquid contact membrane (230a).

In addition, after carbonation, it is possible, without depressurizing the treatment chamber (101), to partially recirculate the composition by selectively recirculating carbon dioxide (C0 ₂ ) using one or more separation membranes. gas-liquid (230b), the sodium hydroxide solution (Sodium Hydroxide (NaOH)) remaining in contact with the material packaged in the treatment chamber (101). Indeed, with reference to FIGS. 1 and 2, during recirculation, on the recirculation circuit, the valves (111b, 11a, 11d, 111a, 403, 415) are opened, the other valves being closed. Thus, only the carbon dioxide (C0 ₂ ) is recirculated, without evacuation of the sodium hydroxide solution (caustic sodium hydroxide (NaOH)), which can not pass through the hydrophobic gas-liquid separation membrane (s) (230b) and remains therefore in contact with the material undergoing treatment.

 ■ When the treatment is a terminal sterilization of thermostable material with default inactivation of prions:

Recirculating, in the same manner as when the treatment is cleaning with simultaneous inactivation of infectious contaminants, the composition formed by the sodium hydroxide solution (Sodium Hydroxide (NaOH)) and the carbon dioxide (C0 ₂ ) in the dense state preferably in the supercritical state.

In this case, there is no need to heat the alkaline solutions of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) because it is at temperatures between 120 and 180 ° C.

Once purified by the filtration membranes (284, 285, 286, 287), the filtered carbon dioxide (C0 ₂ ) can escape through the line (9) controlled by the valve (403). Thanks to the compressor (509) the purified carbon dioxide (C0 ₂ ) is recycled to the treatment chamber (101) via the pipes (9a and 2).

 Soda (purified caustic sodium hydroxide (NaOH)) between the nanofiltration membrane (286) and the reverse osmosis membrane (287) as well as the purified water (237) is recirculated by means of the recirculation pump ( 400) and opening the valves (405, 404, 413, 402) allowing the solutions to pass through the pipes (7b, 7a, 7, 2).

Solutions recirculated by the pump (400), before being introduced into the treatment chamber (101) via the pipes (2) in the form of jets (109, 109a), first pass through the membranes of gas-liquid contact (230a) where they are recarbonated with supercritical carbon dioxide (C0 ₂ ) from the pipe (1a).

In addition, after carbonation, it is possible, without depressurizing the treatment chamber (101), to partially recirculate the composition by selectively recirculating carbon dioxide (C0 ₂ ) using one or more gas separation membranes. liquid (230b), the saturated sodium hydroxide (caustic sodium hydroxide (NaOH)) remaining in contact with the packaged and / or unpackaged material in the treatment chamber (101). In fact, with reference to FIGS. 1 and 2, during the recirculation, on the recirculation circuit, the valves (111b, 111c, 111d, 111a, 403, 415) are opened, the other valves being closed. Thus, only the carbon dioxide (C0 ₂ ) is recirculated, without evacuation of the saturated sodium hydroxide (caustic sodium hydroxide (NaOH)), which can not pass through the hydrophobic gas-liquid separation membrane (s) (230b) and thus remains in contact with material undergoing treatment. In-situ declogging:

 In the state of the art, filtration membranes in general have a major disadvantage because they clog very quickly because of insoluble and soluble contaminants or solid particles formed by precipitation; this can lead to a slowing down of the filtration rate.

Advantageously, the present invention solves this problem, on the one hand, by providing heating means (241) and acoustic emission (242) promoting the dissolution of solid particles of bicarbonate or carbonate and contaminants extracted from the chamber of treatment (101). Indeed, the heating means (241) can heat the recirculated alkaline solutions at temperatures between 60 ° C and 160 ° C, preferably between 80 ° C and 140 ° C. Acoustic means (242) producing ultrasound and megasons making it possible to subject the recirculated alkaline solutions to acoustic emissions of high intensities. Under these conditions of temperature and / or acoustic emission, the alkaline solutions of sodium bicarbonate (NaHCO ₃ ) and sodium carbonate (Na ₂ CO ₃ ) rapidly release carbon dioxide (C0 ₂ ) and are dissolved, allowing thus reforming the sodium hydroxide solution (Sodium Hydroxide (NaOH)) capable of de-fouling the filtration membranes (284, 285, 286, 287) by rapidly dissolving the extracted contaminants.

 Said dissolution of the solid particles of bicarbonate or carbonate and the extracted contaminants is optimized by intermittently closing the valve (404) of the pipe (7a) and recirculating by the pump (232) the pure water (237) by making it pass successively through the pipes (7a, 11a, 11b, 3b) and by opening the valves (411, 231b, 401a). After a sufficient time of recirculation of the pure water (237), the valves (411, 231b, 401a) are closed and the pump (232) is stopped, then the sodium hydroxide solution (purified sodium hydroxide (NaOH)) is purified. between the nanofiltration membrane (286) and the reverse osmosis membrane (287) and the purified water (237) are recirculated through the recirculation pump (400) and by opening the valves (405, 404, 413, 402) allowing the solutions to pass through the pipes (7b, 7a, 7, 2) ·

On the other hand, in order to solve this clogging problem, it is also possible to temporarily interrupt the recirculation of the composition by closing the valve (111) and after recovering and returning the caustic soda solution (Sodium hydroxide (NaOH)). as well as the purified water (237) to the treatment chamber (101), water (20, 5a, 10a) is added via the system (200) followed by the addition of supercritical carbon dioxide (C0 ₂ ) through the pipe (8) so as to remove the contaminants retained on the filters. The valves (231, 231a, 408, 409, 410, 411) being open, the pump (232) is actuated and thus all that is retained by the filtration membranes (284, 285, 286, 287) is recovered in the waste collection chamber (300); which makes it possible to regenerate said filtration membranes (284, 285, 286, 287). In said waste recovery chamber (300), the reverse osmosis membrane (287) is used to filter the effluent from the separation chamber (230) and to obtain pure water which is recirculated back to the the separation chamber (230) through the pipes (13, 13a and 3b) respectively controlled by the valves (301 and 301a, 301b, 401a). Simultaneously, the gas-liquid separation membrane (303) of the same nature as the gas-liquid separation membrane (403a) makes it possible to return only the supercritical carbon dioxide (C0 ₂ ) introduced beforehand through the pipe (8), towards the special carbon dioxide tank (C0 ₂ ) in the tank system (501), through the pipes (14 and 9) respectively controlled by the valves (304 and 414). It follows that it is recovered in the chamber (300), in the upstream portion of the reverse osmosis membrane (287), that dry and non-toxic waste. After a sufficient time of cleaning the filtration membranes (284, 285, 286, 287) the pure water obtained downstream of the reverse osmosis membrane (287) in the chamber (300) is recycled to a specific compartment in the chamber. solvent tank system (200) through the valve-controlled pipe (13) (301 and 301a).

 It should be noted that this interruption of the recirculation to prevent clogging of the filtration membranes (284, 285, 286, 287) can advantageously be carried out after a period of coarse cleaning or preliminary rinsing of contaminated materials.

Step h): repeating steps c) to g) at least once:

^■ When the treatment is cleaning with simultaneous inactivation of infectious contaminants:

Since in the present process of the invention the cleaning is carried out simultaneously with the inactivation of the infectious contaminants, the continuous separation of the contaminants and the regeneration of the composition in its original state, it follows that the degree of removal and inactivation of contaminants increases over time; so gradually depending on the operating time one reaches, without corroding the material treated, a level of low-level, intermediate, high-level disinfection, a level of prion inactivation and a level of terminal sterilization consisting of obtaining a level of sterility assurance corresponding to a probability of existence of microorganism living equal to 10 ^"6 .

 At least intermediate level disinfection or a level of inactivation of prions should be stopped if prion is suspected, when the treated material is thermostable and requires, according to the regulations in force, a terminal sterilization of the prion. water vapor, or when the material is heat-sensitive and needs to be packaged for cold terminal sterilization.

 Said terminal steam sterilization will advantageously be carried out in the treatment chamber (101) using the separation chamber (230) as a boiler and producer of deionized water using the filtration membranes.

On the other hand, the carbonation / decarbonation cycles will be repeated until a terminal sterilization level is reached which is a level of sterility assurance corresponding to a probability of existence of living microorganism equal to 10 ^-6 for different types of material such as than :

 - material that can not be packed;

 - equipment that can be packaged under aseptic conditions;

 - equipment intended to be used immediately after its treatment. When the level of high level disinfection or the level of terminal sterilization is reached, the sodium hydroxide solution (Sodium Hydroxide (NaOH)) between the filtration membranes (286 and 287) is returned by the pump (400) to its specific compartment in the solvent system (200) via the lines (7b, 7, 3 and 3a) controlled respectively by the valves (405, 413, 401 and 401b).

^■ When the treatment is a terminal sterilization of the thermosensitive material with default inactivation of the prions:

All steps c) to g) of the present process of terminal sterilization of thermosensitive materials consisting in putting the material in contact with the sodium hydroxide solution (Sodium Hydroxide (NaOH)), carbonation / decarbonation cycles with mechanical stirring , a recirculation, are repeated for a time sufficient to obtain a total inactivation infectious contaminants including the most resistant that is to say the prions, and at least a level of assurance of sterility corresponding to a probability of existence microorganism living equal to Κ ⁶ i.e. a reduction of at least 12 log of the initial infectious load.

 When the terminal sterilization level is reached, the sodium hydroxide solution (Sodium Hydroxide (NaOH)) between the filtration membranes (286 and 287) is returned by the pump (400) to its specific compartment in the solvent system ( 200) through the lines (7b, 7, 3 and 3a) respectively controlled by the valves (405, 413, 401 and 401b).

"When the treatment is a terminal sterilization of thermostable material with default inactivation of prions:

Similarly, steps c) to g) are repeated for a time sufficient to obtain complete inactivation of the infectious contaminants including the most resistant ones, that is to say the prions, and at least one sterility assurance level corresponding to a probability of existence of live microorganism equal to 10 ^"6, that is to say a reduction of at least 12 Log of the initial infectious load.

 When the terminal sterilization level is reached, the sodium hydroxide solution (Sodium Hydroxide (NaOH)) between the filtration membranes (286 and 287) is returned by the pump (400) to its specific compartment in the solvent system ( 200) through the lines (7b, 7, 3 and 3a) respectively controlled by the valves (405, 413, 401 and 401b).

Step i): Rinsing:

Whatever the type of treatment, the microparticles and nanoparticles of bicarbonate and carbonate are rinsed and neutralized on the materials treated in the treatment chamber (101) by recirculating only the carbonated water (237) and sterile thanks to filtration. by reverse osmosis (287); in this case only the valves (404, 413, 402) are open at the separation chamber (230). Water can be added in this phase by the system (200), through the pipe (5) controlled by the valve (203). The dissolution of carbon dioxide (CO ₂ ) in water is favored by the pores of small diameters of the filtration membranes (284, 285, 286, 287) and by the gas-liquid contact membrane (230a) receiving the dioxide of carbon (C0 ₂ ) in the dense state, preferably in the supercritical state, via the pipe (la). Particularly, when the treatment is a terminal sterilization of the thermostable material with default inactivation of the prions, the carbonated water is in the vapor state, at temperatures between 120 and 180 ° C. Thus, without carbonation of water, this rinsing phase in itself constitutes a sterilization with saturated water vapor.

Step}): drying:

^■ When the treatment is cleaning with simultaneous inactivation of infectious contaminants or when the treatment is terminal sterilization of heat-sensitive material with default inactivation of prions:

 After the rinsing step, the sterile water (237) is returned by the pump

(400) to its specific compartment in the solvent system (200) via the lines (7a, 7, 3 and 3a) respectively controlled by the valves

(404, 413, 401 and 401b).

Supercritical drying is then carried out of the material consisting of initially adding high pressure liquid carbon dioxide (C0 ₂ ) which is immediately recirculated; which makes it possible to entrain the water retained on the surface of the treated material and to trap it in the separation chamber (230); in this case, only the valve (403) is open at said separation chamber (230) preventing any passage of water through the hydrophobic gas-liquid separation membrane (403a). Recirculated carbon dioxide (C0 ₂ ) passes through the pipes (9, 9a, 2) respectively to join the treatment chamber (101).

Only carbon dioxide (C0 ₂ ) remains in contact with the material. Finally the temperature is increased until at least the critical temperature of carbon dioxide (C0 ₂ ) is reached which is 31 ° C, which makes it possible to volatilize the carbon dioxide (C0 ₂ ) and to obtain a dry product. After sufficient drying time, the material is released from the treatment chamber (101).

Preferably, the material is dried using the pharmaceutical grade carbon dioxide (CO ₂ ).

■ When the treatment is a terminal sterilization of thermostable material with default inactivation of prions:

Once the rinsing is complete, the water vapor and condensed water are evacuated through the pipe (10) controlled by the valves (111 and 11a). The discharged water vapor is filtered in the separation chamber (230) and condensed preferably in the heat exchanger (412) to be returned with the already condensed water, through the pump (400), to a compartment specifically reserved for the recycled treatment agents of the treatment agent supply system (200) via the pipes (3 and 3a) controlled by the valves (401 and 401b).

The material is then dried by driving to the separation chamber (230) of the water vapor with carbon dioxide (CO ₂ ) having a temperature of between 100 and 180 ° C. and a pressure of between 1 and 12. bars. These temperatures and pressure make it possible to have the water in the vapor state thus facilitating its transport by the carbon dioxide (CO ₂ ) gas. Carbon dioxide (C0 ₂ ) due to its greater density than that of water vapor drives it in all geometries and allows to dry quickly the sterile material.

During the drying by entrainment of carbon dioxide (C0 ₂ ) in the separation chamber (230), the valve (404) is closed and the separation chamber (230) is maintained at room temperature through heat exchangers (241). Under these conditions, the water vapor condenses and the carbon dioxide (C0 ₂ ) is separated from the water, without decompression, thanks to the hydrophobic membrane gas-liquid separation (403a) and joined by the pipe (9 ) its reserved compartment in the tank system (501), once it has been compressed by the compressor (509) and condensed by the condenser (510).

After a sufficient drying time, then liquid or supercritical carbon dioxide (C0 ₂ ) is added at a temperature of between 12 ° to 34 ° C. and a pressure of between 73 and 300 bar, in order not only to cool the dried material but same time extracting the residual water in the complex geometries.

After sufficient time to cool the equipment to room temperature, it stops adding carbon dioxide (C0 ₂ ) and removed it with the compressor (509).

After complete evacuation of the carbon dioxide (C0 ₂ ) by the compressor (509); the water extracted and condensed in the separation chamber (230) can be sent via the pump (400) to a specific compartment reserved for the recycled treatment agents of the solvent delivery system (200), via the pipes (3 and 3a) controlled by the valves (401 and 401b). Thus, the drying time is considerably reduced because carbon dioxide (CO ₂ ) at very high temperature is a good heat transfer agent and in the liquid or supercritical state has a drying power by extracting water in complex geometries. In addition, it solves the problem of excessively wet packaging after sterilization with water vapor.

But if after the release of the treatment chamber (101) of the material having undergone terminal sterilization, said material needs to be packaged but that is in conditions where it is difficult to set up aseptic conditions or in conditions where there is no at all aseptic conditions, consecutively to the packaging of said material, completely eliminate the risk of recontamination when packaging with carbon dioxide (C0 ₂ ) supercritical.

End of treatment and self-disinfection:

At the end of treatment, after removing all material from the treatment chamber, only sterile water (237) and sterile, non-toxic waste retained by the filtration membranes (284, 285, 286, 287) remain. ). Thanks to the heating means (241) and acoustic emission (242), the temperature in the separation chamber (230) is carried and maintained preferably, but not exclusively greater than 134 ° C. With the aid of the pump (400), the water vapor formed is sent to the treatment chamber (101) thus making it possible to clean and sterilize said treatment chamber (101) as well as all its components and channels used during the treatment. By single opening of the valve (111) of the pipe (10) the water vapor leaving the treatment chamber (101) enters the pipe (10b) and opening the valves (111b, 111c, 111d, 111e 11f) enters the treatment chamber (101) again. Thereafter, the steam is removed from the treatment chamber (101) and recirculated by the pump (400) until the treatment chamber (101) and the pipes (2, 10, 10b) are completely sterilized. ). After supercritical evacuation and drying of the treatment chamber (101), carbon dioxide (CO ₂ ), preferably in the supercritical state, is then added through the pipe (8) controlled by the valve (508) so as to remove by rinsing or reverse filtration sterile and non-toxic waste retained by the filtration membranes (284, 285, 286, 287). We add also, concomitantly with the addition of supercritical carbon dioxide (C0 ₂ ), water from the system (200) through the valve-controlled lines (5, 5a, 10a) (203, 202, 112 to 117). The valves (231, 231a, 408, 409, 410, 411) being open, the pump (232) (which can be a vacuum pump) is actuated and all that is retained by the filtration membranes (284, 285, 286, 287) in the waste recovery chamber (300); which makes it possible to regenerate said filtration membranes (284, 285, 286, 287). In said waste recovery chamber (300), the reverse osmosis membrane (287) is used to filter the effluent from the separation chamber (230) and to obtain pure water which is recirculated back to the the separation chamber (230) through the pipes (13, 13a and 3b) respectively controlled by the valves (301 and 301a, 301b, 401a). Simultaneously, the gas-liquid separation membrane (303) of the same nature as the gas-liquid separation membrane (403a) makes it possible to return only the supercritical carbon dioxide (C0 ₂ ) introduced beforehand through the pipe (8), towards the special carbon dioxide tank (C0 ₂ ) in the tank system (501), through the pipes (14 and 9) respectively controlled by the valves (304 and 414). It follows that in the chamber (300), in the upstream portion of the reverse osmosis membrane (287), is recovered only dry, non-toxic and non-infectious waste. After a sufficient time of cleaning the filtration membranes (284, 285, 286, 287) the pure water obtained downstream of the reverse osmosis membrane (287) in the chamber (300) is recycled to a specific compartment in the chamber. solvent tank system (200) through the valve-controlled pipe (13) (301 and 301a). The non-toxic and non-infectious wastes are then recovered for possible subsequent treatment or sent directly to the sewer through the pipe (12) controlled by the valve (302) as shown in Figure 2. The separation chamber (230) and the waste recovery chamber (300) can then be opened to recover the filtration membranes and further clean said filtration membranes if necessary. In this way, using only two treatment agents (carbon dioxide (CO ₂ ) and sodium hydroxide solution (caustic sodium hydroxide (NaOH)), a contaminated material treatment process is used to simultaneously clean, inactivate type of infectious contaminants including the most resistant ones ie prions, continuously separate soluble and insoluble contaminants and continuously regenerate the treatment agents without corroding the material.

 In addition, the contaminated material treatment method according to the invention allows for the terminal sterilization of packaged contaminated material that is heat-sensitive or thermostable and / or complex geometries.

In addition, for treating both thermosensitive material and thermostable material and / or complex geometries, both products (carbon dioxide (CO ₂ ) and sodium hydroxide solution (sodium hydroxide (NaOH)) caustic) used by the process of treatment of contaminated material according to the invention, can be manufactured on site.

On-site production of carbon dioxide (CO 2) and caustic soda solution (sodium hydroxide (NaOH)):

Thanks to the device (100) of the present invention, both carbon dioxide (CO ₂ ) and sodium hydroxide solution (caustic sodium hydroxide (NaOH)) are prepared on the spot from a solution of sodium bicarbonate ( NaHCO ₃ ).

Said sodium bicarbonate solution (NaHCO ₃ ) is, in fact, readily available from natural sources of mineral water or is easy to manufacture from bicarbonate powders (NaHCO ₃ ). Indeed, by the system (200) of solvents can be added a solution of sodium bicarbonate (NaHCO ₃ ) in the separation chamber (230) in which is embedded a battery of filtration membranes successively comprising a microfiltration membrane (284 ), an ultrafiltration membrane (285), a nanofiltration membrane (286), a reverse osmosis membrane (287). Said separation chamber (230) being provided with heating means such as heat exchangers (241), makes it possible to heat the alkaline solution of sodium bicarbonate (NaHCO ₃ ) at temperatures generally between 60 ° C. and 160 ° C., preferably between 80 ° C and 140 ° C. The separation chamber (230) is also provided with acoustic means (242) producing ultrasound and megasons, makes it possible to subject said alkaline solution to acoustic emissions of high intensities. Under these conditions of temperature and / or acoustic emission, the alkaline solution of sodium bicarbonate (NaHCO ₃ ) rapidly releases carbon dioxide (CO ₂ ) and sodium carbonate (Na ₂ CO ₃ ) is formed.

The addition in the portion (235) of the separation chamber (230), by the system (200) and through the pipe (5) controlled by the valve (203), slaked lime Ca (OH) ) ₂ with sodium carbonate (Na ₂ CO ₃ ) makes it possible to produce sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic; the calcium ions (Ca ²⁺ ) being later stopped by the nanofiltration membrane (286) capable of stopping the divalent ions.

Thanks to one or more hydrophobic membranes (403a) of gas-liquid separation and thanks to the action of the compressor (509), only the carbon dioxide (C0 ₂ ) purified by the pipe (9) controlled by the valve (403); said purified carbon dioxide (C0 ₂ ) is then sent to the treatment chamber (101) through the lines (9a and 2) after its temperature is made lower or equal to 60 ° C by means of the capacitor (510). Said purified carbon dioxide (C0 ₂ ) may further join its specific reservoir in the system (501) through the pipe (9) controlled by the valves (403 and 414). Of course, in the latter case, the carbon dioxide (C0 ₂ ) is first converted to its liquid state by cooling with the capacitor (510).

 Sodium hydroxide solution (Sodium Hydroxide (NaOH)) is recovered after nanofiltration; before it is introduced into the treatment chamber (101), its temperature is of course reduced to a value of less than or equal to 60 ° C. thanks to the heat exchanger (412).

 Pure water is recovered by filtration using the reverse osmosis membrane

(287).

On the other hand, only carbon dioxide (CO ₂ ) can be made in situ by reacting the sodium bicarbonate solution (NaHCO ₃ ) with acids such as hydrochloric acid (HCl) in the separation chamber. and acetic acid (CH ₃ COOH). The carbon dioxide (C0 ₂ ) released is captured by means of one or more gas-liquid separation membranes and a compressor.

On the other hand, carbon dioxide (C0 ₂ ) can be produced in the ambient air; thanks to a compressor, the air is sucked up and brought into contact with the caustic soda solution (sodium hydroxide (NaOH)) with the aid of one or more gas-liquid contact membranes, said carbon dioxide (C0 ₂ ) ; which allows to selectively capture the carbon dioxide (C0 ₂ ) contained in the air.

On the other hand, with reference to Figure 1, only carbon dioxide (C0 ₂ ) can be produced on site as follows:

 - suck the air or fumes through the pipe (6) using a compressor

(205); - using one or more gas-liquid contact membranes (206) to contact air or fumes with sodium hydroxide solution (Sodium Hydroxide (NaOH)) to capture carbon dioxide (C0 ₂ ) as a solution of sodium bicarbonate (NaHCO ₃ ); said sodium hydroxide solution (Sodium Hydroxide (NaOH)) being added by the pump (201) through the pipe (6a) controlled by the valve (208) and gaining the separation chamber (230) through the pipe (6b) controlled by the valve (207).

 - Let the other components of the air or fumes escape through one or more hydrophobic membranes (403a) gas-liquid separation and through the action of the compressor (509);

- heating the alkaline solution of sodium bicarbonate (NaHCO ₃ ) at temperatures generally between 60 ° C and 160 ° C, preferably between 80 ° C and 140 ° C; and releasing carbon dioxide (C0 ₂ ) which is simultaneously purified by the filtration membranes (284, 285, 286, 287).

- thanks to one or more hydrophobic membranes (403a) of gas-liquid separation and thanks to the action of the compressor (509), to release only the carbon dioxide (C0 ₂ ) purified by the pipe (9) controlled by the valve ( 403). Said purified carbon dioxide (C0 ₂ ) can then join its specific reservoir in the system (501) through the pipe (9) controlled by the valves (403 and 414); after being converted to its liquid state by cooling with the aid of the capacitor (510).

On the other hand, the release of carbon dioxide (CO ₂ ) by heating the alkaline solution of sodium bicarbonate (NaHCO ₃ ) can be optimized by acids such as hydrochloric acid (HCI) and acetic acid ( CH ₃ COOH). The invention will now be described with reference to the following examples, given by way of illustration and not limitation.

Example of Caustic Modulation Inactivation of a Composition Comprised of Supercritical Carbon Dioxide (COy) and Soda Solution (Sodium Hydroxide (NaOH))

To evaluate the effectiveness of inactivation of infectious contaminants by modulating the causticity of a composition formed by supercritical carbon dioxide (C0 ₂ ) and caustic soda solution (sodium hydroxide (NaOH)), biological indicators (Bacillus atropheus, Bacillus pumillus, Geobacill stearotherphillus) packaged and having an initial charge of 10 ⁶ spores were impregnated with sodium hydroxide solution (sodium hydroxide (NaOH)) caustic and attached to the axis of rotation of the stirrer of a 250 ml autoclave marketed by TOP INDUSTRIE SA. Supercritical carbon dioxide (CO ₂ ) is then added with mechanical stirring to form the modulable caustic composition.

 The modulation of the causticity of the composition was carried out by successive decompression / compression and / or by variation of temperature around 60 ° C.

 The operating conditions and results (reduction of log) obtained are described in the following table:

Whatever the biological indicator, a reduction of Log greater than 6 is obtained, which corresponds to a total inactivation of the initial charge of 10 ⁶ spores in 1 h at 290 bar or 2 h at 90 bar.

Thus by modulating the causticity of a composition formed by supercritical carbon dioxide (C0 ₂ ) and sodium hydroxide (sodium hydroxide (NaOH)) by successive cycles of carbonation / decarbonation under pressure conditions of 290 bar and temperature of 60 ° C, reached in less than 2 hours, a total inactivation and at least a level of assurance of sterility corresponding to a probability of existence of living microorganism equal to 10 ^"6 that is a reduction of at least 12 log of the initial infectious load, and these operating conditions make it possible to inactivate the prions rapidly without corroding the treated material.

Claims

1. A method for treating thermosensitive and / or thermostable contaminated material and / or complex geometries, capable of using synergistically the modulation of the causticity of a composition formed by carbon dioxide (C0 ₂ ) and sodium hydroxide (Sodium Hydroxide (NaOH)) and continuously regenerating said composition by continuously separating the soluble and insoluble contaminants extracted therefrom with the aid of filtration membranes, to perform simultaneously the cleaning and cleaning operations. inactivation of all known types of infectious contaminants including the most resistant ie prions, without damaging the material; said method being characterized in that it comprises steps of:

 a) introducing contaminated material into a treatment chamber;

b) forming in situ a composition having a caustic power which can be modulated from carbon dioxide (CO ₂ ) and sodium hydroxide solution (sodium hydroxide (NaOH)); and

c) contacting the contaminated material with the composition obtained and simultaneously cleaning the contaminated material and the inactivation of infectious contaminants by modulating the causticity of said composition by subjecting it to successive cycles of decarbonation carbonation; decarbonation (removal of carbon dioxide (C0 ₂ )) to make it caustic; carbonation (addition of carbon dioxide (CO ₂ )) to make it non-caustic and to form microparticles or nanoparticles of bicarbonate and sodium carbonate which are mild detergents and abrasives; and

 d) simultaneously with steps b) and c) subjecting said composition to mechanical agitation;

 e) recirculating, preferably continuously all or part of the composition containing the extracted contaminants, without depressurizing, preferably, but not exclusively, the treatment chamber; and

f) not only continuously and selectively separate the soluble and insoluble contaminants extracted by the composition through a battery of discharge-loading filtration membranes facilitated and capable of being embedded in a separation chamber (230), said filtration (284, 285, 286, 287) for successively or selectively microfiltration, ultrafiltration, nanofiltration, reverse osmosis and regenerate the composition in its original state; but also continuously inactivate the remaining infectious contaminants extracted by the composition, making the composition this time caustic by decarbonation; and;

 g) reintroduce into the treatment chamber a desired fraction or all of the composition renewed and purified to treat the material; and

 h) repeat steps c) to g) at least once;

i) rinsing and neutralizing the bicarbonate and carbonate microparticles and nanoparticles by only recirculating the carbonated water with carbon dioxide (C0 ₂ ); said carbonated water being further sterile by reverse osmosis filtration in the separation chamber (230);

 j) drying the treated material with carbon dioxide

(C0 ₂ );

 k) release the treated material from the treatment chamber.

2. Process for treating contaminated material according to claim 1, characterized in that the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) is introduced in atomized form by one or more ultrasonic spray nozzles (108) for fractionating sodium hydroxide solution (Sodium Hydroxide (NaOH)) in very fine volatile droplets able to diffuse efficiently in the complex geometries of the external surfaces of the contaminated materials.

 3. Process for treating contaminated material according to claim 1, characterized in that during step b) a vacuum is created and the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) is added until its voltage is reached. steam, preferably, but not exclusively, between 18 and 200 torr and at temperatures, preferably, but not exclusively, between 20 and 60 ° C, more preferably between 40 and 60 ° C.

 4. Process for the treatment of contaminated material according to claim 1, characterized in that in step b) the sodium hydroxide solution (sodium hydroxide

(NaOH)) is added at concentrations ranging from 0.01M to 20M, at temperatures, preferably, but not exclusively, at 20 to 180 ° C and at pressures preferably, but not exclusively, greater than 0 bar and less than or equal to 700 bar.

5. Process for treating contaminated material according to the preceding claim, characterized in that during step b) the sodium hydroxide solution (sodium hydroxide (NaOH)) caustic occupies 0.001% to 100%, preferably 0.001% to 30%. % of the total volume of the treatment chamber.

6. Process for treating contaminated material according to claim 1, characterized in that during step b) the carbon dioxide (CO ₂ ) is added at pressures preferably, but not exclusively, between 1 and 700 bar and at temperatures, preferably, but not exclusively, between -78.5 and 60 ° C and at rates, preferably, but not exclusively, between 20kg / h and 400kg / h.

 7. Process for treating contaminated material according to claim 1, characterized in that in step c) the decarbonation / carbonation cycles are obtained by depressurization / pressurization or decompression / compression.

 8. Process for treating contaminated material according to claim 1, characterized in that the carbonation is carried out by means of one or more gas-liquid contact membranes for the diffusion of gases in liquids at the microscopic scale.

 9. Process for treating contaminated material according to claim 1, characterized in that the decarbonation is by decompression or by depressurization using one or more hydrophobic gas-liquid separation membranes releasing only the carbon dioxide and to maintain the sodium hydroxide solution (caustic sodium hydroxide (NaOH)) whose causticity is to be controlled in contact with the contaminated material.

 10. Process for treating contaminated material according to claim 1, characterized in that during step c) the decarbonation is obtained in the treatment chamber (101) by one of the following means or their combinations:

 decompression or by depressurization using hydrophobic membranes of gas-liquid separation leaving only the carbon dioxide to escape and making it possible to maintain the sodium hydroxide solution (Sodium Hydroxide (NaOH)) caustic of which it is desired to control the causticity in contact with the contaminated material;

addition of inert gases intended to replace carbon dioxide (CO ₂ ) in the carbonated solution; said inert gases including but not limited to nitrogen, argon, helium.

- moderate increase in temperature above 60 ° C, preferably between (60 and 70 ° C); - increase in temperature above 70 ° C;

 - action of ultrasounds or megasons; said ultrasound being used at frequencies from 20 KHz to 1 MHz and said megasons being used at frequencies from 1 MHz to 100 MHz.

 without depressurization, at constant supercritical pressure in the treatment chamber, by moderate increase of the temperature above 60 ° C., preferably between 60 and 70 ° C.

 11. Process for treating contaminated material according to claim 1, characterized in that during step f) the decarbonation is obtained in the separation chamber (230) by one of the following means or their combinations:

 decompression or by depressurization using one or more hydrophobic membranes of gas-liquid separation leaving only carbon dioxide to escape and making it possible to maintain the sodium hydroxide solution (Sodium Hydroxide (NaOH)) which is to be controlled causticity in contact with contaminated material;

addition of inert gases intended to replace carbon dioxide (CO ₂ ) in the carbonated solution; said inert gases including but not limited to nitrogen, argon, helium.

 heating at temperatures preferably between 60 ° C and 160 ° C, more preferably between 80 ° C and 140 ° C;

- addition of slaked lime (Ca (OH) ₂ );

 - action of ultrasounds or megas of high intensities; said high intensity ultrasound being used, preferably, but not exclusively, at frequencies from 200KHz to 1MHz and said high intensity megasons being used, preferably, but not exclusively, at frequencies from 10 MHz to 100 MHz.

 12. Process for treating contaminated material according to claim 7, characterized in that the rate of depressurization / pressurization is between 10 bar / hour and 4000 bar / hour.

13. Process for treating contaminated material according to claim 7, characterized in that the decompression / compression cycle rate is between 1 hour cycle at 200 cycles / hour and the pressure variation associated with the decompression / compression cycle is included between 1 bar and 300 bar.

14. A method of treating contaminated material according to claim 1, characterized in that in step c) the time per decarbonation cycle unit is between 1 millisecond and 1h.

 15. Process for treating contaminated material according to claim 1, characterized in that during step d) the stirring means include but are not limited to the use of stirrer magnetically coupled to an electric motor or connected directly to an electric motor, the use of rotating drum magnetically coupled to an electric motor or connected directly to an electric motor by a shaft passing through the wall of the autoclave, the use of jets, the use of stirring by recirculation of the fluid, the use of agitation by heating the fluid, the use of agitation by bubbling in the fluid, the use of ultrasound.

 16. Process for treating contaminated material according to claim 1, characterized in that during steps b) to h) is added to the composition, surfactants or anionic or nonionic surfactants, detergents, oils, enzymes such as that thermostable alkaline proteases, disinfectant / sterilizing additives with anti-aggregating agents, chelating agents, surfactants; said additives including, but not limited to, alcohols such as 60% to 95% ethanol, hydrogen peroxide, chlorine dioxide, sodium hypochlorite, ethylene oxide, sodium dodecyl SDS (5%), formaldehyde, glutaraldehyde, ammonia, β-propiolactone, phenol, phenolics, iodophors, sodium metaperiodate, urea, antimicrobial essential oils, and their mixtures.

 17. Process for treating contaminated material according to claim 1, characterized in that during step i) rinsing is added acetic acid, peracetic acid or other acids such as hydrochloric acid. (HC1).

18. Process for treating contaminated material according to claim 1, characterized in that the treatment method corresponds to a sterilization process in which the level of inactivation reached after step h) is a level of terminal sterilization allowing achieve complete inactivation of infectious contaminants including the most resistant ie prions, and at least equal to a level of assurance of sterility corresponding to a probability of existence of live microorganism equal to 10 ^"6 c that is, a reduction of at least 12 log of the initial infectious load.

19. Process for treating contaminated material according to claim 1, characterized in that the sodium hydroxide (caustic sodium hydroxide (NaOH)) is replaced sodium hypochlorite (NaClO) capable of inactivating prions and forming bicarbonate or carbonate in the presence of carbon dioxide (C0 ₂ ).

20. Process for treating contaminated material according to claim 1, characterized in that when the infectious contaminants do not include the prions, it is possible to replace the sodium hydroxide (caustic sodium hydroxide (NaOH)) with hydroxyl-containing caustics. to form bicarbonate or carbonate in the presence of carbon dioxide (C0 ₂ ); said caustic products including, but not limited to, potassium hydroxide or potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), tetramethyl ammonium hydroxide (N (CH ₃ ) ₄ OH), Lithium Hydroxide (LiOH), Calcium Hydroxide (Ca (OH) ₂ ), Magnesium Hydroxide (Mg (OH) ₂₎ , Barium Hydroxide (Ba (OH) ₂₎ , Cesium Hydroxide (CsOH), Strontium Hydroxide (Sr (OH) ₂ ), Rubidium Hydroxide (RbOH), Copper Hydroxide (Cu (OH) ₂ ) or mixtures thereof.

 21. Apparatus for treating contaminated material for the implementation of a contaminated material treatment method according to any one of claims 1 to 20, characterized in that it comprises:

 a treatment chamber (101) comprising:

 means (107) for receiving the contaminated materials;

 o means for introducing the treatment agent in the form of jets

(109, 109a, 109c) high speed on contaminated equipment;

 means (110) and (107b) for making the hydrostatic pressure around the contaminated material;

 stirring means (104);

 o heating / cooling means such as heat exchangers for regulating the temperature;

 o acoustic emission means;

 spraying means (108) for the treatment agents in atomized form on the contaminated materials;

 one or more gas-liquid separation membranes (230b, 230c) connected to the treatment chamber (101);

 one or more gas-liquid contact membranes (230a) connected to the treatment chamber (101);

at least one separation chamber (230) comprising: o inside and recessed, a battery (28) of easy loading / unloading filtration membranes, said filtration membranes (284, 285, 286, 287) for performing successively or selectively microfiltration, ultrafiltration , nanofiltration, reverse osmosis and regenerate the composition or treatment agent in its original state;

 means for continuously inactivating infectious contaminants extracted and for regenerating filtration membranes such as heating / cooling means (241) and acoustic emission means (242);

 o means (241, 242) for regenerating the filtration membranes; recirculation means (400);

one or more hydrophobic gas-liquid contact membranes (230a, 206) connected to the separation chamber (230);

 one or more hydrophobic gas-liquid separation membranes (403a) connected to the separation chamber (230);

 a system (200) for supplying aqueous or non-aqueous treatment agents comprising specific compartments for the recycled treatment agents;

 - A fluid supply system (500) in the liquid or supercritical state comprising specific compartments (501) for the recycled fluids;

 - A recovery chamber (300) of inactivated and effluent-free contaminants in which is incorporated one or more filtration membranes in this case a reverse osmosis membrane (287); and having on the outside a gas-liquid separation membrane (303) associated therewith;

 one or more hydrophobic gas-liquid separation membranes (303) connected to the recovery chamber (300) of the inactivated contaminants;

 means for controlling the temperature and the pressure;

 an automatic control system making it possible to select the desired treatment.

22. Treatment device according to claim 21, characterized in that stirring means are constituted by a stirrer (104) which can be direct magnetic coupling with integrated motorization (103), or directly driven by a electric motor (103) and having a hollow shaft acting as a stirring shaft and fluid injection.

 23. Treatment device according to any one of claims 21 to 22, characterized in that the hollow shaft of the stirrer (104) passes through the wall of the autoclave (101) with a non-rotating seal avoiding problems leakage or wear posed by the rotary joints of the prior art.

 24. Processing device according to claim 21, characterized in that said system (107) makes it possible to facilitate loading / unloading of the material to be treated and comprises:

 cylindrical baskets (102) intended to receive the contaminated materials; said cylindrical basins (102) being suspended from a hollow shaft (107b) having on its surface nozzles for dispensing jet treatment agents (109); said hollow shaft (107b) further having on its surface horizontal spray arms and connection means for the irrigation of internal channels with complex geometries.

 - A handling means (107a) making it removable.

 25. Processing device according to claim 21, characterized in that the means (110) consist of a cylindrical nozzle system attached to the axis of the stirrer (104) and rotatable by fluid inlet.

 26. Device according to claim 21, characterized in that the agitator (104) is adapted to receive at its end (105) the cylindrical baskets (102) by mechanical coupling of the hollow shaft of the stirrer (104) with the hollow shaft (107b) of the system (107) for loading / unloading the material to be treated.

 27. Treatment device according to claim 21, characterized in that the battery (28) of filtration membranes of the separation chamber (230) comprises metal grids (281, 283, 288) for separating and / or stabilizing and / or support the filtration membranes (284, 285, 286, 287).

28. Treatment device according to claim 27, characterized in that the grids (281, 283, 288) have on their surfaces seals (not shown) inflatable or full-thrust and preferably of toric shape and materials resistant to pressure and temperature, alkalinity or acidity conditions in the separation chamber (230); said materials can be for example PTFE (Teflon ^®) or a rich composite PTFE (Teflon ^®).