FR2872046A1 - SEAWATER COMPOSITION, PROCESS FOR PREPARING THE SAME, USE THEREOF FOR THE HYGIENE OF THE FEMALE GENITAL APPARATUS AND DEVICE FOR THE USE THEREOF - Google Patents

Abstract

The invention relates to a composition based on seawater comprising divalent cations at a concentration higher than that of natural seawater and monovalent cations at a concentration lower than that of natural seawater, its process preparation, its use for the hygiene of the female genital apparatus and a device for its use.

Description

The present invention relates to a composition based on seawater, its

  method of preparation, its use for the hygiene of the female genital sphere, and a device for its use.

  The compositions usually used in this field contain sodium chloride (NaCl) at about 9 g / l so as to obtain an isotonic solution. They contain no trace element or product that may have a beneficial effect on the mucous membranes and are deficient in mineral salts.

  Compositions consisting of seawater enriched by introduction of trace elements in metallic form in colloidal solution, in the form of organic or inorganic salts, or in the form of salts or organometallic complexes or metalloprotein complexes are described in application FR 2 688 133.

  Gynecological compositions containing a natural saline solution, an antibacterial agent and a perfuming agent are described in application FR 2 741 536.

  In the compositions mentioned above, seawater contains extrinsic additives and is therefore not natural.

  Moreover, synthetic solutions containing the same mineral compounds as the blood are commercially available, but these solutions are made from ultra-pure tridistilled water and ultra-pure chemicals, and not from a natural product such as water. 'sea water.

  It has now been found that it is possible to obtain pure complex solutions from seawater containing mineral salts and trace elements in proportions suitable for use in the hygiene of the female genital sphere, while respecting and by strengthening the pH and natural flora of the mucosa.

  In addition, because of the toning and regulating qualities of seawater, said composition contributes to toning the musculo-ligamentous structure that supports the entire genital system.

  The composition according to the invention is composed exclusively of pre-filtered and purified natural seawater, some physicochemical characteristics of which have been modified. Thus, it comprises sea water whose concentration of divalent ions (mainly calcium and magnesium) is greater than that of natural seawater, preferably by a factor of 1.3 to 1.5 of the content. initial. In addition, the concentration of monovalent ions (mainly sodium and potassium) is lower than that of natural seawater. In particular, the concentration of sodium chloride is decreased.

  Advantageously, the levels of trace elements naturally present in seawater, such as for example fluorine, bromine, boron, iodine, strontium, copper, iron, manganese, lithium, sulfur, zinc are preserved.

  Modulation of the ionic concentration is of great interest because the ions of natural seawater, in particular magnesium (Mg 2+), potassium (K +) and calcium (Ca 2+) can act as cofactors in the enzymatic regulation of the metabolism of the skin and mucous membranes.

  Advantageously, the ionic strength of said composition is high, of the order of I = 0.7 M to I = 1.1 M, preferably I = 0.9 M. Because of this high ionic strength, the composition according to the invention may have a regulatory activity against the proliferation of saprophytic sprouts, normally in small proportion, which are likely to develop when the balance of the vulvar and vaginal flora (Doderlin's flora) is disturbed.

  Preferably, the composition according to the invention has a pH of between 1.5 and 6.5, in particular 5.5.

  According to a preferred aspect, said composition comprises: - from about 490 to 580, preferably 530 mg / l of sodium chloride (NaCl) - from about 1700 to 1980 mg / l, preferably 1850 mg / l of magnesium ( Mg2 +) - from about 550 to 650 mg / l, preferably 595 mg / l of calcium 3 (Ca2 +) - from about 230 to 430 mg / l, preferably 325 mg / l of potassium (K +).

  The invention also relates, in another of its aspects, to a process for obtaining said composition.

  The preparation of an isotonic solution from seawater or saline groundwater pre-filtered by, on the one hand, a nanofiltration and diafiltration process, and on the other hand, by electrodialysis on specific membranes has been described by F.Quéméneur et al. in the book Membrane Integration in Processes, French Society of Process Engineering, 2, 2003, 181-188, Lavoisier Technique et documentation Ed., Paris.

  However, the process described does not make it possible to obtain the composition based on pure seawater according to the invention, since the purification of the seawater and the modification of the pH, in particular the lowering of the pH to the desired ranges. , can not be done.

  The partial demineralization of seawater by nanofiltration in order to obtain a solution with reduced overall salinity has been described in an article by M. Pontié published on the URL http://www.desline.com. com / articoli / 5195.pdf Desalinization, 2003, 158, 277-280, Elsevier Science B.V. Ed.

  However, this process does not make it possible to selectively modify the concentration of the different monovalent and / or divalent monovalent cations of seawater.

  It has now been found that a preparation process combining a purification step prior to electrodialysis and nanofiltration steps made it possible to obtain this result.

  The method according to the invention comprises the steps of: a) selectively demineralizing the seawater by electrodialysis, b) acidifying the solution thus obtained by dissociation of the water through ion exchange membranes and c) concentrating the solution thus obtained by nanofiltration.

  According to a preferred aspect of the process, step a) is preceded by a preliminary step making it possible to retain and separate possible polluting elements, in particular hydrocarbon-related polluting elements.

  Preferably, this preliminary step is carried out by filtration of the raw seawater using a granular activated carbon filter, allowing the organic matter to be captured in its pores.

  In a preferred aspect, step a) is carried out in an electrodialysis reactor. Electrodialysis is a physical method of separation or concentration of ions in solution, under the action of an electric field, and using membranes permeable to anions or cations but without any reaction. at the electrodes.

  The electrodialysis reactor used in the process according to the invention comprises compartments intended for the circulation of brine (so-called brine compartments, compartments intended for the circulation of the product (referred to as product compartments) and compartments of electrolyte, anode and cathode in The electrolyte circulating for the solution of the anode and the cathode circulates in. Each of the compartments of the electrodialysis reactor is respectively composed of an anion-permeable membrane, called MEA, and a membrane permeable to cations, called MEC. The MEA membrane passes in the brine compartment the monovalent ions, corresponding to the excess of sodium chloride, while the MEC membrane retains preferentially in the compartment produces the divalent ions, in particular Cal + and Mg2 +.

  Said electrodialysis reactor may for example comprise 25 product compartments and intercalated compartments intended for the brine, or, as required, a larger number of compartments, for example 100 compartments for the product and 100 compartments for the brine. .

  Electrodialysis takes place in the reactor under the action of a controlled electric field.

  The product consists of filtered seawater and mineralized and acidified raw seawater brine.

  The reactor is put in circuit with a tank containing the product connected to the product compartments, a tank containing the brine connected to the brine compartments and a tank containing the electrolyte connected to the electrolyte, anode and cathode compartments.

  The brine can be prepared from mineralized raw seawater with a solution of NaCl to obtain a starting conductivity of 10ms and acidification by addition of hydrochloric acid (0.1N HCl) until a pH value is obtained. equal to 2.

  Preferably, step b) allowing acidification of the product is carried out simultaneously and progressively during the selective demineralisation.

  It is effected by the dissociation of water on both sides of the membranes by proton transfer. In the product compartments, H + ions are generated on the surface of the cationic membranes, while in the brine compartments, OH- ions are produced on the surface of the anionic membranes. This transfer is performed against the field of the electric field generated by the anode and the cathode located on either side of all the membranes of the electrodialysis reactor.

  The contents of the tanks respectively containing the brine, the product and the electrolyte circulates at a constant rate in the electrodialysis reactor.

  Preferably, the flow rate in the brine and product compartments is about 1000 l / h, that of the electrolyte being about 400 l / h. Circulation in the electrodialysis reactor can be carried out for example for a period of 8 hours continuously.

  After step b), the concentration step c) is carried out by circulating the contents of the product tank in a concentration loop consisting of nanofiltration membranes, preferably spiral membranes. The said nanofiltration membranes are preferentially selective with respect to the divalent ions and not very selective with respect to the monovalent ions, that is to say that the divalent ions will be preferentially retained in the contents of the product compartment. Such membranes are preferably of polyamide / polysulfone type.

  The concentration is effected by the separation of the permeate consisting mainly of water molecules as well as a small amount of strongly solvated ions Na + and Cl of the solution flow exerted tangentially on the membrane. The concentrate is reintroduced into the product tank. During step c), the concentration of salts and divalent ions as well as the pH increase proportionally to the filtered permeate.

  According to a preferred aspect, the control of the electrodialysis parameters is carried out by a measurement chain comprising at least an ammeter, a voltmeter, conductivity meters and pH meters.

  PH measurements are made in the brine, product and electrolyte tanks, as well as in the permeate. The conductivity is controlled in particular in the product and brine tanks. FIG. 1 represents the circuit for carrying out the process according to the invention. An electrodialysis reactor I is connected to a product tank II, a brine tank III and an electrolyte tank IV via three supply circuits regulated by pumps. After demineralization and acidification (steps a) and b) of the process), the product is concentrated on a stack of nanofiltration membranes V (step c)).

  Advantageously, said process makes it possible, simultaneously and without addition, to purify the sea water, to reduce the initial sodium chloride content, to increase the content of certain salts and trace elements, to increase the acidity of the medium. by ion transfer through electrodialysis membranes without the addition of acid and then decrease by nanofiltration.

  All of these operations do not require any addition of extrinsic elements to natural seawater.

  The seawater used as starting material can be obtained in a natural marine environment by means of a collection and transfer device comprising, for example, a pump, pipes, a strainer, connectors and a pre-filter. activated carbon, all made of non-corrosive inert materials by sea water and food grade. The raw raw material may be optionally stored before use, for example in polypropylene containers with closed lid.

  The invention also relates, in one of its aspects, to the use of the composition described above for the hygiene or the treatment of the female genital sphere, in particular to promote, by instillation, the elution of the walls. vaginal and cervical.

  Said composition can also be used, for example, for intimate hygiene, for external use, since its composition and its pH are suitable for cleaning the vulvar mucosa.

  According to a later aspect, the invention also relates to a device for the use of the composition described above, for hygienic use, comprising a conditioning reservoir containing said composition and a hand shower for instillation thereof.

  According to a preferred aspect, said device also comprises an overpack bag made individually from a welded film, guaranteeing the sterility of the assembly until its use.

  Preferably, the device according to the invention is disposable.

  An overall view of the device is shown in FIG. 2, in which the conditioning reservoir preferably comprises an ergonomic flexible pouch A acting as a reservoir and a flexible tube 1 serving as a filling site, a diffuser and a cannula extender. said tube being mounted on a hand shower 2. the bag A and the tube 1 are preferably made of a polymer or a copolymer approved by the European Pharmacopoeia, such as, for example, polyvinyl chloride (PVC).

  The bag A and the tube 1 can be made by extrusion. The two parts are assembled by microwave welding, and represent a capacity of about 100 to 200 ml of solution.

  According to a preferred embodiment, the total length of the tube 1 is 10 to 15 cm.

  The tube 1 welded on the tank A accepts at the other end a deformation by a pre-stress action prior to the assembly of the shower 2. Once the assembly is made, the tube 1 matches the contours of the shower 2.

  In a preferred embodiment shown in Figure 3, the flexible tube 1, cannula extension on its end comprises 8 to 12 fine notches 3, transverse to the axis of the tube, spread over two or three rows and cross at 90 one of the others, allowing the jet of the seawater composition under the action of the pressure exerted on the pocket A. The deformed parts 4 of the tube 1 in contact with the two lights 5 of the half-cylindrical channels of the hand shower 2 make it possible to ensure the function check valve and anti-return for the passage of the composition.

  In a preferred embodiment shown in FIG. 4, a single piece constitutes the hand shower 2. It comprises a breakable portion 7 of solid tubular shape at one end, 2 half-cylindrical channels 5 opening into the end of the breakable portion of a part and in a portion of sphere 6 on the other hand, a cylinder 8 constituting the axel of the part, four rounded fins 9, and ends with an ergonomic half-sphere 10.

  The fins 9 are slightly larger in diameter inside the flexible tube 1, mounted on the pocket A. The second end of the tubular shape of the breakable portion is weakened around its connection with the sphere portion, by the junction internal channels 5.

  The sphere portion 6 represents a part of the system making up the valve and non-return function. It also allows the closure of the filling site of the conditioning tank.

  Preferably, said single piece constituting the hand shower is made of polymer, for example a crystal polystyrene. Advantageously, it is manufactured by injection of high-pressure materials at a temperature of the order of 180 C into a mold.

  The breakable portion 7 is of solid tubular shape and comprises 4 fins 11 at its end. These fins are slightly larger in diameter inside the tube 1. The other end of the breakable part is weakened around its connection with the sphere portion 6, by the junction of the channels 5.

  The two channels 5, opening into the sphere portion 6, form a combination of parts fulfilling the seal-valve function with the inside of the flexible tube 1. This flexible tube covers the end of the two channels of the sphere 6 emerging from the opposite side to the breakable part. The elasticity of the flexible tube 1 plays the role of a check valve, and moreover, retains the composition of seawater in the bag out of pressure once the broken tip broken tip.

  In a preferred aspect, a protective sheath caps the shower head before the overwrap.

  Advantageously, the overpack bag of the device according to the invention is preferably made individually from a film of polymer or copolymer usually used in the field, such as for example polyethylene polyvinyl chloride (PET-PVC) multilayer welded, which acts as a barrier and guarantees the sterility of the entire device until it opens before use.

  The sterilization of the assembly (device + overpack bag) can be carried out preferably by steam autoclaving at a temperature of about 123 for 25 min or by ionization techniques, for example, by exposure to a source Gamma radius without dry residue.

  The ionization process that can be used to sterilize the assembly consists, for example, in exposing the packaged and palletized products to gamma rays emitted by a source of Cobalt 60 for a limited time. The emitted photons have two energy levels: 1.17 and 1.33 MeV, that is to say a level of energy lower than that likely to induce radioactivity in the exposed product (10 MeV).

  The source of Cobalt 60 is permanently in the treatment position, that is to say maintained in the air in the treatment cell. An automatic system is used to route the products into the irradiation cell and then pass them in front of the radiation source according to a defined circuit and at an appropriate speed, before taking them out of the cell.

  To use the device, the breakable part which is inside the tube is cut by folding, which releases the passage of the solution to the spray tip. The overwrap is then opened on a pre-cut part and the device is cleared just before use. The first part of the hand shower is, in the case of internal use, gently introduced into the vagina and the solution is expelled by jerky pressure on the pocket. In the case of external use for the toilet, the hand shower is directed towards the vulvar mucosa.

  2872046 10 The device started is discarded after use. The invention is illustrated by the examples below.

  Example 1: Obtaining a composition of seawater 30 I of raw seawater are introduced into a tank connected to the product compartments of the electrodialysis reactor. The same amount of brine, prepared with 6 liters of seawater and 24 liters of tap water plus 400 ml of 0.1N HCl, is added to a vessel connected to the brine compartments of the electrodialysis reactor. 30 l of electrolyte prepared with tap water and sulfuric acid to achieve a conductivity of 20 mS / cm are introduced into a vessel connected to the anode and cathode compartments of the electrodialysis reactor.

  The product, the brine and the electrolyte are circulated at a constant rate using the 3 pumps corresponding to each of these 3 circuits connected to the electrodialysis reactor and simultaneously energized at 45V across the anode. and the cathode of the reactor.

  The conductivity measurement of the product compartment solution decreases in proportion to the demineralization exerted from 53 mS / cm 2 to 11 mS / cm 2 and the time that elapses. The pH of the solution decreases from 8.2 to 4 at the same time. The transfer of ions is accompanied by a transfer of water from the product tank which loses 6% of its initial volume in favor of the brine tank.

  The concentration is then carried out by looping the solution thus obtained in the circuit of a nanofiltration membrane. All the salts and trace elements as well as the pH are increased by the extraction in the solution of the permeate consisting of practically pure water.

  The conductivity measurement and the pH of the product compartment increase proportionally to the concentration of the solution, from 11 mS / cm to 15 mS / cm and the pH from 4 to 5.5.

  The volume of the concentrated solution is reduced by 9.4 I to finally obtain 14.6 liters of an isotonic solution containing 8.7 g / l of all the salts and oligoelements combined.

  The sodium, magnesium, calcium and potassium concentrations of this solution are as follows: 5300 mg / l of NaCl, 1850 mg / l of magnesium, 600 mg / l of calcium and 325 mg / l of potassium (analysis of the sodium at the photometer of flame and other ions by atomic absorption).

  Example 2: Sterilization of the device products previously filled and corked were introduced into their vacuum-welded overpacks and are stored horizontally and flat without overlapping on perforated stainless steel plates. Each of the 20 plates is loaded on slides in a trolley that enters the bottom of the tank of the autoclave that can contain 3. The vertical doors are closed on the carriages and locked at each end of the tank.

  A saturated steam sterilizer is equipped with a device that pre-empts the sterilization chamber and eliminates residual air pockets. The vacuum level is indicated by the device. Steam is generated in the sterilization chamber or in an external steam generator. A subsequent vacuum phase effectively dries the products and their packaging after the sterilization phase. Packaged in an air and water vapor permeable packaging that is impervious to micro-organisms and viruses, products sterilized by this method will remain sterile until the packaging is opened, on the sole condition that it comes out perfectly dry (phenomenon of osmosis). Packing can store packaged products from 24 to 36 months.

Claims (3)

12 CLAIMS   1. Composition based on seawater, characterized in that it comprises divalent cations at a concentration greater than that of natural seawater and monovalent cations at a concentration lower than that of seawater natural.   2. Composition according to claim 1, characterized in that the divalent cations are chosen from calcium and magnesium.   3. Composition according to one of claims 1 or 2, characterized in that the divalent cation concentration is increased by a factor of 1, 3 to 1.5 with respect to natural seawater.   4. Composition according to any one of claims 1 to 3, characterized in that the monovalent cations are chosen from sodium and potassium.   5. Composition according to any one of claims 1 to 4, characterized in that the concentration of sodium chloride is decreased relative to natural seawater.   6. Composition according to any one of claims 1 to 5, characterized in that it has an ionic strength I of the order of 0.7 M to 1.1 M, preferably 0.9M.   7. Composition according to any one of claims 6, characterized in that it has a pH between 1, 5 and 6.5, preferably 5.5.   8. Composition according to any one of the claims, characterized in that it comprises: - from about 490 to 580, preferably 530 mg / l of sodium chloride (NaCl) - from about 1700 to 1980 mg / l preferably 1850 mg / l magnesium (Mg 2+) - from about 550 to 650 mg / l, preferably 595 mg / l calcium (Ca 2+) - from about 230 to 430 mg / l, preferably 325 mg / 1 potassium (K +).   9. A process for preparing a composition according to any one of claims 1 to 8, characterized in that it comprises the steps of: a) selectively demineralize the seawater by electrodialysis, b) acidify the solution thus obtained by dissociation of water using ion transfer through ion exchange membranes, and c) concentrate the solution thus obtained by nano filtration.   10. Process according to claim 9, characterized in that step a) is preceded by a preliminary step making it possible to retain and separate possible polluting elements.   11. The method of claim 10, characterized in that said preliminary step is carried out by filtration of the raw seawater using an activated carbon filter.   12. Method according to any one of claims 9 to 11, characterized in that step a) is carried out in an electrodialysis reactor comprises compartments intended for the circulation of the brine (so-called brine compartments) and compartments intended to the circulation of the product (called product compartments), respectively composed of anionic and cationic membranes, said reactor being in circuit with a vessel containing the product connected to the product compartments, a vessel containing the brine connected to the brine compartments, said anionic membranes passing through in the brine compartments the monovalent ions and said cationic membranes preferentially retaining in the compartments produce the divalent ions.   13. The method of claim 12, characterized in that the product consists of filtered seawater and the brine is mineralized raw seawater and acidified.   14. Process according to any one of claims 9 to 13, characterized in that step b) allowing acidification of the product is carried out simultaneously and progressively during the selective demineralization of step a).   15. The method according to claim 14, characterized in that step b) is carried out by dissociation of the water by transfer of H + ions generated on the surface of the cationic membranes of the compartments produced, while in the compartments brine, OH- ions are produced on the surface of anionic membranes.   16. The method of claim 15, characterized in that said H + ion transfer is carried out against the electric field generated by the anode and the cathode located on either side of all the reactor membranes. electrodialysis.   17. Method according to any one of claims 9 to 16, characterized in that the concentration step c) is carried out by circulating the contents of the product tank in a concentration loop consisting of nanofiltration membranes.   18. The method of claim 17, characterized in that said nanofiltration membrane is preferentially selective to divalent ions and poorly selective to monovalent ions.   19. Use of a composition according to any one of claims 1 to 8 for the hygiene of the female genital sphere.   20. Use according to claim 19 to promote by instillation, the elution of the vaginal walls and the cervix.   21. Use according to claim 19 for intimate hygiene, for external use.   22. Apparatus for using a composition according to any one of claims 1 to 8, comprising a conditioning tank containing said composition and a hand shower for instillation thereof.   23. Device according to claim 22, characterized in that it also comprises an overpack bag.   24. Device according to one of claims 22 or 23, characterized in that it is disposable.   25. Device according to any one of claims 22 to 24, characterized in that the conditioning tank comprises an ergonomic flexible bag (A) acting as a reservoir and a flexible tube (1) acting as a filling site and diffuser .   26. Device according to one of claims 22 to 25, characterized in that the hand shower (2) comprises at one of its closed ends a breakable tip (7).   27. Device according to claim 26, characterized in that the shower comprises a breakable portion (7), a combination of parts making a seal-valve (5, 6), and an ergonomic half-sphere (10).   28. Device according to any one of claims 22 to 27, characterized in that a protective sleeve cap the shower head before overwrapping.   29. Device according to any one of claims 22 to 28, characterized in that the overpacking bag is made unitarily from a welded multi-layer polyethylene-polyvinyl chloride film.