EP3959004A1 - Procédé de fabrication d'une membrane à haut pouvoir de percolation - Google Patents
Procédé de fabrication d'une membrane à haut pouvoir de percolationInfo
- Publication number
- EP3959004A1 EP3959004A1 EP20731529.2A EP20731529A EP3959004A1 EP 3959004 A1 EP3959004 A1 EP 3959004A1 EP 20731529 A EP20731529 A EP 20731529A EP 3959004 A1 EP3959004 A1 EP 3959004A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- mixture
- manufacturing
- aqueous solution
- cationic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
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- B01D71/06—Organic material
- B01D71/08—Polysaccharides
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- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
- B01D71/601—Polyethylenimine
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28028—Particles immobilised within fibres or filaments
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- B01J35/59—Membranes
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- B01J37/02—Impregnation, coating or precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention relates to a method of manufacturing a membrane with high percolation power due to high macroporosity.
- Sorption is the simplest, most effective and the least expensive technique to implement.
- the adsorbents commonly used for sorption are materials such as activated carbon.
- these materials have the disadvantages of being unstable, present poor mechanical properties, to be difficult to recover after sorption thereby generating a 2 nd source of pollution.
- Filter membranes in particular those used in membrane processes such as microfiltration, ultrafiltration, reverse osmosis
- their life cycle in particular their elimination at the end of the cycle
- toxic pollutants such as volatile organic compounds
- a certain number of drawbacks are liable to limit its use: flow rates, cost, clogging phenomena.
- the generation of large volumes of concentrates that are difficult to recover is also a limitation.
- the percolation properties of current filter membranes are sometimes made difficult (in particular as a function of their porosity, of the presence of particles in suspension) by pressure drops and / or clogging problems.
- filter membranes of the “sponge” type providing both a filtering structure (for simplified and low-energy implementation: gravity percolation, for example), as well as a specific reactivity associated with the presence of functional groups.
- adsorbent sponges with high macroporosity can find fields of application in supported catalysis.
- the immobilization of complex and expensive catalytic formulations requires good containment of these metallic or organometallic phases, combined with optimized material transfer properties for optimizing the conditions and performance of catalytic reactions.
- the supports on which palladium nanoparticles were immobilized consisted of inorganic materials such as mesoporous silica, zeolites and activated carbon.
- inorganic materials such as mesoporous silica, zeolites and activated carbon.
- the palladium nanoparticles were often leached out during the chemical reaction; which led to losses of catalyst.
- the losses of such catalysts were increased due to the fact that they were not easily recoverable at the end of the chemical reaction, and this despite the implementation of separation techniques (centrifugation and filtration) costly in time and in energy, and therefore making the catalytic support based on inorganic material inefficient for its use on an industrial scale.
- the inventors have overcome all these drawbacks detailed above with regard to filter materials intended for a wide variety of applications such as the treatment of liquid effluents, but also their use as supports (functionalized or not) for heterogeneous catalysis or for anti-microbial products.
- the inventors have in fact developed a new process for manufacturing a membrane with high percolation power which perfectly meets these objectives.
- the invention relates to a method of manufacturing a membrane which comprises at least the following steps:
- the mixture is left to mature to cause the ionic interaction between positively charged groups of the cationic polymer and negatively charged groups of the anionic polymer, until a membrane is obtained within the mixture in the form of a hydrogel;
- step d) the crosslinked membrane obtained at the end of step d) is dried.
- the cationic polymer has a molecular weight greater than 40,000 g / mol. In addition, it exhibits positive charges over a wide pH range which is between 5 and 8.
- the cationic polymer can be chosen from polyethyleneimine (hereinafter “PEI”), poly (allylamine hydrochloride), chitosans and proteins (for example gelatins).
- the anionic polymer has a viscosity of between 0.4 and 0.5 Pa.s for a 1% solution by mass of this polymer.
- it advantageously exhibits negative charges at neutral or slightly acidic pH (namely for pH values between 5 and 7).
- the anionic polymer can be chosen from poly (acrylic acid), pectin, carrageenan, alginate and poly (styrenesulfonate).
- the mixture of step a) can comprise, in percentages by mass expressed relative to the mass of said mixture:
- Step a) can be carried out by gradually adding the aqueous solution of cationic polymer to a container containing the aqueous solution of anionic polymer.
- step a) at least one solid compound is added to the mixture.
- This solid compound can be chosen from activated carbon, silica and clay.
- This solid compound will give the membrane new reactive functions or new functionalities.
- these examples of solid compounds are porous and carry functional groups having different affinities with respect to contaminants; which makes it possible to broaden the possible applications of the membrane.
- their porous and / or polar / non-polar characteristics can give it properties of immobilization of organic compounds (for example essential oils, perfumes or even any chemical compound used for liquid / liquid extractions).
- the solid compound is rehydrated before its introduction into the mixture in order to facilitate its dispersion in this mixture which is viscous owing to the presence of the two polymers.
- this addition represents, as a percentage by mass expressed relative to the dry mass of the membrane, between 0.05% and 1.2%. More precisely, when the compound is activated carbon or silica, the mass percentage can be between 0.05% and 0.4%, preferably between 0.1% and 0.3%. In the case of clay, the mass percentage can be between 0.4% and 1.2%, preferably between 0.5% and 0.8%.
- Step b) can be carried out at room temperature with stirring at a speed of between 16,000 revolutions / minute and 22,000 revolutions / minute, preferably between 19,000 revolutions / minute and 21,000 revolutions / minute.
- the duration of step b) can be between 30 seconds and 2 minutes, preferably between 40 seconds and 80 seconds.
- the mixture can be poured into a mold (for example a polypropylene box) and the maturation step c) is then carried out.
- a mold for example a polypropylene box
- the geometry of the mold will give a shape to the membrane which will be obtained at the end of the process according to the invention.
- the varied geometries of the molds allow the production of membranes of different shapes and sizes.
- a membrane is formed within the mixture in the form of a hydrogel due to the ionic interaction between positively charged groups of the cationic polymer (for example the amino functions of the PEI, or of a chitosan) and negatively charged groups of the anionic polymer (for example the carboxylic functions of the alginate or the sulfonic functions of a carrageenan).
- hydrogel is meant according to step c), a material forming a wet membrane and consisting of a network of two cationic and anionic polymers. This polymer network has a structure which does not result from ionotropic gelation, but indeed from ionic bonds between the aforementioned groups of opposite charges and which already has macroporosity.
- Step c) can be carried out over a temperature range varying between -80 ° C and 50 ° C (therefore including freezing of the mixture for negative temperatures). This is not critical for the interaction between positively charged groups of the cationic polymer and negatively charged groups of the anionic polymer to take place. Thus, it can be carried out at room temperature, it can also be carried out, in one embodiment of the invention, at a temperature between -10 ° C and -30 ° C. In this last mode, one obtains a mechanically stable membrane with a remarkable elasticity (namely that it can accept important deformations). In the case of freezing, thawing takes place during step d) during which the crosslinking agent is added.
- step c) however has an influence on the reaction kinetics (or in other words on the quality of the ionic interactions between the cationic polymer and the anionic polymer), and consequently on the process of structuring of the membrane; which induces the textural characteristics (in particular the macroporosity characteristics) of the membrane obtained according to the manufacturing process according to the invention.
- step c) advantageously, all the charged groups of the cationic and anionic polymers respectively do not necessarily interact. Indeed, free groups (or charged depending on the intended application) will have to remain for the consecutive step d) of crosslinking, depending on the desired crosslinking, but also because of their involvement depending on the use which is then made of the membrane. resulting from the process of the invention. It is of course within the competence of those skilled in the art to adapt the conditions of step c) to the quality of the expected membrane. Thus, if it is used to retain metal ions, it will be necessary to ensure that reactive groups (cationic and anionic of the starting polymers) remain free.
- the rate of positively charged groups and / or of negatively charged groups which have remained free is less than or equal to 50%, for example example of 30-50%. If it is necessary to control this rate, a person skilled in the art, on the basis of his general knowledge, can in particular act on the ratio of the concentration of the cationic polymer to that of the anionic polymer, over the duration of the step. b).
- the membrane is washed at least once with water, preferably with demineralized water. This makes it possible to remove the reagents and monomers which have not reacted between the various constituents in step c), as well as the labile parts.
- step d) at least one crosslinking agent is added to the mixture which contains the membrane in the form of a hydrogel from step c).
- This step of crosslinking the network formed in step c) generates an additional mesh to form a new crosslinked network which then contributes to reinforcing the structuring of the membrane and in particular to freezing the porous network.
- This additional mesh can be the result of a crosslinking of the chains of the cationic polymer between them, of a crosslinking of the chains of the anionic polymer between them, or of a crosslinking of the chains of the cationic polymer and of the chains of the anionic polymer, according to the crosslinking agent involved, or even a combination of these mechanisms with the use of several crosslinking agents.
- crosslinking takes place between the neighboring chains.
- Those skilled in the art are able to select the crosslinking agent (s) for this step, in particular as a function of the application which is made of the high percolation membrane manufactured. It should be observed that this step d) can involve groups of said cationic and / or anionic polymers, which are also the groups involved in step c); it is therefore in this case necessary that all these groups have not been engaged in step c).
- the crosslinking agent is suitably chosen according to the nature of the cationic polymer.
- the crosslinking agent can be glutaraldehyde.
- the cationic polymer is PEI
- glutaraldehyde the aldehyde function of the latter will react with the free amino functions of the PEI. This is a Schiff base type reaction.
- the percentage by weight of the crosslinking agent can be between 0.1% and 1%, relative to the weight of the mixture from step a).
- the percentage by weight of the crosslinking agent is advantageously between 0.1% and 0.6%.
- step d) the crosslinking agent is advantageously added to the mixture with slow stirring (for example by subjecting the mixture to a “back and forth” movement: between 20 and 40 movements per minute).
- the crosslinked membrane is washed at least once with water, preferably with demineralized water. This makes it possible to eliminate the reagents and monomers which have not reacted between the various constituents, as well as the labile parts.
- step e) the membrane thus obtained is dried.
- the drying is advantageously carried out at ambient temperature under an air flow (for example with an extractor hood).
- This process does not require a complex and energy-consuming device; which makes the originality and the interest of the process according to the invention.
- a membrane which has the following properties:
- a porosity such that the percentage of void is between 90% and 96%, preferably around 95%;
- the manufacturing process according to the invention has the advantage of not requiring any sophisticated drying process to maintain the high porosity of the membrane.
- the process according to the invention makes use of simple steps of agitation, gelation and crosslinking, as well as of drying at room temperature. It does not necessarily require a freeze-drying step or the production of a cryogel.
- the sophisticated drying step as described above is perfectly optional in the context of the invention and is implemented only if it is desired to have a membrane having a bi-structure, namely a macroporous structure with a micro- or meso-porous surface.
- the manufacturing process according to the invention has the advantage of obtaining a mechanically stable membrane with good elasticity, in particular when, in step c), the mixture is allowed to mature by freezing it.
- the method according to the invention allows the easy manufacture of membranes under better energy conditions.
- the invention also relates to a membrane with high percolation power capable of being obtained by the above process, in particular as obtained by this process.
- it can be an adsorbent membrane, it can also be a membrane not involving any interaction of its groups.
- a subject of the invention is also the use of the membrane obtained according to the manufacturing process for the treatment of liquid or gaseous effluents.
- a subject of the invention is also the use of the membrane obtained according to the manufacturing process as a support for heterogeneous catalysis. This support has the advantage of being able to easily recover the catalysts at the end of their life cycle thanks to easy removal from the membrane, for example by thermal degradation. This thus allows the recycling of precious metals which are used as catalyst for heterogeneous catalysis.
- a subject of the invention is also the use of the membrane obtained according to the manufacturing process as an anti-microbial support.
- the membrane can easily retain anti-microbial compounds such as metal cations (for example Ag (l), Zn (II), Cu (II), Ni (II)) which have biocidal properties.
- the membrane can also exhibit antimicrobial properties if it is chemically modified by the grafting of quaternary amines, for example at the level of the cationic polymer. This chemical modification may have been carried out on the cationic polymer before the implementation of the manufacturing process according to the invention or even before or after the drying step.
- the grafting of quaternary amines is perfectly within the reach of a person skilled in the art, as are these antimicrobial properties obtained by the quaternization of cationic polymers.
- the membrane obtained with the process according to the invention on which metal cations have been adsorbed or which has been chemically modified by quaternization so that it has biocidal properties can thus be used as a filter medium for microbial decontamination. .
- FIG. 1 shows a graph of the changes in the binding capacity noted “q eq " of chromium (VI) (hereinafter abbreviated “Cr (VI)” and of total chromium (hereinafter “Cr (total”) as a function of respectively the residual concentration C eq in Cr (VI) and Cr (total) after experiments of adsorption of chromium ions on a membrane obtained according to a 1 st embodiment of the manufacturing process according to the invention.
- FIG. 2 represents a photograph of a membrane obtained according to a 2 nd embodiment of the manufacturing method according to the invention.
- FIG. 3 is a graph showing the changes as a function of the hydrogenation reaction time of 3-nitrophenol (hereinafter abbreviated "3-NP") of the relative residual concentration of palladium noted “C t / Co” for 3 membranes d 'different thicknesses and which were obtained according to this 2 nd embodiment of the manufacturing process according to the invention.
- 3-NP 3-nitrophenol
- FIG. 4 is a graph of the modeling of the kinetic profiles by the pseudo first order equation (ln (Ct / Co) as a function of the reaction time established from the relative residual concentrations of palladium recorded.
- FIG. 5 represents a graph of the breakthrough curves obtained with other experiments on the hydrogenation reaction of 3-NP.
- FIG. 6 shows a photomicrograph of a membrane produced according to the invention illustrating the macroporosity of the material (scanning electron microscope).
- FIG. 7 represents a photograph illustrating the high percolation power (by gravity drainage) of a membrane produced according to the invention during the flow of a liquid.
- FIG. 8 shows a photograph of a membrane produced according to the invention (plate, 20 x 10 cm).
- FIG. 9 represents a photograph of the internal macroporosity of the membranes produced according to the invention (in section, after cutting with a punch).
- the membrane was washed 5 times with deionized water.
- the washed membrane was suspended in 300 mL of demineralized water to which was added 4 mL of an aqueous solution of glutaraldehyde at a mass content of 50% so as to effect crosslinking of the membrane.
- the membrane was subjected to moderate agitation of 30 "back and forth" movements per minute for 24 hours.
- the membrane was rinsed (6 times) with 300 mL of deionized water, then dried at room temperature for 2 days.
- the membrane thus obtained exhibited the following characteristics: a porosity (measured with a pycnometer) of 93.4%; 94% stability to attrition;
- pHpHpzc a zero charge point pH
- the stability of the membrane was determined by subjecting a sample of the membrane in the form of a 25 mm diameter disc immersed in 20 mL of water to stirring at 150 rpm for 72 hours. Then, the membrane was dried and weighed. Stability is the percentage of membrane remaining at the end of this agitation relative to the initial mass of membrane. The value of 94% testifies to a very good stability to attrition of the membrane and to the maintenance of its integrity when it is subjected to strong agitation in water.
- the water flow was determined by measuring the time required for 100 mL of water to pass through a membrane sample with an area of 4.64 cm 2 , at 20 ° C and a pressure of 0.006 bar.
- the value of the water flow (in natural percolation) of 33.6 mL / (cm 2 .min) testifies to the excellent percolation properties of the membrane.
- FIG. 7 illustrates the natural flow by gravity drainage through the macroporosity of membranes with high percolation power.
- the membrane thus obtained was subjected to sorption experiments with a solution containing Cr (VI) ions in order to characterize its adsorption properties.
- the device used for these experiments consisted of a device operating continuously for the recirculation of solutions containing metal ions which included:
- a support configured to contain the membrane and allow the circulation of the metal ion solution through said membrane;
- the Cr (VI) concentration was determined with an ultraviolet spectrophotometer sold by the company Shimadzu under the trade name UV-1650PC at a wavelength of 540 nm by the colorimetric method using diphenylcarbazone.
- the total Cr concentration (ie the sum of the Cr (VI) and Cr (III) ions) was determined by atomic emission spectrometry with induced plasma with a spectrometer sold by the company Horiba under the trade name Activa.
- the concentration of Cr (III) was determined by subtracting the concentration of Cr (total) from the concentration of Cr (VI).
- the adsorption isotherm was determined with the device described above by circulating in a loop at 20 ° C and continuously for 96 hours 50 mL of Cr (VI) solutions at a pH of 2 and at initial concentrations. between 20 and 300 mg / L. The circulation rate was 15 mL / minute.
- FIG. 1 is a graph of the changes in the binding capacity q eq of Cr (VI) and of Cr (total) as a function of the residual concentration C eq in Cr (VI) and Cr (total) respectively.
- the maximum adsorption capacity exceeds 300 mg Cr (VI) / g.
- This maximum binding capacity is very high (representing more than 6 mmol Cr (VI) / g of adsorbent).
- the slope at the origin for Cr (VI) is almost vertical. This demonstrates the strong affinity of the membrane obtained with the manufacturing process according to the invention for chromate ions.
- the slope at the origin for Cr (total) is lower. This is linked to mechanisms of in situ reduction of Cr (VI) on the membrane in an acidic medium.
- a volume of 100 mL of a 4% alginate solution (by mass) was diluted with 400 mL of demineralized water so as to obtain a 1st solution.
- the mixture was poured into a polypropylene mold avoiding the formation of bubbles and the whole was left at room temperature for 24 hours.
- a membrane was obtained due to the gelation reaction of the alginate with the PEI.
- the membrane obtained was washed 5 times with demineralized water in order to remove the free reactants. 300 mL of demineralized water were added to the washed membrane, then 2.5 mL of an aqueous solution of glutaraldehyde at a mass content of 50% so as to reinforce the crosslinking of the membrane.
- the membrane was subjected to moderate agitation consisting of a "back and forth" motion of 30 strokes / minute for 24 hours.
- the membrane was washed 4 times with deionized water, then dried at room temperature for 2 days.
- the membrane thus obtained exhibited the following characteristics: a porosity (measured with a pycnometer) of 70.93%;
- Stability was determined in the same way as for the 1st set of experiments. The value of 97% testifies to a very good stability to attrition of the membrane and to the maintenance of its integrity when it is subjected to strong agitation in water.
- the water flow was determined in the same way as for the 1 st series of experiments.
- the value of 24.8 mL / (cm 2 .min) shows excellent percolation properties of the membrane.
- FIG. 2 represents a photograph of a sample of this adsorbent membrane 1 which was thus obtained.
- the sample is 55 mm in length and has a diameter of 25 mm.
- the membrane was cut into 25 mm diameter disks.
- a disc (of dry mass 250 mg) was then placed in the support configured to contain the membrane of the device described in the 1st series of experiments so as to produce a fixed bed column.
- One liter of a solution of Palladium (II) (hereinafter abbreviated: "Pd (II)") of variable concentration, between 10 and 50 mg / L, the pH of which has been adjusted to 1 with acid sulfuric acid was circulated in a loop within this device for 24 hours with a flow rate of 30 mL / min.
- the optimum conditions for the binding of palladium on the membrane (in other words "the best maximum yield of use of palladium") were obtained when its concentration was 28 mg Pd / L.
- the column was rinsed 4 times with deionized water at a pH of 1.
- the membrane was not dried before proceeding with the reduction of the metal.
- the reduction of the Pd (II) immobilized on the membrane was carried out by hydrazine hydrate (chemical formula: IShH ⁇ PhO) at a concentration of 0.03 mol / L in 200 mL of an alkaline solution (at a concentration of 0.5 mmol / L of NaOH) with stirring at 60 ° C. for 5 hours.
- hydrazine hydrate chemical formula: IShH ⁇ PhO
- the catalytic membrane A membrane on which palladium was adsorbed was obtained. This membrane is hereinafter abbreviated "the catalytic membrane”.
- the size of the palladium nanoparticles varied between 4.5 and 10.5 nm.
- the catalytic membrane was recirculated in a loop for 12 minutes with 100 mL of a solution of 3-NP at 50 mg 3-NP / L the pH of which was adjusted to 2.84 in the presence of formic acid at a concentration of 0.2% by mass.
- the formic acid concentration was set in molar excess with respect to 3-NP (formic acid / 3-NP molar ratio of 160/1).
- the recirculation rate was 50 mL / min.
- the 3-NP concentration was measured spectrophotometrically at 332 nm. To do this, the samples taken were acidified with 20 ⁇ L of a 5% by mass solution of sulfuric acid prior to the spectrophotometric analysis.
- FIG. 3 is a graph showing the changes as a function of the hydrogenation reaction time of the relative residual concentration of palladium noted “C t / Co” for the 3 membranes tested:
- FIG. 4 is a graph of the modeling of the kinetic profiles by the pseudo first order equation (ln (Ct / Co) as a function of the reaction time for the 3 catalytic membranes tested:
- the catalytic membrane was supplied with this solution of 3- NP at these same circulation rates of 20 or 30 mL / minute but by regenerating it (by simple rinsing with demineralized water using a volume corresponding to approximately 9 times the volume occupied by said membrane) when the volume of 3-NP which had circulated through the catalytic membrane had reached the values of 40 mL and 80 mL.
- FIG. 5 represents a graph of the breakthrough curves obtained with these experiments. This is the change in the residual concentration of 3-NP as a function of the volume of the 3-NP solution passed through the catalytic membrane when:
- the breakthrough curves show a progressive increase in the residual concentration of 3-NP as a function of the volume of the 3-NP solution which has passed through the catalytic membrane. Increasing the flow rate increases the slope of the breakthrough curve (due to insufficient residence time in the catalytic membrane).
- This catalytic reaction for hydrogenation of 3-NP clearly illustrates the possibility of using the membranes with high percolation power obtained with the manufacturing process according to the invention for the immobilization of catalytic metals and the synthesis of catalytic supports to be used in dynamic regime at high filtration rate, with confinement of nanoparticles.
- these membranes have the advantage of being able to easily recover the catalysts at the end of their life cycle, for example by thermal degradation of the membranes. The precious metals which constitute the catalysts are thus recycled.
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Abstract
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FR1904290A FR3095353B1 (fr) | 2019-04-24 | 2019-04-24 | Procédé de fabrication d’une membrane adsorbante à haut pouvoir de percolation |
PCT/FR2020/050701 WO2020217029A1 (fr) | 2019-04-24 | 2020-04-24 | Procédé de fabrication d'une membrane à haut pouvoir de percolation |
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EP3959004A1 true EP3959004A1 (fr) | 2022-03-02 |
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US (1) | US20220193617A1 (fr) |
EP (1) | EP3959004A1 (fr) |
FR (1) | FR3095353B1 (fr) |
WO (1) | WO2020217029A1 (fr) |
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US5502082A (en) * | 1991-12-20 | 1996-03-26 | Alliedsignal Inc. | Low density materials having good compression strength and articles formed therefrom |
US20050069572A1 (en) * | 2002-10-09 | 2005-03-31 | Jennifer Elisseeff | Multi-layered polymerizing hydrogels for tissue regeneration |
PL222739B1 (pl) * | 2013-04-26 | 2016-08-31 | Politechnika Gdańska | Kompozycja chitozanowa i sposób wytwarzania hydrożelowej membrany chitozanowej |
US10364163B2 (en) * | 2014-06-06 | 2019-07-30 | University Of Houston System | Porous nanocomposite polymer hydrogels for water treatment |
CN106832549A (zh) * | 2017-02-17 | 2017-06-13 | 安徽民祯活性包装材料有限公司 | 一种果蔬保鲜膜的制备方法 |
CN108639564B (zh) * | 2018-05-24 | 2020-06-12 | 青岛农业大学 | 一种可食用复合膜及其制备方法和用途 |
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2019
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US20220193617A1 (en) | 2022-06-23 |
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