WO2003018193A1 - Procede de preparation d'un materiau solide composite a base d'hexacyanoferrates, et procede de fixation de polluants mineraux le mettant en oeuvre - Google Patents
Procede de preparation d'un materiau solide composite a base d'hexacyanoferrates, et procede de fixation de polluants mineraux le mettant en oeuvre Download PDFInfo
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- WO2003018193A1 WO2003018193A1 PCT/FR2002/002906 FR0202906W WO03018193A1 WO 2003018193 A1 WO2003018193 A1 WO 2003018193A1 FR 0202906 W FR0202906 W FR 0202906W WO 03018193 A1 WO03018193 A1 WO 03018193A1
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- hexacyanoferrate
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
-
- 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
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Definitions
- the present invention relates to a process for the preparation of a solid composite material fixing mineral pollutants based on insoluble hexacyanoferrates.
- the present invention relates to a process for the preparation of a composite solid material fixing mineral pollutants, based on hexacyanoferrates and cationic polymers, deposited in a film layer on a support. Even more precisely, the present invention relates to a process for the preparation of a composite solid material fixing mineral pollutants formed from a mechanically and chemically stable solid support, coated with a film of an anion exchange polymer, to which a thin layer of insoluble hexacyanoferrate is fixed.
- the present invention also relates to a method for fixing at least one mineral pollutant contained in a solution on said composite solid material fixing mineral pollutants.
- the hexacyanoferrates in particular the hexacyanoferrates (II) of Cu, Ni and Co are among the most commonly used mineral fixers, in particular in the nuclear industry because of the high affinity they have for cesium.
- Inorganic fixing agents of the hexacyanoferrate type have therefore in particular been used to separate, recover and fix the metal ions and in particular the radioactive alkali metal ions such as cesium 137 with long half-life from various industrial and nuclear effluents, for example from strongly acid solutions resulting from the reprocessing of irradiated fuels and from the solutions already mentioned above.
- insoluble hexacyanoferrates are used in most processes treatment of liquid radioactive waste by co-precipitation.
- the document FR-A-2 765 812 describes the method of preparation and use in column of a material composed of metallic hexacyanoferrate fixed on a solid support chemically and mechanically stable, coated with a thin film of organic polymers exchangers of anions for fixing at least one mineral pollutant, in particular from a liquid or an effluent from the nuclear industry.
- the product first prepared, then packaged in the form of a column, allows the total and irreversible fixation of cesium 137.
- the hexacyanoferrate anion is adsorbed on the anion exchange polymer covering a solid support in the form of a film, by interactions of electrostatic type and, therefore, strongly adheres to the support.
- This bond involves adsorption phenomena in the pores as in the impregnated hexacyanoferrates.
- 1 hexacyanoferrate is carried out uniformly over the entire modified surface of the support. All the possible exchange sites for the polymer are exchanged, the composition and properties of the material are perfectly controlled and reproducible, unlike the materials of the prior art. There is no longer any residual hexacyanoferrates on the surface capable of being released and subsequently disturbing the fixing process.
- the material has a contact surface of the same order of magnitude as the specific surface of the selected support, thus the reactivity of the copper hexacyanoferrate is increased.
- the distribution coefficient of cesium is high (Kd> 100,000) and comparable to those of hexacyanoferrates impregnated with quantities of hexacyanoferrate of 1 to 2% by mass relative to the mass of support. This is in particular the reason why " it is possible to easily store the material of this document which is stable and essentially mineral.
- the method of fixing at least one metal cation (for example Cs + ) can be implemented separately, either in “column” mode or in "batch” mode, with stirring.
- the reactants such as copper sulphate and sodium ferrocyanide
- the reactants are previously mixed to form a mixed hexacyanoferrate formed of copper, sodium and potassium.
- This hexacyanoferrate is then introduced at very low flow rate into a column containing the mineral support. Once the hexacyanoferrate has been fixed on the silica, a certain number of purification steps are carried out in “batch”, thus forcing recourse to a new column setting for decontamination.
- This process must, moreover, make it possible to prepare a material whose properties are stable, perfectly controlled and without random variations, and in which the polymer is fixed in an adherent and stable manner to the support, even without resorting to grafting operations and / or complicated and long crosslinking and carried out in "batch" mode. It is obvious that the material prepared by the process must also meet the criteria and requirements which are for the most part already satisfied by the solid composite material of the prior art represented by FR-A-2 765 812. In particular, this material must be chemically and mechanically stable in order to be able to be thus conditioned in a column allowing continuous implementation of the fixing process, of pollutants, of decontamination.
- the solid composite material fixing mineral pollutants must also have excellent fixing properties, in particular of decontamination, that is to say analogous, or even superior in particular to those of hexacyanoferrates not impregnated on a support.
- the solid material fixing mineral pollutants must also combine good mechanical stability with a high reaction speed, unlike products in compact form, the low specific surface of which leads to slow reaction rates.
- the solid material fixing mineral pollutants, based on metal hexacyanoferrates must present among other things excellent mechanical and chemical stabilities, a high coefficient of affinity or of decontamination, a great reactivity, as well as a good selectivity.
- the composite solid material fixing mineral pollutants must be able to be easily stored and / or vitrified without risk by known methods.
- the material prepared by this process must have a composition and properties that are perfectly reproducible and controlled.
- the present invention therefore aims to provide a process for the preparation of a composite solid material fixing mineral pollutants based on metal hexacyanoferrates, which does not have the drawbacks, defects, disadvantages, and limitations processes for the preparation of composite solid materials fixing mineral pollutants of the prior art, as represented essentially by the document FR-A-2 765 812, which overcomes the problems of the processes of the prior art and which fulfills, inter alia , the set of needs mentioned above.
- the present invention also aims to provide a method for fixing at least one mineral pollutant contained in a solution which uses said composite solid material and which can be carried out continuously, in particular with a reduced duration and a high efficiency. .
- a process for the preparation of a composite solid material fixing mineral pollutants, based on metal hexacyanoferrate comprising a solid support coated with a film of an anion exchange polymer to which is fixed an insoluble metal hexacyanoferrate forming a thin layer, said method essentially comprising at least one step of bringing said solid support into contact with at least one liquid reagent, and optionally at least one step washing, with an avage liquid, characterized in that all of the process steps are carried out continuously in a single container, such as a column, in which the support forms a fluidized bed, the fluidization of which is provided by said at least one reagent or washing liquid.
- the process according to the invention is carried out entirely continuously, in a single container, such as a column, this means that there is no there is no transfer of the material from one container to another during the process, that all the stages of preparation are carried out, successively, continuously, without breaking, without interruption, unlike the processes of the prior art, where certain stages are carried out in “batch” mode, and others are carried out continuously with each time a change of container, and a transfer of the material.
- the method according to the invention makes it possible to prepare large quantities of material, for example up to hundreds of kilograms, in a relatively short reaction time.
- process steps generally covers any operation aimed at obtaining the targeted material, namely synthesis, purification, or the like.
- preparation generally covers any operation aimed at obtaining the targeted material, namely synthesis, purification, or the like.
- Such a method however essentially comprises at least one step of bringing the solid support into contact with at least one liquid reagent and at least one step of washing with a washing liquid.
- the solid support forms a fluidized bed, the fluidization of which is ensured by said at least one liquid reagent or washing liquid.
- Fluidization is generally ensured by a very high flow rate (80 to 280 ml / min) of this reagent or washing liquid sent into the previously fixed bed of solid support, against the current from bottom to top in the bed of solid support.
- the synthesis of the material, and in particular the deposition of the insoluble metal hexacyanoferrate on the support, is greatly facilitated by the implementation of the fluidized bed, which ensures both the chemical reaction, as well as a perpetual movement of the support. .
- the method according to the invention allows, in particular, to obtain a homogeneous, uniform deposit of metal hexacyanoferrate on the solid support coated with cationic polymer obtained in the same container, during the previous step of the same continuous process .
- the uniformity of the deposit on the support thanks to the implementation of the fluidized bed, no longer requires compaction thereof and avoids the problems due to the preferential paths encountered in the prior art.
- the material prepared by the process according to the invention essentially due to the use of a fluidized bed during its preparation, thus has inherent, improved properties, compared to the prior art, in which the preparation of the material is not made fully continuous in a single column, and in a fluidized bed.
- the material prepared by the process according to the invention is coated with a homogeneous and uniform layer of hexacyanoferrate, which is not the case in analogous materials of the art anterior prepared in "batch” mode and, moreover, without using a fluidized bed. It was also noted that the material prepared by the process of the invention exhibited distribution constants, for example with respect to a solution loaded with radioactive cesium, much higher than those obtained with the products prepared in " batch ”, for example 10 4 mL / g instead of 10 3 mL / g.
- the material according to the invention has a structure substantially similar to that described in document FR-A-2 765 812, namely, the material prepared by the process according to the invention has a specific structure in which the mineral fixer as such, ie the metal hexacyanoferrate, is in the form of a thin layer which is immobilized on a polymer phase fixed on a support, said support being solid and advantageously, chemically and mechanically stable, and being protected and isolated from the action of the medium by the underlying polymer layer. Therefore, the material prepared according to the invention is also chemically and mechanically stable and combines these stabilities with a high reaction rate, and is perfectly suited for column packaging • for fixing and decontamination. It will be seen later that, in fact, this column is preferably advantageously according to the invention the same as that in which the material is prepared.
- the mechanical stability of the material prepared according to the invention has proved perfect column, after washing with pure water for several days, corresponding to more than 10,000 column volumes.
- the hexacyanoferrate anion is adsorbed on the polymer, by interactions of electrostatic type, and therefore strongly adheres to the support.
- the bond which exists between the anionic part of the metal hexacyanoferrate, and the support coated with the anion exchange polymer is an electrostatic type bond, which is not a weak bond of a mechanical nature essentially involving phenomena adsorption in the pores as is the case in impregnated hexacyanoferrates, for example on silica gel.
- the deposition of the hexacyanoferrate is, as already indicated, carried out uniformly over the entire modified surface of the support.
- the material prepared according to the invention also has a contact surface which is of the same order of magnitude as the specific surface of the chosen support. Consequently, the reactivity of hexacyanoferrate is increased.
- the distribution coefficient of the material prepared according to the invention which is preferably 10,000 to 100,000 (mg / L) for one gram of material, is high and is comparable to that of massive hexacyanoferrates, but the amounts of exacyanoferrates used are advantageously much lower than those of hexacyanoferrates impregnated on silica.
- the material prepared according to the invention generally comprises an amount of metal hexacyanoferrate fixed from 1 to 10% by weight, preferably from 2 to 3% by weight relative to the mass of the support, this value is to be compared to the 30% value for the hexacyanoferrates impregnated on silica mentioned above.
- the quantity of ferrocyanide which is fixed and rejected after its use is limited, and the same efficiency is obtained for a quantity, for example ten times less, of hexacyanoferrate, since all the fixed product is effective.
- the solid support can be chosen from the supports known to those skilled in the art and suitable for the use described; these solid supports can be organic or mineral and are generally chosen from chemically and mechanically stable solid supports.
- the support will thus preferably be chosen from mineral oxides such as silica, alumina, titanium oxide, zirconium oxide, diatomaceous earth, glasses, and zeolites; a preferred support is silica, readily available at a reasonable cost.
- the support may be in any form, but because it must be fluidized, it will preferably be in the form of particles such as grains, beads or spheres; or fiber.
- the particle size of the support, in the form of particles, defined by the size of the particles, that is to say the diameter in the case of spherical particles, can vary within wide limits and will generally be from 1 to 500 ⁇ m, preferably greater than or equal to 10 ⁇ m, more preferably still greater than or equal to 30 ⁇ m, for example.
- the specific surface of the support can also be variable, for example from 10 to 500 m 2 / g, preferably 30 to 500 m 2 / g.
- the support is preferably a porous support to allow better fixation of the polymer.
- the average pore size of the support is variable, and is preferably 100 to 1000 ⁇ .
- the anion exchange polymer of the composite solid material fixing mineral pollutants according to the invention is derived from an organic polymer which has been optionally provided with cationic groups by any process known to those skilled in the art.
- This organic polymer is preferably chosen from polyvinylimidazoles, copolymers of vinylimidazole with at least one other monomer, for example a vinyl monomer, polyethyleneimines, polyamines and any polymer carrying a cationic group or the like or capable of being provided with it. .
- Any polymer is suitable on the condition that it forms a film, or film very adherent to the surface of the support, for example by adsorption in the pores or by covalent bond using a suitable grafting, and that it is or that it can be a carrier of cationic groups.
- the polymer is a non-crosslinked polymer, which comprises as anion exchanger groups only quaternary ammonium groups, and which does not contain primary, secondary and tertiary amino groups.
- said cationic polymer, the anion exchanger is a Polybrene ® or bromide hexadimethrine or poly (dibromide N, N, N ', N' -tétraméthyltriméthylènehexamêthylènediammonium) (C ⁇ 3 H 30 Br 2 N 2) x .
- CAS No [2 8728-55-4] which is a water-soluble polymer, widely used in biochemical applications and which contains only quaternary ammonium groups.
- the polybrene formula is as follows:
- the preferred polymers adhere to the support, in an excellent manner, without crosslinking or fixing by covalent bond. Since the preferred polymer does not have primary and secondary and tertiary groups, the formation of unstable metal complexes is avoided, as well as the subsequent release of metal ions, such as copper, from the material.
- the properties of the composite material are perfectly controlled, stable and do not undergo random variations.
- the film is strongly adherent to the support and this film is extremely stable. It may be thought that the excellent adhesion of the preferred polymers, such as polybrene, to the support, comes from the interaction between the NR 4 + of the polymer and the silanol groups of the support.
- the metal hexacyanoferrate which is attached to the anion exchange polymer can be any hexacyanoferrate known to those skilled in the art, it can be chosen, for example, from copper, cobalt, zinc, cadmium, nickel, iron hexacyanoferrates and the like. mixed hexacyanoferrates relating to these salts.
- the process for the preparation of the invention of a solid composite material fixing mineral pollutants, based on metal exacyanoferrate, comprising a solid support coated with a film of an exchange polymer anions, to which is fixed an insoluble metal hexacyanoferrate forming a thin layer is absolutely not limited to steps, operating parameters of these steps, reagents, and possible particular washing liquids.
- the process according to the invention can be, for example, any process for the preparation of a composite solid material defined above, in which while retaining substantially the same steps, the same reagents, and the same washing liquids, the adaptation is carried out consisting in carrying out all of said steps continuously in a single container, such as a column, in which the support forms a fluidized bed, the fluidization of which is ensured by the liquid reagents or washing liquids, if any.
- a preparation process which can be adapted to be carried out in accordance with the process of the invention, continuously, and in a fluidized bed is, for example, the process described in the document.
- Such a process may include a crosslinking step which is difficult and time-consuming to carry out with heating to approximately 60 ° C. This is the reason why, in a preferred embodiment of the invention, the preparation process is carried out without crosslinking, preferably using particular cationic polymers.
- Such a method comprises the following successive steps:
- the anion exchange polymer is preferably chosen from anion exchange polymers, non-crosslinked, comprising as anion exchange groups only quaternary ammonium groups and not comprising no primary, secondary and tertiary amino groups.
- Polyethyleneimines (PEI) can also be chosen, but this involves tedious intermediate and final rinsing steps.
- the adsorption of the polymer which is soluble in water, takes place in an aqueous medium, from an aqueous solution and not in an organic medium, without prior drying, under vacuum, of the support, and this contact time is reduced, for example to 1 hour;
- the adhesion of the polymer to the support is stable, which eliminates the steps of crosslinking, carried out at 60 ° C., (very long) and of fixing by covalent bonding, in addition, the step of creation of cationic groups does not exist either, since the polymer advantageously comprises from the outset the necessary cationic groups.
- an acid pH step must be used to protonate it.
- a strongly adherent polymer film is obtained in a single adsorption step by simple contact, without placing under vacuum, of a duration, for example, close to 1 hour, without prior drying and crosslinking, instead of having to resort to at least three long and difficult stages the duration of which can go up to 48 hours, which are energy consuming and require vacuum, drying and a heater.
- a duration for example, close to 1 hour
- the invention finally relates to a method for fixing at least one mineral pollutant such as a metal cation contained in a solution, in which a composite solid material fixing the mineral pollutants is first prepared, based on hexacyanoferrate from metal, comprising a solid support coated with a film of an anion exchange polymer to which an insoluble metal hexacyanoferrate is fixed by the process described above without a final drying step, then said solution is continuously contacted with said composite solid material fixing mineral pollutants, in the same container, such as a column, where said material was prepared.
- a composite solid material fixing the mineral pollutants is first prepared, based on hexacyanoferrate from metal, comprising a solid support coated with a film of an anion exchange polymer to which an insoluble metal hexacyanoferrate is fixed by the process described above without a final drying step, then said solution is continuously contacted with said composite solid material fixing mineral pollutants, in the same container, such as a column, where said material was prepared.
- This fixing process has the advantage of being able to be carried out continuously following, preferably, immediately, immediately after, the process for preparing the composite solid material; the latter remains in the same container, which eliminates a long, difficult transfer operation, as well as column packaging of the material also long and difficult.
- composition of the product obtained is such that there is no need at the end of the preparation to have recourse to a final stage of drying the material before decontamination, fixing the pollutants, since there is no There are no excess ferrocyanides.
- Decontamination, fixing can therefore be carried out according to the invention immediately after preparation, without drying, in the same device.
- the contacting of the material and the solution to be depolluted can be carried out in the column for example by percolation of the solution through the material, or else in a particularly advantageous manner by means of a (in a) similar fluidized bed.
- said fluidized bed being formed by the composite solid material, the fluidization of which is ensured by the solution containing the mineral pollutant; that is to say, in this case, it is the entire fixing process, including the synthesis, which is carried out in the same fluidized bed and in the same container, such as a column.
- the fixing process can be carried out, preferably, immediately after this in the same container, preferably also in a fluidized bed, without loss of time, transfer and other conditioning step.
- the fixing method according to the invention is very simple, because it only implements one device, namely a single container such as a column, which is extremely advantageous, in particular, in the case of the treatment of radioactive fluids. In addition, the overall duration of the process is greatly reduced.
- the method for fixing pollutants according to the invention has all the other advantages inherent in the material prepared. These advantages being essentially linked to the preparation in a fluidized bed, which have already been indicated above, namely in particular clearly higher partitioning constants and the absence of preferential paths.
- the invention will now be described in more detail in the following, with particular reference to the preparation process in its preferred embodiment.
- the first step of this process consists in impregnating a solid support with an organic polymer solution on said solid support.
- the solid support is one of those which have already been mentioned above, a preferred carrier is silica Lichrospher ® 100 from Merck ®, the polymer is also one of the preferred polymers which have been mentioned above, still preferred polymers being a polybrene ® (PB), preferably a polybrene ® of molecular mass 4,000 to 6,000 g / mol supplied by the company Sigma Aldrich ® or else a polyethyleneimine of molecular mass (10,000 g / mol) supplied by the same company .
- PB polybrene ®
- this solid support is placed in a container, such as a column, and forms at the start of the process a fixed bed.
- the fluidization of this bed is created by circulating in this fixed bed a current (against the current) of liquid reagent or possibly a washing liquid.
- the techniques for creating a fluidized bed are well known to those skilled in the art.
- the reagent or liquid enters the container or the column by an inlet orifice and crosses the fixed bed at a rate sufficient to cause its fluidization, without entraining, however, the particles from which the bed is formed and leaves by an outlet.
- the container such as a column
- the container is generally vertical and is, for example, in the form of a straight vertical cylinder, into which the liquid or liquid reagent enters through an inlet orifice provided at the base of the cylinder and crosses, in ascending, vertical flow, the bed which is thus fluidized, and the liquid is discharged at the top of the column, through an outlet orifice provided in the other base of the cylinder.
- the polymer solution is a solution in water, for example in demineralized water.
- the solution generally has a concentration of 20 to 100 g / l.
- the impregnation is carried out by bringing the solid support into contact with the polymer solution at a flow rate, for example, from 80 to 280 ml / min, sufficient to cause fluidization, for a sufficient time, which is surprisingly according to the invention short, for example 1 hour (instead of 24 to 48 hours in "batch" mode), whereby a uniform coating of polymer is obtained on the solid which isolates and protects the solid support, which follows its forms "and porosities, and which retains its specific surface.
- the fixing of the polymer on the solid support is essentially governed by an adsorption phenomenon with interactions of electrostatic type, this fixing is according to the invention relatively strong without the need for grafting by covalent bonds.
- film is meant as already indicated above, a uniform coating over the entire surface of the solid support and which substantially retains the specific surface of the latter.
- This film generally has a thickness of 2 to 3 nm.
- This step is carried out again continuously, preferably immediately after the previous step, it suffices for this to simply replace the stream of demineralized water with an alkali metal hexacyanoferrate solution.
- the starting alkali metal hexacyanoferrate is preferably chosen from sodium or potassium hexacyanoferrates (II) and (III).
- the aqueous solution of alkali metal hexacyanoferrate used at a variable concentration that is to say that the concentration of the salt of hexacyanoferrate (II) or (III) of alkali metal in particular potassium or sodium is preferably from 1 to 100 g / 1, for example from 50 g / 1.
- the aqueous solution of hexacyanoferrate used is prepared in such a way that the mass ratio of the salt of hexacyanoferrate (II) or (III) of alkali metal, in particular potassium or sodium, to the quantity of the impregnation support essentially consisting of the initial solid support such as silica, is preferably 5 to 10%.
- the impregnation does not have to be carried out at a defined, adjusted pH, controlled for example by a buffer. It is a solution in water, preferably pure, demineralized water.
- the flow rate of the solution is, for example, from 80 to 280 ml / min, so as to ensure or maintain the fluidization.
- the solid support thus coated with a film of anion exchange polymer to which an alkali metal hexacyanoferrate is attached is then subjected to a washing operation. Washing is carried out continuously, preferably immediately after the previous step.
- the purpose of the washing operation is to remove the alkali metal hexacyanoferrate salts which have not been fixed on the polymer and makes it possible to obtain a composite material fixing mineral pollutants in which there is no longer any free, unbound hexacyanoferrate which can be released.
- Washing is carried out with demineralized water.
- the amount of rinse solution used is variable and can range from 100 to 1000 ml per gram of product treated.
- the flow rate of the rinsing solution is such that the fluidization is adequately ensured.
- the next step is the addition of an aqueous solution of metal salt to the solid support coated with a film of an anion exchange polymer, to which the hexacyanoferrate anion is attached.
- This step is also according to the invention carried out continuously, preferably immediately after the previous step, replacing the rinsing solution with a solution of metal salt.
- the metal salt contained in this aqueous solution is a salt whose metal corresponds to the insoluble hexacyanoferrate which it is desired to obtain as has already been indicated above.
- This metal is chosen, for example, from copper, cobalt, zinc, cadmium, nickel and iron, etc.
- the metal salt will therefore be for example a nitrate, a sulphate, a chloride, an acetate of one of these metals at a concentration in the aqueous solution preferably from 0.01 to 1 mol / 1, more preferably from 0, 02 to 0.05 mol / 1.
- the amount of salt used is moreover preferably about 0.4 mmol / g of treated support.
- the addition of the aqueous solution of the metal salt does not have to be done at a defined pH, using of a buffer solution.
- the aqueous solution is a solution in pure water, demineralized.
- the final material is washed, which thus comprises the solid support coated with a film of an anion exchange polymer to which an insoluble metal hexacyanoferrate is attached, forming a thin layer.
- This last washing step is carried out in the same manner and under the same conditions as the washing step already described above, using pure demineralized water.
- This step is carried out continuously, and preferably immediately after the previous step.
- an alkali metal salt for example sodium, the anion of which is preferably the same as that of the metal salt used in the previous step, and optionally , in addition, the corresponding acid: it is possible to use, for example, sodium nitrate and nitric acid.
- This washing operation makes it possible to remove the excess metal salt and to obtain a stable final product with a perfectly defined composition. It must be followed by a final step of rinsing with demineralized water.
- drying is continued until the mass of the support remains substantially constant. However, this drying step is preferably generally omitted if one proceeds to it, and continuously fixing the pollutants contained in a solution.
- the content by weight of mineral fixer that is to say of insoluble metal hexacyanoferrate fixed on the anion exchange polymer is generally from 1 to 10%, for example 3% relative to the mass of the mineral support such as silica . It has been observed by analysis by neutron activation that the atomic ratio of M 2 / Fe can vary from 1 to 5 without the fixing properties, in particular of decontamination being affected.
- the solid composite material. fixing mineral pollutants prepared by the process according to the invention is preferably immediately after its preparation - the possible final drying step being omitted - used in fixing at least one mineral pollutant, for example of a cation metallic contained in a solution, wherein said solution is brought into contact with said composite solid material fixing mineral pollutants.
- this fixing is carried out continuously in the same container, such as a column where the solid material has been prepared. Therefore, no conditioning, transfer is necessary.
- the materials prepared according to the invention because of their excellent properties such as excellent exchange capacity, excellent selectivity, a reaction speed . high are particularly suitable for such use.
- the material prepared according to the invention can be used in particular over a very wide range of PH.
- aqueous nitric solutions with a concentration ranging, for example, from 0.1 to 3M, acidic or neutral solutions up to a pH 8, basic solutions, etc.
- concentration ranging, for example, from 0.1 to 3M
- silica does not generally resist at a basic pH
- a solid support for example made of Ti0 2
- the use of the composite material can then be extended, for example, to pH 10.
- the mineral pollutant capable of being fixed in the fixing method according to the invention can be any mineral pollutant, that is to say for example any pollutant derived (based) from a metal or an isotope, preferably from a radioactive isotope, of this metal, likely to be in solution.
- This pollutant is preferably chosen from anionic complexes, colloids, cations and their mixtures.
- a pollutant such as a cation derived from an element chosen from Tl, Fe, Cs, Co, Ru, Ag, ... and the isotopes, in particular the radioactive isotopes of these- Ci, among which we can cite 58 C o, 60 C o, 55 " 59 Fe, 134 C s, 137 C s," 3, ⁇ os , ⁇ o 5 , ⁇ o 7 Ru>
- the metal cation is in particular Cesium Cs + or Thallium Tl 2+ .
- the anionic complex is for example
- a preferred use of the material prepared according to the invention is the fixation of cesium which contributes to a large part of the gamma activity of liquids from the nuclear industry and which is selectively fixed by the hexacyanoferrates.
- the concentration of pollutant (s) such as cation (s) can vary between wide limits: for example it can be for each of thereof of 0.1 picogram to 100 mg / 1 of 'preferably
- the solution to be treated by the fixing process of the invention is preferably an aqueous solution which, in addition to the pollutant (s) such as one or more cation (s) to be fixed, may contain other salts in solution such than NaNo 3 or LiN0 3 or alternatively A1 (N0 3 ) 3 or any other soluble salt of alkali or alkaline earth metal at a concentration of up to 2 moles / l.
- the solution may also contain, as indicated above, acids, bases, and even organic compounds.
- the solution to be treated can also be a solution in a pure organic solvent such as ethanol (absolute alcohol), acetone or the like, in a mixture of these organic solvents, or in a mixture of water and one or more several of these water-miscible organic solvents.
- a pure organic solvent such as ethanol (absolute alcohol), acetone or the like
- the material prepared according to the invention thus has the advantage of being able to treat solutions which cannot be treated with organic resins.
- This solution can consist of a process liquid or an industrial or other effluent which can originate in particular from industry and nuclear installations or from any other activity linked to nuclear power.
- nuclear installations and activities using radionuclides which can be treated by the process of fixing the invention, for example, may be cited the cooling water from power stations, and all the various effluents coming into contact with radioisotopes such as all washing water, solutions for regenerating resins, etc.
- the fixing method according to the invention can also be implemented in other fields of activity, industrial or other, non-nuclear.
- hexacyanoferrates selectively fix thallium and this property could be exploited in the purification of cement effluents to reduce or eliminate the releases and emissions of this element which is a violent poison.
- the contact time of the solution to be treated with the exchanger material is variable and can range from 1 minutes to 1 hour with continuous operation according to the invention.
- this duration is notably shorter than in the analogous processes carried out in batch or partly in batch, partly continuously, in different containers.
- the solid composite fixing material (exchanger) prepared according to the invention in which, for example, the metal cations of the exacyanoferrate have been exchanged by the cations in the solution can be directly stored, because its very high mechanical and chemical stabilities and its essentially mineral nature allow such storage without degradation of the product leading to hydrogen fumes, or it can be treated by a process allowing conditioning for long-term storage, for example by vitrification. Vitrification is particularly suitable in the case where the fixed cations are radioisotopes and the support is silica.
- the material prepared according to the invention thanks to its specific structure, and unlike the exchanger materials of the prior art based on hexacyanoferrate, can be vitrified without danger because the quantities of mineral fixative are limited and decontamination in air safe.
- the anion exchange polymer is a polybrene (PB) having the following structure and characteristics: Molar mass 4,000 to
- a silica support (Silica Gel 100 ® ) supplied by the company Merck®, having a particle size of 0.063 to 0.200 mm, and a porosity of 100 ⁇ m, is impregnated with polybrene (PB) supplied by the SIGMA Company
- the anion exchange film support is brought into contact with, impregnated with, a concentrated solution of sodium hexacyanoferrate II (50 g / 1) in water (no buffer); - the support is then rinsed with demineralized water; a copper hexacyanoferrate (II) is formed on the film surface by adding an aqueous solution of 2.10 "2 M copper (II) nitrate in demineralized water;
- the ion-exchange polymer is a polyethyleneimine (PEI) supplied by the company Sigma Aldrich.
- PEI polyethyleneimine
- Example 1A The procedure is the same as in Example 1A, except that the polymer produced is different and crosslinked in a fluidized bed.
- the elementary analysis of the final product obtained is also given in Table I below.
- Elemental composition of the materials prepared according to the invention based on copper hexacyanoferrate (the percentages are percentages by mass per g of silica)
- the material was prepared in “batch” as follows:
- silica support (Silica Gel 100 ®) supplied by the company Merck® having a particle size of 0.063 to 0.200 mm, and a porosity of 100 .mu.m, is impregnated with polyethylimine (PEI) supplied by SIGMA ALDRICH ® Company, contacting in “batch” for a period of 10 h in a solution at 15% by mass of polymer in demineralized water, and then crosslinked for 2 h at reflux at 60 ° C. with an agent crosslinking the diglycidyl ether of the 1-4 butane diol (BUDGE) sold by the company Aldrich - The support thus coated is rinsed with demineralized water, and dried under vacuum;
- PKI polyethylimine
- the anion exchange film support is brought into contact in “batch” with, impregnated with, a concentrated solution of sodium hexacyanoferrate II (50 g / 1) in water for 4 h; the support is then rinsed with demineralized water; a copper hexacyanoferrate (II) is formed on the film surface by addition of an aqueous solution of 2.10 "2 M copper (II) nitrate in demineralized water for 4 h; the excess of hexacyanoferrate (II) is eliminated by washing with a 2 M sodium nitrate solution, then a 0.1 M nitric acid solution and then with demineralized water.
- the procedure for preparing the material is mixed: it was prepared in "batch” and in column with packing of the phase (which is different from the fluidized bed according to the invention), as follows: - a silica support (Silica Gel 100 ® ) supplied by the company Merck®, having a particle size of 0.063 to 0.200 mm, and a porosity of 100 ⁇ m, is impregnated with polyethylimine (PEI) supplied by the company SIGMA ALDRICH ® , by placing in “batch” contact for a period of 10 h in a solution at 15% by mass of polymer in demineralized water, and then crosslinked for 2 h at reflux at 60 ° C. with an agent crosslinking the diglycidyl ether of 1-4 butane diol (BUDGE) sold by the company Aldrich
- the anion exchanger film support is packed in a column and brought into contact and impregnated by percolation at a low flow rate ranging from
- Kd the higher the value of Kd, the more the Cs * is retained in the solid phase.
- a Kd value greater than 10,000 for contact times of 24 h represents an excellent affinity of cesium for the solid phase.
- the radioactive effluents treated are real effluents from the OSIRIS cell of the SACLAY nuclear studies center, the characteristics of which relating to radioactivity are mentioned in Table II.
- it is the water for cooling the cell which is designated by “OSI” in the table and whose pH is neutral, and on the other hand the rinsing, regeneration, resins solution. which is designated by “BF6” in the table and which is constituted by a 0.1 M nitric acid solution.
- OSI water for cooling the cell
- BF6 rinsing, regeneration, resins solution.
- a 134 Cs tracer was added to the OSI solution.
- the solution is filtered, its radioactivity is measured by gamma spectrometry and is compared with that of the starting solution.
- Kd the higher the value of Kd, the more the Cs + is retained in the solid phase.
- Radioactive solution which is an “OSI” solution, or a “BF6” solution as defined above
- OSI an “OSI” solution
- BF6 a “BF6” solution as defined above
- the decontamination factor is the activity of the solution before passing over the phase over the activity of the solution after passing over the phase (3).
- the first filter is a frit which retains particles larger than 20 ⁇ m
- the next is a filter with lower porosity.
- a peristaltic pump placed in series draws at a flow rate of 1.5 to 5 mL / min. the solution to a stainless steel column (30 * 5 mm) containing 1 g of composite. This column is closed at each end by a frit and shielded over its entire height by a leaden castle with a thickness of 5 cm.
- 50 ml of eluate are collected in a bottle of eluate every 250 ml of treated solution.
- the entire assembly is placed in a retention tank with a volume of 10 mL.
- the radioactivity of the eluates, as well as of the control, is then measured by gamma spectrometry.
- the product prepared in "batch” has a decontamination coefficient much lower than that of the products synthesized in a fluidized bed, in accordance with the invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UA2004021276A UA76178C2 (en) | 2001-08-22 | 2002-08-20 | Method for preparing a composite solid material based on metal hexacyanoferrate and method for fixing mineral pollutants using this material |
EP02774878A EP1419009A1 (fr) | 2001-08-22 | 2002-08-20 | Procede de preparation d'un materiau solide composite a base d'hexacyanoferrates, et procede de fixation de polluants mineraux le mettant en oeuvre |
JP2003522699A JP2005500158A (ja) | 2001-08-22 | 2002-08-20 | ヘキサシアノ鉄塩に基づく複合固体材料の調製方法、及びこれを使用して無機汚染物質を固定する方法 |
US10/486,829 US20040178385A1 (en) | 2001-08-22 | 2002-08-20 | Method for preparing a composite solid material based on hexacyanoferrates, and method for fixing mineral pollutants using same |
EA200400327A EA005634B1 (ru) | 2001-08-22 | 2002-08-20 | Способ получения композиционного сложного материала на основе гексацианоферратов и способ связывания загрязняющих примесей с использованием такого материала |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR01/11005 | 2001-08-22 | ||
FR0111005A FR2828819B1 (fr) | 2001-08-22 | 2001-08-22 | Procede de preparation d'un materiau solide composite a base d'hexacyanoferrates, et procede de fixation de polluants mineraux le mettant en oeuvre |
Publications (1)
Publication Number | Publication Date |
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WO2003018193A1 true WO2003018193A1 (fr) | 2003-03-06 |
Family
ID=8866661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2002/002906 WO2003018193A1 (fr) | 2001-08-22 | 2002-08-20 | Procede de preparation d'un materiau solide composite a base d'hexacyanoferrates, et procede de fixation de polluants mineraux le mettant en oeuvre |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040178385A1 (fr) |
EP (1) | EP1419009A1 (fr) |
JP (1) | JP2005500158A (fr) |
EA (1) | EA005634B1 (fr) |
FR (1) | FR2828819B1 (fr) |
UA (1) | UA76178C2 (fr) |
WO (1) | WO2003018193A1 (fr) |
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WO2008002282A1 (fr) * | 2006-06-29 | 2008-01-03 | Fos International S.A. | procédé de décontamination de déchets radioactifs liquides (variantes) et sorbant sélectif vis-à-vis du Cs |
WO2012177269A1 (fr) * | 2011-06-23 | 2012-12-27 | Cellresin Technologies, Llc | Matériau adsorbant tel qu'un film, une fibre, un tissu tissé ou non tissé |
EP2794490A4 (fr) * | 2011-12-23 | 2015-08-26 | Tusaar Inc | Système pour un chargement fluidifié dynamique d'un ligand sur un support de carbone et procédés associés à ce système |
WO2016202869A1 (fr) * | 2015-06-17 | 2016-12-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Materiaux monolithiques inorganiques alveolaires echangeurs cationiques, leur procede de preparation, et procede de separation les mettant en œuvre |
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FR2828818B1 (fr) * | 2001-08-22 | 2003-12-05 | Commissariat Energie Atomique | Materiau solide composite fixant des polluants mineraux, son procede de preparation et procede de fixation de polluants mineraux le mettant en oeuvre |
FR2859924B1 (fr) * | 2003-09-23 | 2006-02-03 | Commissariat Energie Atomique | Dispositif et procede de fixation de polluants mineraux |
FR2945756B1 (fr) * | 2009-05-20 | 2011-08-05 | Commissariat Energie Atomique | Materiau solide nanocomposite a base d'hexa-et octacyanometallates, son procede de preparation et procede de fixation de polluants mineraux le mettant en oeuvre. |
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JP5725621B2 (ja) * | 2012-01-18 | 2015-05-27 | 大日精化工業株式会社 | 放射性ヨウ素・放射性セシウムの除去方法及び放射性ヨウ素・放射性セシウムの除去用の親水性樹脂組成物 |
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JP6211838B2 (ja) * | 2013-07-12 | 2017-10-11 | ユニチカトレーディング株式会社 | セシウムイオン吸着用水処理担体及びその製造方法 |
US10435528B2 (en) | 2013-09-17 | 2019-10-08 | Aquanano Llc | High-capacity anion exchange materials |
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WO2016043808A1 (fr) * | 2014-09-17 | 2016-03-24 | Aquanano Llc | Matériau échangeur d'anions à haute capacité |
JP7486148B2 (ja) | 2018-12-20 | 2024-05-17 | 日揮ユニバーサル株式会社 | 汚染物質除去剤、汚染物質除去部材、及び汚染物質の除去方法 |
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2001
- 2001-08-22 FR FR0111005A patent/FR2828819B1/fr not_active Expired - Fee Related
-
2002
- 2002-08-20 JP JP2003522699A patent/JP2005500158A/ja active Pending
- 2002-08-20 WO PCT/FR2002/002906 patent/WO2003018193A1/fr active Application Filing
- 2002-08-20 US US10/486,829 patent/US20040178385A1/en not_active Abandoned
- 2002-08-20 UA UA2004021276A patent/UA76178C2/uk unknown
- 2002-08-20 EP EP02774878A patent/EP1419009A1/fr not_active Withdrawn
- 2002-08-20 EA EA200400327A patent/EA005634B1/ru not_active IP Right Cessation
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US3345305A (en) * | 1963-11-08 | 1967-10-03 | Saint Gobain Techuiques Nouvel | Method of preparation of solution containing barium 137 |
GB1115258A (en) * | 1967-02-22 | 1968-05-29 | Saint Gobain Techn Nouvelles | Method of cesium removal |
US5601722A (en) * | 1994-05-18 | 1997-02-11 | Agency Of Industrial Science And Technology | Method for the preparation of an ion exchanger for cesium ions and method for the regeneration thereof |
FR2737426A1 (fr) * | 1995-08-03 | 1997-02-07 | Stmi Soc Tech Milieu Ionisant | Procede de preparation de ferrocyanures et ferricyanures de metaux impregnes sur un support |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008002282A1 (fr) * | 2006-06-29 | 2008-01-03 | Fos International S.A. | procédé de décontamination de déchets radioactifs liquides (variantes) et sorbant sélectif vis-à-vis du Cs |
WO2012177269A1 (fr) * | 2011-06-23 | 2012-12-27 | Cellresin Technologies, Llc | Matériau adsorbant tel qu'un film, une fibre, un tissu tissé ou non tissé |
US9821291B2 (en) | 2011-06-23 | 2017-11-21 | Cellresin Technologies, Llc | Material such as film, fiber, woven and nonwoven fabric with adsorbancy |
US10035128B2 (en) | 2011-06-23 | 2018-07-31 | Cellresin Technologies, Llc | Material such as film, fiber, woven and nonwoven fabric with adsorbancy |
EP2794490A4 (fr) * | 2011-12-23 | 2015-08-26 | Tusaar Inc | Système pour un chargement fluidifié dynamique d'un ligand sur un support de carbone et procédés associés à ce système |
WO2016202869A1 (fr) * | 2015-06-17 | 2016-12-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Materiaux monolithiques inorganiques alveolaires echangeurs cationiques, leur procede de preparation, et procede de separation les mettant en œuvre |
FR3037583A1 (fr) * | 2015-06-17 | 2016-12-23 | Commissariat Energie Atomique | Materiaux monolithiques inorganiques alveolaires echangeurs cationiques, leur procede de preparation, et procede de separation les mettant en œuvre. |
Also Published As
Publication number | Publication date |
---|---|
FR2828819B1 (fr) | 2003-10-24 |
EA005634B1 (ru) | 2005-04-28 |
EA200400327A1 (ru) | 2004-08-26 |
US20040178385A1 (en) | 2004-09-16 |
UA76178C2 (en) | 2006-07-17 |
EP1419009A1 (fr) | 2004-05-19 |
JP2005500158A (ja) | 2005-01-06 |
FR2828819A1 (fr) | 2003-02-28 |
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