(EN) ASPIRABLE GEL AND METHOD FOR REMOVING CONTAMINATION FROM AN ORGANIC LAYER ON THE SURFACE OF A S

专利摘要:
Aspirating gel for removing a contaminating species, for example a radioactive contaminating species, contained in an organic layer on the surface of a material, consisting of a colloidal solution preferably comprising: - 1% to 25% by weight, preferably 5% to 20% by weight, for example 10% by weight, based on the total mass of the gel, of at least one inorganic viscosifying agent; - 13% to 99% by weight, preferably 80% to 95% by weight, for example 90% by weight, based on the total mass of the gel of an organic solvent selected from terpenes and mixtures thereof; optionally, from 0.01% to 10% by weight, relative to the total mass of the gel, of at least one dye and / or pigment; optionally, from 0.1% to 2% by weight, relative to the total mass of the gel, of at least one surfactant; - optionally from 0.1% to 10% by weight, preferably 0.1% to 5% by weight, relative to the total mass of the gel, of at least one radionuclide extracting agent, preferably chosen from zeolites and clays. Decontamination process using this gel.
公开号:FR3054840A1
申请号:FR1753083
申请日:2017-04-07
公开日:2018-02-09
发明作者:Alban GOSSARD；Fabien Frances
申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
IPC主号:

专利说明:

Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
Extension request (s)
Agent (s): BREVALEX.
FR 3 054 840 - A1
104) SUCTION GEL AND METHOD FOR REMOVING CONTAMINATION CONTAINED IN AN ORGANIC LAYER ON THE SURFACE OF A SOLID SUBSTRATE.
©) Suction gel to remove a contaminating species, for example a radioactive contaminating species, contained in an organic layer on the surface of a material, consisting of a colloidal solution comprising, preferably consisting of:
- 1% to 25% by mass, preferably 5% to 20% by mass, for example 10% by mass, relative to the total mass of the gel, of at least one inorganic viscosifying agent;
- 13% to 99% by mass, preferably 80% to 95% by mass, for example 90% by mass, relative to the total mass of the gel of an organic solvent chosen from terpenes and their mixtures;
- optionally, from 0.01% to 10% by mass, relative to the total mass of the gel, of at least one dye and / or pigment;
- Optionally, from 0.1% to 2% by mass, relative to the total mass of the gel, of at least one surfactant;
- optionally from 0.1% to 10% by mass, preferably 0.1% to 5% by mass, relative to the total mass of the gel, of at least one agent extracting radionuclides, preferably chosen from zeolites and clays.
Decontamination process using this gel.
SUCTION GEL AND METHOD FOR REMOVING CONTAMINATION CONTAINED IN
AN ORGANIC LAYER ON THE SURFACE OF A SOLID SUBSTRATE.
DESCRIPTION
TECHNICAL AREA
The present invention relates to a gel for eliminating contamination, for example radioactive contamination, contained in an organic layer on the surface of a solid substrate.
More precisely, by organic layer is meant a layer made of an organic material, constituted by an organic material.
In the present, the terms contamination, for example radioactive contamination, contaminant, for example radioactive contaminant, or else contaminating species, for example radioactive contaminating species are used interchangeably.
The contaminating species which can be eliminated by the gel according to the invention can in particular be radioactive and / or chemically toxic contaminating species and / or toxic due to their shape and / or their size, such as dust, microparticles, nanoparticles, or fibers.
In particular, the gel according to the invention can be used to remove asbestos, contained in an organic layer on the surface of a solid substrate.
The present invention further relates to a method for removing contamination, for example radioactive contamination, contained in an organic layer on the surface of a solid substrate.
This organic layer may be an organic surface layer contaminated with a solid substrate constituted by an organic material.
More specifically, in this case, the organic layer of contaminated surface is an integral part of the solid substrate and the organic layer and the solid substrate consist of the same organic material.
This solid substrate constituted by an organic material may be a solid substrate or a layer, such as a layer of paint or epoxy resin, for example a layer of paint or epoxy resin forming a coating on a surface of a (other ) solid substrate.
Or, this organic layer may be a layer constituted by an contaminated organic material, lying on a surface of a solid substrate, this layer being in particular in the form of a stain or discrete stains of contaminated organic material contaminating said surface, for example a stain of contaminated oil or bitumen which stains said surface.
In this case, the contaminated surface layer and the solid substrate are not made of the same organic material and the solid substrate can be made of any material: metal, resin, paint, etc.
The technical field of the invention can be defined, in general as that of decontamination, for example radioactive decontamination of surfaces, with a view to eliminating contamination from these surfaces, for example radioactive decontamination, namely contaminating species , for example contaminating radioactive species.
The invention applies, in particular, to the decontamination of contaminated surfaces in the context of dismantling and cleaning up nuclear installations, or in the context of asbestos removal from buildings.
PRIOR STATE OF THE ART
As part of the clean-up and dismantling of nuclear installations, various decontamination steps are necessary.
The diversity of the materials present in nuclear installations as well as the surface condition of these materials make decontamination operations difficult and require adapting the treatment methods to the materials and the targeted contamination.
In particular, one of the most important problems that arises is the decontamination of contaminated organic matrices composed of contaminated organic materials, such as paints or epoxy resins, or the decontamination of surfaces contaminated with traces of contaminated organic matrices, such as contaminated bitumen or oil stains which are often present on the sites of nuclear installations.
Difficulties are encountered mainly when the contamination is embedded in the organic matrix.
The decontamination processes used today for the decontamination of organic matrices such as murals or epoxy resins use in particular conventional techniques for cleaning surfaces using wipes - used dry or impregnated with decontaminating solutions and / or degreasers or wipers, which are carried out manually in often very sensitive nuclear environments.
Many fairly rudimentary mechanical decontamination processes are also used. These are decontamination processes that use techniques such as cutting, sanding or pickling. These techniques prove to be tedious and painful in terms of implementation, generate dust, and are often not very effective on relatively thick organic layers.
These mechanical decontamination processes are being optimized and are today often coupled with thermal processes using, for example, lasers or thermal lances.
These optimized mechanical processes nevertheless remain relatively restrictive from the point of view of the arduousness of the work. In addition, the contribution of a thermal process can significantly increase the cost of implementation.
Other decontamination processes use aqueous or organic chemical solvents. These methods can also allow the decontamination of contaminated organic matrices by applying the solvents directly to the surfaces of these matrices.
These decontamination processes which use chemical solvents are however not very used on decontamination sites, due to the large production of contaminated effluents.
With regard now to the removal of traces of contaminated organic matrices, such as contaminated oil or bitumen stains which contaminate the surfaces of nuclear installations, there is not, here again, adequate decontamination processes. , especially since these traces of organic matrices are generally sticky and fixed to the support on which they are found. This is particularly the case for contaminated bitumen stains.
There are certainly vacuum systems that allow the recovery of labile dust on a substrate, but these systems are therefore not suitable for sticky deposits. In addition, following the implementation of these suction systems, a scrubber is generally used, but it produces a large amount of effluent.
Finally, for strongly adherent tasks, human intervention is necessary with tedious and tedious washing operations using wipes or scraping.
Among the documents of the prior art which describe the use of an organic solvent, mention may be made of the document FR-A1-2 957 929 [5],
This document relates to a method for treating a solid surface, in particular an anti-fouling treatment method suitable for treatment for curative and / or preventive purposes of a solid surface. The purpose of this process is in particular the elimination and / or prevention of graffiti and tags.
According to this method, a composition is applied to the surface comprising at least one ester of a carboxylic acid which is an ester called an odd acid ester. This composition can be in the form of a microemulsion.
There is no mention or suggestion that this composition may be in the form of a gel.
Among the documents of the prior art which describe the use of an organic solvent, in the form of a gel, mention may be made of the document WO-A1-99 / 09134 [3],
This document relates to a cleaning composition for removing long-chain compounds such as bitumen, tar, wax and chewing gum which comprises an inert gel matrix inside which is enclosed a nonaqueous liquid solvent in which the long chain compound is soluble.
The gel matrix is formed for example by silica or clay, but not by alumina.
The solvent can be chosen from saturated and unsaturated hydrocarbons, alcohols, glycols, aldehydes, ketones, ethers, terpenes, phthalates, esters, or halogenated hydrocarbons.
The gel in this document is not a gel that can be described as a suction gel.
Furthermore, in this document, there is no description of the process which is used to apply or apply the gel.
The only example given in this document relates to the elimination of chewing gum, the composition of which is very far from that of the contaminated surface layers which generally consist of an epoxy resin or a paint, and that of stains from contaminated organic material, which generally consist of contaminated oil or bitumen.
Furthermore, the long-chain compounds, for example chewing gum, eliminated in this document are not contaminated by contaminating species, for example by radioactive contaminating species, and therefore do not contain such species.
Finally, there is no mention or suggestion in this document that the gel described therein can be used to solve the specific problem of removing contamination, such as radioactive contamination, contained in a layer of organic material.
Furthermore, in the context of nuclear decontamination, gelled formulations which make it possible to overcome the problems associated with the pulverulent nature of dry waste, and to increase the efficiency of the process using a gel have been the subject of documents FR-A1-2 827 530 [1] and FR-A1-2 891 470 [2],
These documents describe inorganic colloidal gels called “aspirable gels”, specifically formulated to be sprayed, then to dry by fracturing, while trapping and confining the radioactive contamination in the form of non-pulverulent flakes, aspirable, and directly packaged and storable.
Document [1] describes a gel consisting of a colloidal solution comprising an inorganic viscous agent, generally silica or alumina, an active treatment agent which is for example an inorganic acid or base such as sodium hydroxide or potassium hydroxide, and optionally an oxidizing agent having a normal Eosuperior redox potential greater than 1.4 V in a strong acid medium such as Ce (IV), Co (III), or Ag (II).
Document [2] describes a gel consisting of a colloidal solution comprising an inorganic viscous agent, generally silica or alumina, a surfactant, an inorganic acid or base, optionally an oxidizing agent having normal potential. Reduction Eosuperior to 1.4 V in a strong acid medium such as Ce (IV), Co (III), or Ag (II).
These inorganic colloidal gels, due to the various constituents entering into their composition have a rheology which allows them to be sprayed on a contaminated surface, then their adhesion to this surface, even vertical, without running.
This thus allows prolonged contact between the contaminant and the active decontamination agent, without the mechanical properties of the substrate being altered.
Following its spraying, the dry gel fractures and produces dry residues, called "flakes", adhering to the substrate and which are then removed by brushing or suction to be directly conditioned.
The decontamination processes which use these aspirable gels are therefore dry decontamination processes, generating no liquid effluent and few dry solid residues. Indeed, these dry solid residues represent on average only a quarter of the mass of gel initially sprayed. In addition, these methods limit the time of exposure of operators to radioactive contamination, because of their easy implementation by spraying then suctioning of dry residues, and because the presence of the operator is not required during drying the gel.
The gels described in documents [1] and [2] are however specifically intended for the elimination of radioactive contamination, which is on the surface of a substrate, whether it is an organic substrate or other . This radioactive contamination is not contained in a layer of organic material.
The gels in these documents are in no way specifically adapted to the elimination of contamination, for example radioactive contamination, contained in a layer of organic material, or even capable of being adapted to the elimination of contamination, for example radioactive contamination, contained in a layer of organic material.
There is no mention or suggestion in the documents [1] and [2] that the gels in these documents can solve the extremely specific problem of eliminating contamination, for example radioactive contamination , contained in a layer of organic material, integrated in an organic matrix, which is a problem completely different from the problem of eliminating contamination, for example radioactive contamination at the surface.
The inventors have demonstrated that the aspirable gels described in documents [1] and [2], although they have been used for a few years in the field of nuclear surface decontamination, on surfaces made of materials such as steels, such as stainless steel, aluminum or lead, were not at all effective in removing contamination, for example radioactive contamination, contained in a layer of organic material, integrated into an organic matrix, in other words when it came to decontaminating organic matrices such as murals or bitumen stains.
Documents FR-A1-2962046 and WO-A1-2012 / 001046 [6] relate to a “aspirable” biological decontamination gel and a method for biological decontamination of surfaces using this gel.
This gel consists of a colloidal solution comprising at least one inorganic viscosity agent, at least one biological decontamination agent, at least one super-absorbent polymer, at least one surfactant, and the remainder of solvent.
The documents FR-A1-3003763 and WO-A1-2014 / 154818 [7] relate to an oxidizing alkaline gel of “aspirable” biological decontamination and a method of biological decontamination of surfaces using this gel.
This gel consists of a colloidal solution comprising at least one inorganic viscosity agent, an active biological decontamination agent consisting of the combination of a specific mineral base, such as sodium hydroxide, and an oxidizing agent stable in a specific basic medium, such as sodium hypochlorite, optionally a surfactant, and the rest of the solvent. In addition, this gel does not contain superabsorbent polymer.
The gels of documents [6] and [7] are however specifically intended for the biological decontamination of surfaces, in particular the so-called post-event decontamination of surfaces. This biological contamination is found on the surface of a substrate, whether it is an organic substrate or other. This biological contamination is not contained in a layer of organic material.
The gels in these documents are in no way specifically adapted to the elimination of contamination, such as radioactive contamination, contained in a layer of organic material, or even capable of being adapted to it. removal of contamination, such as radioactive contamination, contained in a layer of organic material.
There is no mention or suggestion in the documents [6] and [7] that the gels in these documents can solve the extremely specific problem of removing contamination, such as radioactive contamination, contained in a layer of organic material, integrated in an organic matrix, which is a problem completely different from the problem of eliminating biological contamination, on the surface.
Document FR-A1-3 027 310 [4] relates to a suction gel for removing graffiti and a method for removing graffiti.
This gel consists of a colloidal solution comprising an organic viscosifying agent, one or more organic solvents chosen in particular from alkyl acetates, optionally a surfactant, and optionally at least one dye and / or pigment.
The gel described in document [4] is however specifically intended for the removal of graffiti containing no contamination, for example no radioactive contamination.
The gel in this document is in no way suitable for eliminating contamination, for example radioactive contamination, contained in a layer of organic material, or even capable of being adapted to the elimination of contamination, such as radioactive contamination, contained in a layer of organic material.
There is no mention or suggestion in the document [4], that freezing this document could solve the extremely specific problem of removing contamination, such as radioactive contamination, contained in a layer of organic material, integrated into an organic matrix, which is a problem completely different from the problem of removing graffiti.
In view of the above, there is therefore a need for a suction gel and a method for eliminating contamination, for example radioactive contamination, contained in a surface layer of an organic material, integrated in an organic matrix.
In other words, there is a need for aspirable gel formulations which can decontaminate surfaces composed of organic materials, for example surfaces composed of paint or epoxy resin, or surfaces contaminated with contaminated organic materials, such as bitumen stains or oil that can be encountered in particular, but not only, in nuclear installations.
The object of the present invention is to provide a suction gel which meets, among other things, these needs.
The object of the present invention is also to provide a suction gel which does not have the drawbacks, defects and disadvantages of gels of the prior art and which solves the problems of gels of the prior art, such as document gels [ 1 and 2],
STATEMENT OF THE INVENTION
This object, and others still are achieved, in accordance with the invention, by a suction gel to eliminate a contaminating species, for example a radioactive contaminating species, contained in a layer constituted by an organic material, on the surface of a substrate. solid, consisting of a colloidal solution comprising, preferably consisting of:
1% to 25% by mass, preferably 5% to 20% by mass, for example 10% by mass, relative to the total mass of the gel, of at least one inorganic viscosifying agent;
13% to 99% by mass, preferably 80% to 95% by mass, for example 90% by mass, relative to the total mass of the gel, of one or more organic solvent (s) chosen (s) ) among terpenes;
optionally, from 1% to 40% by mass, preferably from 10 to 20% by mass relative to the total mass of the gel, of ethanol;
optionally, from 0.01% to 10% by mass, relative to the total mass of the gel, of at least one dye and / or pigment;
optionally, from 0.1% to 2% by mass, relative to the total mass of the gel, of at least one surfactant;
optionally, from 0.1% to 10% by mass, preferably 1% to 5% by mass, relative to the total mass of the gel, of at least one agent extracting from the contaminating species, for example from at least one agent extracting radionuclides, preferably chosen from zeolites and clays.
The sum of the percentages by mass of all the components, constituents of the gel is obviously 100% by mass.
The gel according to the invention has never been described in the prior art.
The gel according to the invention is first of all fundamentally defined in that it is a gel called "aspirable gel".
The term "aspirable gel", as already mentioned above is a term commonly used in this field of technology, it has a widely accepted meaning.
A suction gel is inherently different from a gel that is not suction.
The gel according to the invention is then characterized by the fact that it contains one or more specific organic solvent (s) chosen from terpenes and their mixtures.
These solvent (s), chosen from terpenes, constitute the active principle of the gel according to the invention. They allow the organic materials of the contaminated surface layer to dissolve.
Thanks to the intrinsic properties of the specific solvent (s) of the gel according to the invention, which are terpenes, the gel according to the invention makes it possible to:
completely dissolve a contaminated organic matrix, for example in the form of stains, which is then incorporated, in the same way as the contamination, in the final solid waste, namely the gel after drying which is in the form of aspirable flakes.
by attacking an organic layer of contaminated surface, for example over a few microns, and allowing the incorporation of the dissolved layer and of the contaminants present in the gel and therefore in the final solid waste, namely the gel after drying.
This (s) solvent (s) of the gel according to the invention, chosen (s) from terpenes is (are) little (even non) toxic (s), harmful (s).
In other words, according to the invention, care has been taken that the solvent (s) of the gel is (are) specifically chosen (s) from the least toxic solvents, and the least harmful, or even not toxic, and not harmful, in order to protect the operators who use the gel according to the invention.
This is another characteristic which fundamentally differentiates the gel according to the invention from a number of gels of the prior art in which solvents, for example essences, toxic or harmful, are used.
This terpene solvent (s) of the gel according to the invention is (are) in addition solvents which give off an odor which is not or not very foul, or unpleasant.
In other words, great care has been taken that the solvents of the gel according to the invention are chosen from the solvents whose odor is the least foul, the least unpleasant, or even not at all foul or unpleasant.
In other words, the solvents of the gel according to the invention are chosen from solvents which have a limited or even zero “stench”.
The solvent or the mixture of terpene solvent (s) of the gel according to the invention also generally has a volatility compatible with a good drying time of the gel, that is to say a volatility which guarantees a drying speed not too high, and therefore a sufficient drying time to ensure at least partial dissolution of the organic material of the layer, absorption of contamination, for example a drying time of about 20 hours.
The presence of ethanol in the gel makes it possible, if desired, to reduce the drying time, for example up to approximately 5 hours.
Most of the terpenes mentioned above have low volatility, are not very volatile and therefore make it possible, when used alone in the gel according to the invention, to obtain a sufficient drying time, for example a drying time of approximately 20 hours.
Again, the presence of ethanol in the gel, in combination with one or more low volatility terpenes, allows, if desired, to reduce the drying time up to about 5 hours.
However, some of the terpenes mentioned above have a high volatility, give gels which dry too quickly, and do not allow, when used alone in the gel according to the invention, to obtain a sufficient drying time. is for example the case of ocimene.
These terpene solvents which have high volatility such as ocimene are therefore generally used in combination, in admixture with another terpene solvent (such as limonene) which has low volatility in order to obtain a sufficient drying time.
It is precisely the combination of such a terpene solvent with high volatility with another terpene solvent with lower volatility which makes it possible to "slow down" the drying of the gel and to achieve a good drying time, a sufficient drying time.
In the same way, it is generally made so that the volatility of the solvent or of the mixture of terpene solvents possibly in combination with ethanol, is such that the gel does not dry too slowly and that its drying time is not too long and does not exceed, for example, 8 hours.
Those skilled in the art can easily identify, from the solvents of the gel according to the invention, chosen from the terpenes mentioned above, the solvents having low volatility, and the solvents having high volatility in order to define a formulation having a duration drying time that is not too long, and does not exceed, for example, 8.
Those skilled in the art also know that ethanol is a solvent which has high volatility.
A preferred gel according to the invention comprises from 35% to 98% by mass, preferably 60 to 85% by mass, for example 70% by mass, relative to the total mass of the gel, of one or more terpene (s ) chosen from, for example, d-limonene, l-limonene, alphapinene or beta-pinene, from 1% to 25% by mass, preferably 5% to 20% by mass, for example 10% by mass, relative to the total mass of the gel, of an inorganic viscosifier, preferably alumina, and from 1% to 40% by mass, preferably 10% to 20% by mass, for example 20% by mass , based on the total mass of the gel, of ethanol.
Surprisingly, and although the organic solvents of the gel according to the invention, which are terpenes, are chosen from solvents that are not very toxic (or even non-toxic), these solvents alone or as a mixture nevertheless exhibit high efficiency for dissolving the material of the organic layer containing the contamination, for example radioactive contamination, whatever this material, for example resin paint or the like.
In other words, the solvent for the gel according to the invention, which is chosen from terpenes, is relatively non-toxic and has strong dissolving properties vis-à-vis organic materials but also degreasing properties.
The terpenes can in particular be terpene hydrocarbons, and oxygenated terpene compounds.
The terpene (s) of the gel is (are) also chosen (s) according to the nature of the organic material which constitutes the contaminated layer so as to allow the most effective dissolution of this material.
By terpenes is also meant the isomers, in particular the optical isomers thereof.
Among the terpenes, mention may in particular be made of ocimene, α-pinene, β-pinene, limonene, menthol, menthone, terpineol, isoborneol, camphor, nerol, citronellal, citronellol, myrcene, myrcenol, linalol, geraniol, and isomers including the optical isomers thereof.
The gel according to the invention comprises, as organic solvent chosen from terpenes, preferably as the only organic solvent chosen from terpenes, d-limonene.
Indeed, d-limonene has, among all terpenes, the best power of solubilization with respect to organic materials, in particular with respect to bitumens.
A particularly preferred gel according to the invention comprises from 35% to 94% by mass, preferably from 70% to 80% by mass, relative to the total mass of the gel, of d-limonene, and from 1% to 40% by mass, preferably from 10% to 20% by mass, relative to the total mass of the gel, of ethanol which makes it possible to adjust the drying time.
The gel according to the invention meets the needs listed above, it allows in particular, while being aspirable, to eliminate contamination, for example radioactive contamination, contained in a layer of organic material.
In particular, the gel according to the invention allows effective decontamination of surfaces composed of organic materials, of the paint or epoxy resin type or else of surfaces contaminated with contaminated organic materials such as bitumen or oil stains.
Unlike the gels of the prior art, the gel according to the invention thanks to the specific solvents it contains, ensures decontamination, for example radiological decontamination, by complete or partial dissolution of the organic material containing the contaminants, for example the radioactive contaminants, and incorporating the dissolved organic material containing the contaminants, for example radioactive contaminants, into the gel.
The gel according to the invention has the same effectiveness, whether the treated layer is a contaminated surface layer of a solid substrate constituted by a contaminated organic material, or else that the treated layer is a layer constituted by a contaminated organic material such that '' a layer forming a coating on a surface of a substrate, or alternatively that the treated layer is a layer constituted by an contaminated organic material, being on a surface of a substrate, this layer being in particular in the form of a stain of contaminated organic material staining said surface, for example a stain of oil or bitumen or contaminated fat which stains said surface.
In the latter case where the treated layer is in particular in the form of a stain of contaminated organic material contaminating a surface, the gel according to the invention has an excellent effectiveness whatever the material of this surface and whatever the surface condition of said surface, whether this surface is smooth, rough, dense or porous. The examples given below show that the gel according to the invention is just as effective in decontaminating a dense surface of epoxy resin as a porous concrete surface, by removing from this surface a stain of contaminated bitumen.
The gel according to the invention allows a migration of the contaminants, of the contamination, for example of the radioactive contamination, present in the contaminated organic layer up to the gel and, consequently, up to the final solid waste constituted by the dry gel. , in order to decontaminate said organic layer.
The gel according to the invention, as already indicated above, is a suction gel which has all the advantageous properties - mentioned above - inherent in gels called so-called suction gels such as document gels [1], [2 ], [6], [7] and [4] with the fundamental difference, however, that with the gel according to the invention, a contamination, such as radioactive contamination, contained in a surface layer made of an organic material is eliminated. and that the composition of the gel is therefore adapted accordingly.
As indicated above, the gels of these documents [1], [2], [6], [7], are aqueous gels specifically designed for the elimination of radioactive or biological contamination found in the surface of a substrate, and in which the solvents and the active decontamination agent are completely different from those of the gel according to the invention.
There is no indication in documents [1], [2], [6], and [7], which could lead a person skilled in the art to modify the gels of these documents in such a substantial manner in order to use them to remove contamination, for example radioactive contamination, contained in a surface layer of organic material.
Similarly, the gel of document [4] is a gel specifically designed for the removal of graffiti containing no contamination, in particular no radioactive contamination, on the surface of a substrate.
The freezing of the document [4] simply has an action of dissolving the graffiti and not an action of transfer, migration in the gel, of a contamination, for example of a radioactive contamination, contained in the gel.
There is no indication in document [4] which could lead a person skilled in the art to modify the gel of this document in order to use it for contamination, for example radioactive contamination, contained in a surface layer in an organic material.
The gel according to the invention is a colloidal gel, the active principle of which allows the total or partial dissolution of the organic material, and the rheology of which is adapted to the application, preferably by spraying onto the surfaces to be treated.
This is one of the advantages of the gel according to the invention that it can be applied very easily, by spraying.
The gel according to the invention gradually dries, extending the contact time between the pickling and dissolving active agent, namely the solvent and the organic material, for example paint, and forms flakes which are easily detached from the surface by brushing / aspiration - hence the name aspirable gel - thus removing contamination, for example radioactive contamination, and dissolved organic material. In the case where the layer of organic material is in the form of a stain or discrete stains of contaminated organic material staining the surface of a solid substrate, for example in the form of stains of contaminated oil or bitumen which stains the surface of the solid substrate, this is done without the material of the solid substrate being altered.
The cleaning operator can thus allow the gel to act on the surfaces to be treated while going to treat other surfaces, without having to be physically present during drying, or to scrub laboriously the surface using a solvent.
In summary, the gels according to the invention therefore meet all of the needs mentioned above, and they have all the advantageous properties known of gels called "aspirable" gels.
In other words, the combination - which can be described as synergistic - of one or more inorganic viscosifying agent (s) with the specific solvent for the gel according to the invention chosen from terpenes and their mixtures, provides a gel with rheological properties, as well as properties of dissolution of organic material, absorption, migration of contamination, for example radioactive contamination, in the gel, and excellent drying, dry gel being furthermore easily vacuumable.
The gel according to the invention, although it contains a viscosity agent generally exclusively inorganic, mineral, without viscosity agent, organic, can be qualified as organic gel.
Indeed, the organic matter content of the gel according to the invention is high, at least equal to 70% by mass, for example equal to 90% by mass, since it contains at least 70% by mass, for example 90% by mass of organic solvents.
The gel according to the invention is a colloidal solution, which means that the gel according to the invention contains inorganic, inorganic solid particles of viscosifying agent, the elementary primary particles of which have a size generally of 2 to 200 nm. These solid, mineral, inorganic particles act as viscosants to allow the solution to gel and thus adhere to the surface to be treated, whatever its geometry, shape, size, and wherever the layers are. treat.
Advantageously, the inorganic viscosity agent can be chosen from metal oxides such as aluminas, metalloid oxides such as silicas, metal hydroxides, metalloid hydroxides, metal oxyhydroxides, metalloid oxyhydroxides, aluminosilicates, clays such as smectite, and mixtures thereof.
In particular, the inorganic viscosity agent can be chosen from aluminas (AI2O3) and silicas (SiO ₂ ).
The inorganic viscosifier may comprise only a single silica or alumina or a mixture of these, namely a mixture of two or more different silicas (mixture SiO ₂ / SiO ₂ ), a mixture of two or more different aluminas (AI ₂ O3 / AI ₂ C> 3 mixture), or a mixture of one or more silica (s) with one or more alumina (SiOz / AbCh mixture).
Advantageously, the inorganic viscosifying agent can be chosen from fumed silicas, precipitated silicas, hydrophilic silicas, hydrophobic silicas, acid silicas, basic silicas such as silica TixosiT 73, sold by the company Rhodia, and their mixtures.
Among the acidic silicas, mention may especially be made of fumed or fumed silica silica Cab-O-Sil ¹ 'M5, H5 or EH5, sold by the company CABOT, and fumed silicas sold by the company EVONIK INDUSTRIES under the name AEROSIL '.
Among these fumed silicas, preference will also be given to AEROSIL 380 silica with a specific surface of 380 m ² / g which offers the maximum viscosity properties for a minimum mineral load.
The silica used can also be a so-called precipitated silica obtained for example by the wet method by mixing a solution of sodium silicate and an acid. The preferred precipitated silicas are marketed by the company EVONIK INDUSTRIES under the name of SIPERNAT 22 LS and FK 310 or also by the company RHODIA under the name of TIXOSIL 331, the latter is a precipitated silica whose average specific surface is between 170 and 200 m ² / g.
Advantageously, the inorganic viscous agent consists of a mixture of a precipitated silica and a fumed silica.
A particularly preferred viscosifier is chosen from aluminas. Indeed, it has been found that the combination of one or more aluminas with the specific solvent for the gel according to the invention chosen from terpenes and their mixtures makes it possible to obtain a gel having rheological properties, as well as properties of dissolution of the organic material, absorption, migration of contamination, for example radioactive contamination, into the gel, and even better drying, the dry gel also being easily aspirated.
In particular, the rheological properties of the gel are better when the gel comprises one or more aluminas as an inorganic viscous agent, rather than a silica or a clay, as in the gel of document [3],
The aluminas can be chosen from calcined aluminas, ground calcined aluminas, pyrogenated aluminas, and their mixtures.
The fumed aluminas are particularly preferred because the properties of the gel mentioned above, and in particular the rheological properties, are even better with these fumed aluminas, in particular when these fumed aluminas have a fine particle size, namely generally from 10 nm to 100 nm.
By way of example, mention may be made of the product sold by the company EVONIK INDUSTRIES under the trade name "Aeroxide® Alu C" which is pyrogenated fine alumina.
Advantageously, according to the invention, the inorganic viscous agent consists of one or more alumina (s), preferably representing from 5% to 25% by mass relative to the mass of the gel.
In this case, the alumina (s) is (are) preferably at a concentration of 7% to 15% by mass relative to the total mass of the gel to ensure drying of the gel at a temperature between 20 ° C. and 50 ° C and a relative humidity between 20% and 60% on average in 30 minutes to 24 hours.
The nature of the mineral viscous agent, in particular when it consists of one or more alumina (s), unexpectedly influences the drying of the gel according to the invention and the particle size of the residue obtained.
Indeed, the dry gel is in the form of particles of controlled size, more precisely of millimeter solid flakes, the size of which generally ranges from 1 to 10 mm, preferably from 2 to 5 mm, in particular thanks to the aforementioned compositions of the present invention, in particular when the viscosity agent consists of one or more alumina (s).
Note that the size of the particles generally corresponds to their largest dimension.
In other words, the solid mineral particles of the gel according to the invention, for example of the silica or alumina type, in addition to their role as viscosants, also play a fundamental role during the drying of the gel because they ensure the fracturing of the gel to achieve to dry waste in the form of flakes.
A particularly preferred gel according to the invention consists of a colloidal solution comprising, preferably consisting of:
5% to 25% by mass, preferably 7% to 15% by mass, relative to the total mass of the gel, of at least one alumina, preferably of at least one fumed alumina, more preferably of at least minus a pyrogenic alumina having a fine particle size;
35% to 94% by mass, preferably from 65% to 83% by mass, relative to the total mass of the gel, of d-limonene;
from 1% to 40% by mass, preferably from 10 to 20% by mass, relative to the total mass of the gel, of ethanol.
Such a gel unexpectedly has a particularly advantageous combination of properties, namely excellent efficiency, in particular excellent power of solubilization of organic materials, mainly due to d-limonene, and excellent rheological, drying, and shape properties. dry residue due to alumina, in particular pyrogenic.
The addition of ethanol also makes it possible to adjust the drying time as desired.
The gel according to the invention can also optionally contain at least one dye and / or at least one pigment.
Advantageously, the pigment is a mineral pigment. In this regard, reference may be made to document WO-A1-2014 / 154817.
There is no limitation as to the mineral pigment which is incorporated in the decontamination gel according to the invention.
Generally, the mineral pigment is chosen from mineral pigments which are stable in the gel.
The term “stable pigment” is generally understood to mean that the pigment does not exhibit a stable change in its color over time, when the gel is stored for a minimum of 6 months.
There is no limitation as to the color of this pigment, which is usually the color it will impart to the gel. This pigment can be black, red, blue, green, yellow, orange, purple, brown, etc., and even white.
Generally, the gel therefore has a color identical to the color of the pigment it contains. It is however possible that the gel has a color which differs from the color of the pigment it contains, but this is not sought.
The pigment, especially when it is white, is generally different from the inorganic viscosity agent.
Advantageously, the mineral pigment is chosen so that it gives the gel (that is to say the gel in the wet state, before drying) a color different from the color of a surface to be decontaminated on which the gel is applied.
Advantageously, the mineral pigment is a micronized pigment, and the average particle size of the mineral pigment can be from 0.05 to 5 μm, preferably from 0.1 to 1 μm.
The fact that the pigment is micronized makes it possible to prevent it from modifying the rheology and the ability to spray the gel (“sprayability”) because the pigment then has the same micrometric size which is generally that of the viscosifying agent. inorganic, such as alumina aggregates.
Advantageously, the mineral pigment is chosen from oxides of metal (metals) and / or metalloid (s), hydroxides of metal (metals) and / or metalloid (s), oxyhydroxides of metal (metals) and / or of metalloid (s), ferrocyanides and ferricyanides of metal (metals), metal aluminates (metals), and mixtures thereof.
Preferably, the mineral pigment is chosen from iron oxides, preferably micronized, and their mixtures.
The iron oxides can have different colors, they can be for example yellow, red, purple, orange, brown, or black.
In fact, iron oxide pigments are known to have good covering power and great resistance to acids and bases.
For incorporation into a decontamination gel, iron oxides have the best performance in terms of stability and coloring power. Thus, an iron oxide content of 0.1%, even 0.01% by mass is sufficient to strongly color the gel without modifying the properties.
As already indicated above, the fact that the iron oxide pigment is preferably micronized makes it possible to prevent it from modifying the rheology and the sprayability of the gel (“sprayability”) because the pigment then has a micrometric size, namely a size which is generally that of the inorganic viscous agent, such as alumina aggregates.
Micronized iron oxides are available from Rockwood® under the trade name Ferroxide®.
Mention may be made inter alia of Ferroxide® 212 M which is a micronized red iron oxide with an average particle size of 0.1 μm and Ferroxide® 228 M which is a micronized red iron oxide with an average particle size of 0.5 pm.
In addition and / or instead of iron oxides, other oxides or hydroxides of colored metals or metalloids can be incorporated into the gel according to the invention, depending on the pH of the gel, mention may in particular be made of the oxide vanadium (V2O5) which is orange, manganese oxide (MnCE) which is black, cobalt oxide which is blue or green, and rare earth oxides. However, iron oxides are preferred for the reasons specified above.
Among the oxyhydroxides, there may be mentioned goethite, that is to say iron oxyhydroxide FeOOH, which is very colored.
By way of example of metal ferrocyanide, mention may be made of Prussian blue, that is to say ferric ferrocyanide, and by way of example of aluminate, mention may be made of cobalt blue, that is i.e. cobalt aluminate.
The incorporation in the gel according to the invention of a mineral pigment makes it possible to better visualize the wet gel then the dry residues whatever the substrate on which the gel is applied.
The gel may optionally additionally contain at least one surfactant (i.e. a single surfactant or a mixture of surfactants), preferably this or these surfactant (s) ) is (are) chosen from the family of nonionic surfactants such as block copolymers, block like ethylene oxide and propylene oxide block copolymers, and ethoxylated fatty acids; and their mixtures.
For this type of gel, the surface-active agents are preferably block copolymers sold by the company BASF under the name PLURONIC ¹ '.
Pluronics ¹ 'are block copolymers of ethylene oxide and propylene oxide.
These surfactants influence the rheological properties of the gel, in particular the thixotropic nature of the product and its recovery time and avoid the appearance of sagging.
The surfactants also make it possible to control the adhesion of the dry waste, and to control the size of the flakes of dry residue to guarantee the non-pulverulent nature of the waste.
The gel can optionally contain, in addition, from 0.1% to 10% by mass, preferably 1% to 5% by mass, relative to the total mass of the gel, of at least one extractant of the species. contaminant, for example of at least one agent extracting radionuclides, preferably chosen from zeolites and clays.
This optional extracting agent such as a zeolite or a clay can be used in the case where the contaminating species is a radionuclide, but this optional extracting agent can also be used in the case of contaminating species other than the radionuclides, such as example of metals, such as toxic metals or heavy metals.
The invention further relates to a method for eliminating a contaminating species, for example a radioactive contaminating species, contained in a layer constituted by an organic material on the surface of a solid substrate, in which at least one cycle is carried out comprising following successive steps:
a) applying the gel according to the invention, as described above, on said layer consisting of an organic material;
b) the gel is maintained on the layer consisting of an organic material at least for a sufficient time so that the gel dissolves part or all of the organic material of the layer consisting of an organic material, absorbs the contaminating species, for example the radioactive contaminating species (so that the contaminating species migrates into the gel), and so that the gel dries and forms a dry and solid non-pulverulent residue containing the organic material of the layer constituted by an organic material which has been dissolved, and the contaminating species, for example the radioactive contaminating species;
c) removing the dry and solid residue containing the organic material from the organic layer which has been dissolved, and the contaminating species, for example the radioactive contaminating species.
There is no limitation as to the contaminating species which can be eliminated by the process according to the invention, in particular as regards its form and its chemical composition. Thus, the contaminating species which can be eliminated by the process according to the invention can be an organic or inorganic (mineral) species.
The contaminating species which can be removed by the process according to the invention can be a solid or liquid contaminating species.
The contaminating species which can be eliminated by the process according to the invention, can in particular be a radioactive contaminating species, and / or chemically toxic, and / or toxic due to its shape and / or its size.
The toxic contaminating species due to its shape and / or its size, can be a contaminating species which is in the form of solid particles such as microparticles, or nanoparticles, for example in the form of fibers such as microfibers or nanofibers, in the form of nanotubes, or in the form of crystals such as nanocrystals.
These fibers can form a wool, such as glass wool or a wool known as rock wool.
The toxic contaminating species can in particular be in the form of a dust.
It should be noted that certain dusts of chemically non-toxic compounds, such as, for example, cereal or wood dust are toxic simply because they occur precisely in this form of dust.
The contaminating species can be chosen from metals and metalloids in the form of metal, metalloid, or ionic, preferably from so-called “heavy metal” metals, and toxic metals and metalloids in the form of metal, metalloid, or ionic ; compounds of these metals and metalloids such as organometallic compounds, metal salts, metal oxides, metal carbides, etc. ; ceramics; and glasses for example in the form of glass wool.
Within the meaning of the invention, the term “heavy metals” is understood to mean all the elements traditionally designated by this denomination as well as the elements designated by the denomination of metallic trace elements, or ETMs.
The so-called "heavy metals", and the toxic metals and metalloids are in particular antimony, arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, tellurium, thallium and tin.
The contaminating species can in particular be asbestos.
The radioactive contaminant species can be any chemical compound containing a radionuclide, whether in ionic, molecular or particulate form.
According to a first variant, the layer constituted by an organic material containing a contaminating species, for example a radioactive contaminating species, can be a surface layer, of a solid substrate constituted by said (the same) organic material.
In other words, according to this first variant, the surface layer forms an integral part of the substrate.
This surface layer generally has a thickness of 1 to 10 µm.
This organic material can be chosen from paints, lacquers, organic polymers, organic resins such as epoxy resins.
This solid substrate constituted by an organic material can be a solid solid substrate or a layer, such as a layer of paint or epoxy resin, for example a layer of paint or epoxy resin forming a coating on a surface of a substrate. .
Or, according to a second variant, this layer constituted by an organic material containing a contaminating species, for example a radioactive contaminating species can be a layer constituted by an organic material containing a contaminating species, for example a contaminating radioactive species, being on a surface of a solid substrate, this layer being in the form of a stain or discrete stains of the organic material containing a contaminating species, for example a radioactive contaminating species.
In this second variant, the discrete task or tasks of the organic material containing a contaminating species, for example a radioactive contaminating species is (are) completely dissolved (s) by the gel.
In this second variant, the organic material can be chosen from sticky organic materials.
Sticky organic materials are well known to those skilled in the art, who has no trouble determining which of the organic materials are sticky, which adhere to a surface on which they are found.
In the present, sticky organic materials are generally defined as materials which cannot be removed from a surface on which they are located by a simple suction.
The organic material can in particular be chosen from oils such as hydrocarbon oils, bitumens, tars and greases.
In this second variant, the solid substrate can be a porous substrate, preferably a porous mineral substrate, or a non-porous substrate.
The effectiveness of the gel and of the process according to the invention is just as good in the presence of a non-porous and / or non-mineral surface as in the presence of a porous and / or mineral surface. Whatever the solid substrate (porous, mineral or not), the discrete task or tasks of the organic material containing a contaminating species, for example a radioactive contaminating species is (are) completely dissolved (s) by the gel (see examples) .
Advantageously, in this second variant, the substrate is made of at least one material chosen from metals and alloys such as stainless steel, galvanized steel, or zinc; painted steels; organic polymers such as plastics or rubbers such as poly (vinyl chloride) or PVC, polypropylenes or PP, polyethylenes or PE, in particular high density polyethylenes or HDPE, poly (methyl methacrylate) s or PMMA, poly (vinylidene fluoride) s or PVDF, polycarbonates or PC; the glasses ; cementitious materials such as pastes, cements, mortars and concretes; plasters; the bricks ; tiles ; raw or cooked earth; natural or artificial stones; coatings; fiberglass, fiber cement; asphalt; tar ; slate; cellulose-based materials such as wood; and ceramics.
The substrate can be painted or not.
Advantageously, the gel is applied to the surface layer at the rate of 100 g to 10000 g, preferably from 500 g to 5000 g of gel per m ² of surface, which generally corresponds to a thickness of gel deposited on the surface included. between 0.1 mm and 1 cm preferably between 0.5 mm and 5 mm.
Advantageously, the gel is applied to the surface layer by spraying, with a brush or with a trowel.
Advantageously (during step b)), the drying is carried out at a temperature of 1 ° C to 50 ° C, preferably from 1 ° C to 40 ° C, more preferably from 15 ° C to 25 ° C, and in relative humidity from 20% to 80%, preferably from 20% to 70%.
Advantageously, the gel is maintained on the surface layer for a period of 2 hours to 72 hours, preferably 4 to 48 hours, more preferably 6 to 24 hours.
Advantageously, the dry and solid residue is in the form of particles, for example flakes, of a size from 1 to 10 mm, preferably from 2 to 5 mm.
Advantageously, the dry and solid residue is removed from the surface of the solid substrate by brushing and / or suction.
Advantageously, the cycle described above can be repeated for example from 1 to 10 times by using the same gel during all the cycles or by using different gels during one or more cycle (s).
Advantageously, during step b), the gel, before total drying, is rewetted with a solvent, preferably with the solvent for the gel applied during step a), which then generally avoids repeating the application of the gel. on the surface and results in a saving of reagent and a limited amount of waste. This rewetting operation can be repeated for example from 1 to 10 times.
The method according to the invention has all the advantageous properties inherent in the decontamination gel which it implements and which have already been widely explained above.
The method according to the invention makes it possible to eliminate the contaminating species, for example the radioactive contaminating species, contained in a surface layer of an organic material while being much less painful and much less expensive than the conventional methods used previously for this purpose. , namely in particular:
processes using high pressure means, which are expensive and “technical” (complex), processes using wipes soaked in harmful solvents, the use of which is long and laborious.
Thus, the gel according to the invention can be sprayed using a simple paint spray gun found on the market while sandblasting devices, for example, require adjustments and special training. These sandblasting devices are complex and costly to maintain.
In addition, the method according to the invention is a dry method which avoids the spillage of solvent or stripper while optimizing the working time of the cleaning operator. Indeed, it is able to treat several areas at once quickly, due to the gel drying time and its implementation advantageously by spraying.
In summary, the method and the gel according to the invention exhibit inter alia, in addition to the advantageous properties specifically due to the specific solvent contained in the gel, the following other advantageous properties:
applying the gel preferably by spraying. Spraying makes it possible to treat large areas quickly and easily and requires fewer operators, adhesion to the walls, obtaining the maximum effectiveness in removing the contamination at the end of the gel drying phase, including in the case of contaminated stains entering the substrate, especially in the case of porous surfaces.
In general, we make sure that the drying time is greater than or equal to the time necessary to remove the surface layer or stains. In the case of deep contamination, rewetting is sometimes used.
the treatment of a very wide range of materials (see examples), the absence of mechanical or physical alteration of the materials of the solid substrate at the end of the treatment, the implementation of the process under variable climatic conditions (see examples ), reduction in the volume of waste, ease of recovery of dry waste.
The examples given below show in particular that the gel according to the invention because of its specific formulation and its simple, reliable and easy implementation, is effective in particular for the elimination of a large variety of contaminated stains over a large variety of materials.
Other characteristics and advantages of the invention will appear better on reading the detailed description which follows, this description being given by way of nonlimiting illustration, in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 (A, B, C, D, E) presents photographs which show the elimination of a bitumen stain on a smooth surface, as it was carried out in Example 2, using the gel according to the invention, said “Limo-1” gel prepared in Example 1.
Figure 2 (A, B, C, D, E, F, G) presents photographs which show the elimination of a bitumen stain on a porous surface, as it was carried out in example 2, using the gel according to the invention, called “Limo-1” gel, prepared in Example 1.
Figure 3 (A, B, C) presents photographs which show the elimination of a stain of bitumen contaminated with ¹³⁷ Cs bonded to a smooth surface, as it was carried out in Example 4, using the gel according to the invention, called “Limo-1” gel prepared in Example 1.
FIG. 4A, illustrates Example 6, and presents a photograph of the surface of an epoxy resin before the deposition of a layer of gel according to the invention, known as “Limo-1” gel prepared in Example 1, on the surface of an epoxy resin (on the left) and after the deposition of a layer of gel, the drying of this layer and the elimination of the glitter of dry gel (on the right).
FIG. 4B, illustrates Example 6, and shows the surface profiles corresponding to the surfaces photographed in FIG. 4A, before the deposition of a layer on the surface of the epoxy resin (on the left) and after the deposition of a layer of gel, drying this layer and removing the glitter of dry gel (right).
FIG. 5 is a graph which shows the change in viscosity (in Pa.s) as a function of the shear rate (1 / s), for the gel according to the invention, known as “Limo-1” gel prepared in l 'example 1 (see example 6).
FIG. 6 is a graph which shows the evolution of the shear stress (in Pa) as a function of the deformation (in Pa) for the gel according to the invention, called “Limo-1” gel prepared in Example 1 (see example 6).
FIG. 7 is a graph which shows the evolution of the loss of mass (in%) as a function of time (in min.) Of the gel according to the invention, called “Limo-1” gel prepared in Example 1, deposited with a thickness of 2 mm (see example 7).
FIG. 8 is a photograph of the flakes obtained after drying of the gel according to the invention, known as “Limo-1” gel prepared in Example 1 (see Example 7).
DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
The gel according to the invention can be easily prepared at room temperature.
For example, the gel according to the invention can be prepared by preferably adding progressively, the inorganic viscous agent (s), for example alumina (s) and / or silica (s) (s), or to the terpene solvent (s) optionally mixed (s), with ethanol, or to the mixture of the organic solvent (s) (with optionally ethanol) and of the any adjuvant (s).
The possible adjuvants are generally the surfactant (s), the dye (s) and / or pigment (s), and the extractant agent (s) from the contaminating species, for example the radionuclide extracting agent.
This mixture of the solvent (s) and the optional adjuvant (s) can be produced by mechanical stirring, for example by means of a mechanical stirrer equipped with a three-blade propeller. The rotation speed is for example 200 revolutions / minute, and the duration of the stirring is for example from 3 to 5 minutes.
The addition of the inorganic viscous agent (s) to the solvent or solvents, or to the mixture of the solvent (s) and the optional adjuvant (s) can be carried out by simply pouring the viscosifying agent (s) into said solvent (s) or said mixture.
When adding the inorganic viscosity agent (s), to the solvent (s), or to the mixture of the solvent (s) and the optional adjuvant (s) ), this or these solvent (s) or this mixture are generally maintained with mechanical stirring.
This agitation can, for example, be carried out by means of a mechanical agitator equipped with a three-blade propeller.
The stirring speed is generally gradually increased as the viscosity of the solution increases, finally reaching a stirring speed of, for example, between 400 and 600 revolutions / minute, without there having been projections.
After the end of the addition of the mineral viscosant (s), the stirring is further continued, for example for 2 to 5 minutes, so as to obtain a perfectly homogeneous gel.
It is quite obvious that other protocols for preparing the gels used according to the invention can be implemented with an addition of the components of the gel in a different order from that mentioned above.
Generally, the gel used according to the invention must have a viscosity of less than 200 mPa.s under a shear of 1000 s ¹ so as to allow spraying on the surface to be decontaminated, at a distance (for example at a distance of 1 to 5 m) or nearby (for example at a distance of less than 1 m, preferably from 50 to 80 cm). The viscosity recovery time must generally be less than one second and the viscosity under low shear greater than 10 Pa.s to avoid sinking on a wall.
It should be noted that the optional surfactant of the gel according to the invention positively and notably influences the rheological properties of the gel used according to the invention. This surfactant allows in particular that the gel used according to the invention can be applied by spraying and avoids the risks of spreading or sagging during the treatment of vertical surfaces and ceilings. This surfactant also makes it possible to limit the phenomenon of bleeding observed during the conservation of the gel.
The gel thus prepared is then applied to the surface layer containing a contaminating species, for example a radioactive contaminating species, to be treated.
According to the second variant of the method according to the invention, this surface layer containing a contaminating species, for example a radioactive contaminating species is a layer lying on a surface of a solid substrate, this layer being in the form of a stain or discrete stains of organic material containing a contaminating species, for example a radioactive contaminating species.
In this second variant, there is almost no limitation as to the material which constitutes the substrate, in fact the gel according to the invention makes it possible to treat without any damage, all kinds of materials, even fragile.
The gel according to the invention does not generate any alteration, erosion, attack, chemical, mechanical or physical of the material of the treated substrate. The gel according to the invention is therefore in no way detrimental to the integrity of the treated materials and even allows their reuse. This substrate material can therefore be chosen from the materials already listed above, for example from metals or alloys such as stainless steel, polymers such as plastics or rubbers among which mention may be made of PVC, PP, PE in particular. HDPE, PMMA, PVDF, PC, glasses, cements, mortars and concretes, plasters, bricks, natural or artificial stone, coatings, ceramics.
In all cases, whatever the material which constitutes the substrate, for example stainless steel, painted, lacquered steel, glass, ceramic, concrete, PVC, in this second variant, the task or discrete tasks of the organic material containing a species contaminant, for example a radioactive contaminant species is (are) completely dissolved by the gel.
There is also no limitation as to the shape, the geometry and the size of the layer to be treated and of the solid substrates of the first and of the second variants, the gel according to the invention indeed allows the treatment of large surfaces size, of complex geometries, presenting for example hollows, angles, corners.
The gel according to the invention ensures the effective treatment not only of horizontal surfaces, but also of vertical surfaces such as walls, facades, piers of bridges, doors, or inclined or overhanging surfaces such as ceilings.
The gel according to the invention also guarantees complete and effective removal of the contamination whatever the organic material of the contaminated layer and the nature of the contamination.
Compared to existing techniques which use liquids such as solutions, the invention implements a gel, which is particularly advantageous for the treatment of materials of large area, non transportable and implanted outside. Indeed, the method according to the invention due to the implementation of a gel, allows cleaning in situ avoiding the spreading of chemical solutions in the environment and the dispersion of contaminating species.
The gel according to the invention can be applied to the surface to be treated by all the application methods known to those skilled in the art.
Conventional methods are spraying, for example with a spray gun, or applying by means of a brush, or a trowel.
For the application by spraying of the gel on the surface to be treated, the colloidal solution can for example be conveyed by means of a low pressure pump, for example a pump which implements a pressure less than or equal to 7 bars, or approximately 7.10 ⁵ Pascals.
The bursting of the gel jet on the surface can be obtained for example by means of a flat jet or round jet nozzle.
The distance between the pump and the nozzle can be any, for example it can be from 1 to 50 m, in particular from 1 to 25 m.
The sufficiently short viscosity recovery time of the gels used according to the invention allows the sprayed gels to adhere to all surfaces, for example to walls.
The amount of gel deposited on the surface to be treated is as indicated above.
The amount of gel deposited per unit area and, consequently, the thickness of the gel deposited influences the drying rate.
Thus, when a film is sprayed, layer of gel with a thickness of 0.5 mm to 1 cm on the layer to be treated, the drying time, which is then generally the effective contact time, is sufficient to good treatment of the layer, leading to dissolution of the layer and absorption of contaminating species.
The effective contact time is the period during which the active principle contained in the gel which is none other than the solvent (s) will interact with the layer.
The drying time is not only related to the thickness of the gel layer applied, but also to the climatic conditions, namely the relative humidity and the temperature.
A person skilled in the art can easily determine, depending on the climatic conditions, and within the thickness range mentioned above, the thickness of the gel layer to be applied to the surface layer so that the gel is effective, that the layer is dissolved and the contaminating species are absorbed by the gel.
So if we are at 20% RH relative humidity, and at 40 ° C, it is possible that the drying of a gel layer with a thickness of 0.5 mm applied to a layer is too fast to allow the dissolution of this layer and the absorption of contaminating species in the gel. On the contrary, if one is at 15 ° C, and at 50% RH, the drying of a layer of the same thickness of the same gel allows a dissolution of this layer and the absorption of the contaminating species in the gel.
Furthermore, it has been surprisingly shown that the amount of gel deposited when it is within the ranges mentioned above and, in particular, when it is greater than 500 g / m ² and in particular within the range of 500 at 5000 g / m ² , which corresponds to a minimum thickness of gel deposited, for example greater than 500 μm for an amount of gel deposited greater than 500 g / m ² , after gel drying allowed the gel to be fractured in the form of millimeter flakes, for example of a size from 1 to 10 mm, preferably from 2 to 5 mm which can be aspirated.
The quantity of gel deposited and therefore the thickness of gel deposited, preferably greater than 500 g / m ^2, ie 500 μm, is the fundamental parameter which influences the size of the dry residues formed after drying of the gel and which thus ensures that residues Millimetric dry particles and not powdery residues are formed, such residues being easily removed by a mechanical process and preferably by suction.
However, it should also be noted that when the gel contains a surfactant at low concentration, the drying of the gel is improved and leads to a phenomenon of homogeneous fracturing with a size of the dry mono-dispersed residues and an increased aptitude of the residues dry to come off the support.
The gel is then maintained on the surface to be treated for the entire time necessary for its drying.
During this drying step which can be considered to constitute the active phase of the process according to the invention, the solvent (s) contained in the gel, evaporates (s) up to 1 '' obtaining a dry and solid residue.
The drying time depends on the composition of the gel in the concentration ranges of its constituents given above, but also, as has already been specified, on the amount of gel deposited per unit area, that is to say of the thickness of gel deposited.
The drying time also depends on the climatic conditions, namely the temperature, the ventilation and the relative humidity of the atmosphere in which the solid surface is found.
The method according to the invention can be implemented under extremely wide climatic conditions, namely at a temperature T of 1 ° C to 50 ° C and at a relative humidity RH of 20% to 80%.
The gel drying time according to the invention is therefore generally from 15 minutes to 24 hours, preferably from 1 hour to 24 hours at a temperature T of 1 ° C to 50 ° C and at a relative humidity RH of 20% to 80%.
It should be noted that the formulation of the gel used according to the invention in particular when it contains surfactants such as "Pluronics ¹ '" generally provides (that is to say in particular generally under reasonable climatic conditions, such as as indicated above) a drying time which is substantially equivalent to the contact time between the gel and the surface layer which is necessary, required to dissolve the organic material.
In other words, the formulation of the gel ensures a drying time which is none other than the time necessary to dissolve the organic material and absorb the contaminating species. At the end of the drying of the gel, the gel fractures in a homogeneous manner to give dry solid millimeter residues, for example of a size of 1 to 10 mm, preferably from 2 to 5 mm not powdery, generally in the form of solid glitter. The dry and solid residues contain the contaminating species, for example the radioactive contaminating species, and the organic material which has been dissolved from the surface layer.
Dry residues, such as flakes, obtained after drying have poor adhesion to the surface of the cleaned material. Therefore, the dry residues obtained after drying of the gel can be easily recovered by simple brushing and / or suction. However, dry residues can also be removed by gas jet, for example by compressed air jet.
No rinsing is generally necessary and the method according to the invention does not generate any secondary effluent.
However, a slight rinsing, for example with water, of the treated surfaces, without mechanical action such as brushing, may exceptionally be necessary to possibly remove traces of residual paint and small gel residues.
According to the invention, there is thus first of all a significant saving in chemical reagents compared to a decontamination process by washing with a solution. Next, since a waste in the form of a directly aspirable dry residue is obtained, a rinsing operation with water or with a liquid is generally avoided. This obviously results in a reduction in the quantity of effluents produced but also a significant simplification in terms of treatment and outlet channel. In particular, according to the invention, the waste obtained at the end of the treatment is not entrained in the rainwater drainage networks in violation of the regulations.
Due to the composition of the gel used according to the invention, the waste produced, once dry, represents only a small volume and is essentially mineral. They can therefore be stored or sent to an evacuation system without prior treatment.
For example, in the common case where 1000 grams of gel are applied per m ² of treated surface, the mass of dry waste produced is less than 300 grams per m ² .
The invention will now be described with reference to the following examples, given by way of illustration and not limitation.
Examples.
Example 1.
In this example, the formulation of a gel according to the invention, called “Limo1” gel, used in Examples 2 to 7 is described.
The gel according to the invention, called “Limo-1” gel, is a gel the composition of which is as follows:
10% by mass of alumina;
90% by mass of an active agent which is d-limonene.
The alumina is the Aeroxide® Alu C alumina marketed by EVONIK INDUSTRIES® which is a pyrogenic alumina with a specific surface of 100 m ² / g (BET), and the d-limonene is the d-limonene marketed by the company MERCK®.
This gel is prepared according to the following protocol:
The d-limonene is first weighed in a suitable container.
The d-limonene is stirred using a mechanical stirrer, equipped with a three-blade stirrer, at a speed of 200 rotations / min., For 3 to 5 minutes.
The alumina, in a proportion of 10% by mass, is then gradually added to the d-limonene, stirred using the mechanical stirrer. As the alumina is added, the viscosity of the stirred medium increases.
The speed of rotation is therefore also gradually increased as the viscosity of the stirred medium increases, reaching approximately 400 to 600 revolutions / min when all of the alumina has been added, so that it there are no projections.
The gel thus prepared is finally kept under stirring for 5 minutes, and left to stand for a period of at least one hour before its use.
Example 2.
In this example, the capacity of the gel according to the invention, known as “Limo-1” gel, prepared in Example 1, is shown to remove bitumen stains both on a dense surface and on a porous surface. Bitumen stains are carried out by depositing on the dense surface and on the porous surface, and under a heavy load, a small bitumen bit previously warmed. The charge is left for 24 hours to allow good adhesion of the bitumen stains to the smooth surface and to the porous surface.
The gel according to the invention, called “Limo-1” gel, is then deposited, here with a spatula, in sufficient quantity on each of the bitumen stains and then it is left to dry for 48 hours. The solid waste obtained after drying is finally recovered by brushing.
Figure 1 shows the results obtained on a smooth epoxy resin surface.
It is observed that, in one pass of the “Limo-1” gel, the entire bitumen stain could have been eliminated. One pass consists of depositing the gel on the bitumen stain, drying the applied gel, then brushing the solid waste obtained after drying.
Figure 2 shows the results obtained on a porous surface (concrete).
It is observed that two successive passes of the “Limo-1” gel were necessary in order to eliminate the bitumen stain.
It is indeed necessary to optimize the ratio of gel quantity / size of the bitumen task in order to be able to minimize the number of gel passes to be carried out.
These results thus demonstrate the capacity of a gel according to the invention to completely or almost completely eliminate an organic matrix from a dense or porous surface.
Example 3.
In this example, we describe the protocol for artificial contamination of bitumen with ¹³⁷ Cs, which has been developed, and we then describe the preparation of a dense support or surface in epoxy resin contaminated by an adherent stain of this contaminated bitumen artificially by ¹³⁷ Cs.
Bitumen contamination was set at 40,000 Bq / g in order to best simulate the bitumen tasks present on the ground in nuclear installations.
This protocol includes the following successive steps:
mL of an aqueous solution of ¹³⁷ Cs at around 40,000 Bq / mL are deposited at the bottom of a dish (such as a Petri dish) with a fairly high rim.
This solution is then allowed to evaporate. The ¹³⁷ Cs contamination is therefore deposited in a labile manner at the bottom of the cup.
Next, 2 grams of uncontaminated bitumen are placed in the cup, then this cup is placed on a hot plate brought to 100 ° C. for about 1 minute. The bitumen becomes much less viscous, almost liquid, and spreads out at the bottom of the cup.
The bitumen can then be stirred slowly in the cup using a spatula, to integrate homogeneously, into the bitumen, the ¹³⁷ Cs contamination deposited at the bottom of the cup as described above. The cup is held in place with an insulating clamp to avoid contact between the user and the system constituted by the hot plate and the hot cup.
Small beads of contaminated bitumen thus prepared, still warm, are then deposited on the surfaces to be contaminated.
A sheet of parchment paper (which does not stick to the bitumen) is placed on the bitumen beads thus deposited, then a light load is applied to these bitumen beads in order to flatten them as much as possible.
Finally, let cool and stand for 24 hours.
Measurements of radiological activity, namely a γ count, are carried out on each system consisting of a support, surface, and a task of contaminated bitumen, before carrying out the decontamination operation.
Example 4.
In this example, the removal of a bitumen spot contaminated with ¹³⁷ Cs bonded to a dense surface is carried out, and the decontamination power of the gel according to the invention, known as “Limo-1” gel, described, is thus shown. in Example 1, on a support, dense surface contaminated with an adherent stain of bitumen artificially contaminated with ¹³⁷ Cs.
Bitumen artificially contaminated with ¹³⁷ Cs is prepared, according to the protocol described in Example 3, and then, in accordance with Example 3, a support or dense surface is prepared in epoxy resin contaminated with an adherent stain of bitumen artificially contaminated with ¹³⁷ Cs (FIG. 3A). After a first count of the radiological activity, a “Limo-1” gel is applied to the contaminated bitumen task with a spatula and then left to dry for 48 hours.
We then obtain glitter which we can easily brush (FIG. 3B).
A second count of the radiological activity is then carried out and a first Decontamination Factor (FD) can be calculated.
Recall that FD = Value of initial contamination / value of final contamination.
We then obtain an FD of 23 for an initial contamination of 4600 Bq.
The application of a second layer of gel makes it possible to increase this FD up to 156. There therefore remains only a very low contamination on the smooth support (FIG. 3C).
The values of the radiological activities measured during the radiological decontamination operation carried out in Example 4 are grouped in Table I below.
Gel Limo-1 Initial contamination (support + bitumen)(± 15%) 4600 Bq Contamination after 1 gel pass (± 5%) 199 Bq FD_1 23 Contamination after 2 frost passes(± 5%) 29 Bq FD_2 156
Table I: Values of the radiological activities measured during the decontamination of a dense surface.
These results clearly show the effectiveness of the gel according to the invention, called “Limo-1” gel for the decontamination of a support with a dense surface such as a support made of epoxy resin contaminated with a stain of contaminated bitumen.
Example 5.
In this example, the removal of a bitumen stain contaminated with ¹³⁷ Cs bonded to a porous surface is carried out, and the decontamination power of the gel according to the invention, known as “Limo-1” gel, described, is thus shown. in Example 1, on a support, porous surface contaminated by an adherent stain of bitumen artificially contaminated with ¹³⁷ Cs.
Bitumen artificially contaminated with ¹³⁷ Cs is prepared, according to the protocol described in Example 3, and then, in accordance with Example 3, a support or porous concrete surface contaminated by an adherent task is prepared with this bitumen artificially contaminated with ¹³⁷ Cs.
After a first count of the radiological activity, a “Limo-1” gel is applied to the contaminated bitumen task with a spatula and then left to dry for 48 hours.
This gives you glitter that you can easily brush off.
A second count of the radiological activity is then carried out and a first
Decontamination factor (FD) can be calculated.
Recall that FD = Value of initial contamination / value of final contamination.
This gives an FD of 2 for an initial contamination of 5500 Bq. The application of a second layer of gel achieves an FD of 27.
The application of a third layer of gel achieves an FD of 85.
There therefore remains only a very low contamination on the porous support.
The values of the radiological activities measured during the radiological decontamination operation carried out in Example 5 are grouped in Table II below.
Gel Limo-1 Initial contamination (gel + bitumen)(± 15%) 5500 Bq Contamination after 1 gel pass(± 15%) 2300 Bq FD_1 2 Contamination after 2 frost passes(± 5%) 205 Bq FD_2 27 Contamination after 3 frost passes(± 15%) 65 Bq FD_3 85
Table II: Values of the radiological activities measured during the decontamination operation of a porous surface.
These results clearly show the effectiveness of the gel according to the invention, called “Limo-1” gel for the decontamination of a support with a porous surface such as a concrete support contaminated with a stain of contaminated bitumen.
Example 6.
In this example, the capacity of the gel according to the invention, called “Limo-1” gel, is shown to chemically attack an organic matrix such as an epoxy resin matrix.
For this, an optical profilometer is used which will make it possible to characterize the surface condition of an epoxy resin before and after application of the gel.
FIG. 4A thus presents a photograph of the surface of an epoxy resin before the deposition of a layer on the surface of the epoxy resin (on the left) and after the deposition of a layer of gel, the drying of this layer and elimination of dry gel flakes (right).
FIG. 4B shows the surface profiles corresponding to the surfaces photographed in FIG. 4A, before the deposition of a layer on the surface of the epoxy resin (on the left) and after the deposition of a layer of gel, the drying of this layer and removing the dry gel flakes (right).
It is observed that the epoxy resin is clearly degraded on the right-hand side of FIG. 4A which shows the surface obtained following the deposition, drying and elimination of the flakes of the “Limo-1” gel.
This degradation is obtained over a thickness of a few micrometers (Figure
4B).
These results thus demonstrate that the “Limo-1” gel according to the invention attacks the epoxy resin over a few microns thick.
This property will thus allow the gel according to the invention to release and then to capture the contaminants embedded under the surface (on the subsurface) of this type of organic matrix.
Example 7.
In this example, it is shown that the gel according to the invention, known as “Limo-1” gel prepared in Example 1, can be applied by spraying.
A rheological study of the “Limo-1” gel according to the invention, prepared in Example 1 was carried out and makes it possible to show that this process is suitable for use by spraying.
So that this type of gel can be applied according to a spraying process, it must have the properties of a shear thinning fluid, thixotropic, with a very short recovery time (less than a second), and that it has a threshold stress (typically greater than 10-15 Pa).
Different rheological measurements were carried out using a TA Instruments® AR-IOOO rheometer in “Vane” geometry and are presented in this example.
First, the viscosity of the gel was measured as a function of the shear rate.
After a pre-shear of 5 minutes at a shear rate of 20 s ' ¹ , then from 1 minute to 0.015 s' ¹ , several shear rate steps ranging from 0.015 s ¹ to 100 s ¹ are performed with a measurement of viscosity every 30 seconds.
FIG. 5 gives the evolution of the viscosity (Pa.s) of the “Limo-T” gel according to the invention as a function of the shear rate (s ^_1 ) for shear rates between 0.015 and 100 s ¹ . We observe a linear fall (in logarithmic scale) of the viscosity with the shear rate, characteristic of the behavior of a shear-thinning fluid with threshold stress.
FIG. 6 represents the value of shear stress as a function of the deformation obtained at a shear rate imposed for the gel according to the invention, known as “Limo-1” gel described in example 1. A low shear rate ( 0.015 s ¹ ) is applied constantly in order to deform the gel from rest and thus to determine the flow threshold. An already almost stationary flow is observed with values of shear stress greater than 60 Pa. The threshold stress of the material with very high deformation will therefore be much greater than 20 Pa, which will allow the gel to hold on a wall for thicknesses between 0 and at least 2 mm.
In conclusion, this example shows that the “Limo-1” gel according to the invention does indeed have the appropriate rheological properties allowing it to be very easily sprayable on horizontal surfaces or not.
Example 8.
In this example, it is shown that the gel according to the invention, called “Limo-1” gel prepared in Example 1, is aspirable after application and drying.
In other words, in this example, it is a question of showing that the gel according to the invention, known as “Limo-1” gel prepared in Example 1, fractures well by producing non-pulverulent flakes of millimeter size which can be easily aspirated.
To carry out this study, the Limo-1 gel is put to dry in a Binder® climatic chamber whose temperature and percentage of relative humidity are set at 25 ° C and 50% respectively.
The gel is spread on a machined stainless steel basket so as to obtain a controlled thickness of 2 mm of gel in the basket.
In the climatic chamber, a Sartorius® precision balance is installed, as well as a Moticam® camera surrounded by a circular LED lamp (VWR) which is placed on top of the balance.
The Moticam® scale and camera are connected to a computer placed outside the climatic chamber, thus allowing the simultaneous acquisition, during drying in a controlled atmosphere, of the mass and images of the gel-filled basket.
It should be noted that the nacelle containing the gel is placed in the precision balance and that all the doors of the balance are closed, except for the door opposite the air supply blower of the climatic chamber, which is 3 cm open, to maintain the controlled atmosphere in the interior of the scale, while limiting the air flow linked to the functioning of the climatic chamber. The recording of the mass during drying then makes it possible to draw a curve which gives the loss of mass as a function of time and which therefore represents the kinetics of drying.
The evolution of mass loss as a function of time is presented in Figure 7, and a photograph representing the final size of the gel flakes is presented in Figure 8.
It is thus observed that a thickness of 2 mm of the "Limo-1" gel dries in a few hours, more exactly in about 1200 minutes, or 20 hours. It also appears that the number of flakes formed and above all their size is in good agreement with the fact that these flakes are of millimeter sizes and are not powdery.
REFERENCES [1] FR-A1-2 827 530.
[2] FR-A1-2 891 470.
[3] WO-A1-99 / 09134.
[4] FR-A1-3 027 310.
[5] FR-A1-2 957 929.
[6] FR-A1-2962046 and WO-A1-2012 / 00104.
[7] FR-A1-3003763 and WO-A1-2014 / 154818.

权利要求:
Claims (32)
[1" id="c-fr-0001]
1. Suction gel to remove a contaminating species contained in a layer constituted by an organic material, on the surface of a solid substrate, constituted by a colloidal solution comprising, preferably constituted by:
1% to 25% by mass, preferably 5% to 20% by mass, for example 10% by mass, relative to the total mass of the gel, of at least one inorganic viscosifying agent;
13% to 99% by mass, preferably 80% to 95% by mass, for example 90% by mass, relative to the total mass of the gel, of one or more organic solvent (s) chosen (s) ) among terpenes;
optionally, from 1% to 40% by mass, preferably from 10% to 20% by mass, relative to the total mass of the gel, of ethanol;
optionally, from 0.01% to 10% by mass, relative to the total mass of the gel, of at least one dye and / or pigment;
optionally, from 0.1% to 2% by mass, relative to the total mass of the gel, of at least one surfactant;
optionally, from 0.1% to 10% by mass, preferably 1% to 5% by mass, relative to the total mass of the gel, of at least one agent extracting from the contaminating species, for example from at least one agent extracting radionuclides, preferably chosen from zeolites and clays.
[2" id="c-fr-0002]
2. Gel according to claim 1, in which the terpenes are chosen from terpene hydrocarbons, oxygenated terpene compounds, and isomers, in particular the optical isomers thereof.
[3" id="c-fr-0003]
3. Gel according to claim 2, in which the terpenes are chosen from ocimene, α-pinene, β-pinene, limonene, menthol, menthone, terpineol, isoborneol, camphor, nerol , citronellal, citronellol, myrcene, myrcenol, Iinaloi, geraniol, and the isomers including the optical isomers thereof.
[4" id="c-fr-0004]
4. Gel according to claim 3, comprising, as organic solvent chosen from terpenes, preferably as the only organic solvent chosen from terpenes, d-limonene.
[5" id="c-fr-0005]
5. Gel according to claim 4, comprising, as solvent, from 35% to 94% by mass, relative to the total mass of the gel, of d-limonene, and from 1% to 40% by mass relative to the total mass of the gel, of ethanol.
[6" id="c-fr-0006]
6. Gel according to any one of the preceding claims, in which the inorganic viscous agent is chosen from metal oxides such as aluminas, metalloid oxides such as silicas, metal hydroxides, metalloid hydroxides, metal oxyhydroxides, metalloid oxyhydroxides, aluminosilicates, clays such as smectite, and mixtures thereof.
[7" id="c-fr-0007]
7. Gel according to claim 6, in which the inorganic viscous agent is chosen from fumed silicas, precipitated silicas, hydrophilic silicas, hydrophobic silicas, acidic silicas, basic silicas, and their mixtures.
[8" id="c-fr-0008]
8. The gel of claim 6, wherein the inorganic viscosity agent consists of one or more alumina (s).
[9" id="c-fr-0009]
9. Gel according to claim 8, in which the alumina (s) is (are) chosen (s) from fumed aluminas, preferably from pyrogenated aluminas with fine particle size.
[10" id="c-fr-0010]
10. The gel of claim 8 or 9, wherein the alumina (s) represents (s) from 5% to 25% by mass, preferably from 7% to 15% by mass relative to the total mass of the gel .
[11" id="c-fr-0011]
11. Gel according to any one of the preceding claims, in which the surfactant is chosen from nonionic surfactants such as block copolymers, block copolymers such as block copolymers of ethylene oxide and propylene oxide, and ethoxylated fatty acids; and their mixtures.
[12" id="c-fr-0012]
12. Gel according to any one of the preceding claims, consisting of a colloidal solution comprising, preferably consisting of:
5% to 25% by mass, preferably 7% to 15% by mass, relative to the total mass of the gel, of at least one alumina, preferably of at least one fumed alumina, more preferably of at least minus a pyrogenic alumina having a fine particle size;
35% to 94% by mass, preferably from 65% to 83% by mass, relative to the total mass of the gel, of d-limonene;
from 1% to 40% by mass, preferably from 10% to 20% by mass, relative to the total mass of the gel, of ethanol.
[13" id="c-fr-0013]
13. Method for eliminating a contaminating species contained in a layer constituted by an organic material on the surface of a solid substrate, in which at least one cycle is carried out comprising the following successive steps:
a) applying the gel according to any one of claims 1 to 12, on said layer consisting of an organic material;
b) the gel is maintained on the layer consisting of an organic material at least for a sufficient time so that the gel dissolves part or all of the organic material of the layer consisting of an organic material, absorbs the contaminating species (so that the contaminating species migrates in the gel), and so that the gel dries and forms a dry and solid non-pulverulent residue containing the organic material of the layer constituted by an organic material which has been dissolved, and the contaminating species;
c) removing the dry and solid residue containing the organic material from the organic layer which has been dissolved, and the contaminating species.
[14" id="c-fr-0014]
14. The method of claim 13, wherein the contaminating species is a radioactive contaminating species and / or chemically toxic, and / or toxic due to its shape and / or its size.
[15" id="c-fr-0015]
15. The method of claim 14, wherein the contaminant species toxic due to its shape and / or size, is a contaminant species in the form of solid particles such as microparticles, or nanoparticles, for example in the form of fibers such as microfibers or nanofibers, in the form of nanotubes, or in the form of crystals such as nanocrystals.
[16" id="c-fr-0016]
16. Method according to any one of claims 13 to 15, in which the contaminating species is chosen from metals and metalloids in the form of metal, metalloid, or ionic, preferably from so-called "heavy metal" metals, and toxic metals and metalloids in the form of metal, metalloid, or ionic; compounds of these metals and metalloids such as organometallic compounds, metal salts, metal oxides, metal carbides, etc. ; ceramics; and glasses for example in the form of glass wool.
[17" id="c-fr-0017]
17. The method of claim 16, wherein the metals called "heavy metals", and toxic metals and metalloids are antimony, arsenic, cadmium, chromium, copper, lead, mercury, nickel , selenium, tellurium, thallium and tin.
[18" id="c-fr-0018]
18. The method of claim 13, wherein the contaminating species is asbestos.
[19" id="c-fr-0019]
19. Method according to any one of claims 13 to 18, in which the layer constituted by an organic material containing a contaminating species is a surface layer of a solid substrate constituted by said (the same) organic material, preferably this organic material is chosen from paints, lacquers, organic polymers, and organic resins such as epoxy resins.
[20" id="c-fr-0020]
20. The method of claim 19, wherein the solid substrate constituted by an organic material is a solid solid substrate or a layer, such as a layer of paint or epoxy resin, for example a layer of paint or epoxy resin forming a coating on a surface of a substrate.
[21" id="c-fr-0021]
21. Method according to any one of claims 13 to 20, in which the layer consisting of an organic material containing a contaminating species is a layer lying on a surface of a solid substrate, this layer being in the form of a task or discrete tasks of organic material containing a contaminating species.
[22" id="c-fr-0022]
22. The method of claim 21, wherein the organic material is chosen from sticky organic materials.
[23" id="c-fr-0023]
23. The method of claim 21 or 22, wherein the organic material is chosen from oils, such as hydrocarbon oils, bitumens, tars and greases.
[24" id="c-fr-0024]
24. Method according to any one of claims 21 to 23, in which the substrate is a porous substrate, preferably a porous mineral substrate, or a non-porous substrate.
[25" id="c-fr-0025]
25. Method according to any one of claims 13 to 24, in which the gel is applied to the surface layer at a rate of 100 g to 10000 g, preferably from 500 g to 5000 g of gel per m ² of surface, which generally corresponds to a thickness of gel deposited on the surface of between 0.1 mm and 1 cm, preferably between 0.5 mm and
5 mm.
[26" id="c-fr-0026]
26. Method according to any one of claims 13 to 25, in which the gel is applied to the surface of the solid substrate by spraying, with a brush, or with a float.
[27" id="c-fr-0027]
27. Method according to any one of claims 13 to 26, in which during step b), the drying is carried out at a temperature of 1 ° C to 50 ° C, preferably from 1 ° C to 40 ° C , more preferably from 15 ° C to 25 ° C, and at a relative humidity of 20% to 80%, preferably from 20% to 70%.
[28" id="c-fr-0028]
28. Method according to any one of claims 13 to 27, in which the gel is maintained on the surface for a period of 2 to 72 hours, preferably from 4 to 48 hours, more preferably from 6 to 24 hours.
[29" id="c-fr-0029]
29. Process according to any one of claims 13 to 28, in which the dry and solid residue is in the form of particles, for example flakes, of a size from 1 to 10 mm, preferably from 2 to 5 mm.
[30" id="c-fr-0030]
30. Method according to any one of claims 13 to 29, in which the dry and solid residue is removed from the surface of the solid substrate by brushing and / or suction.
[31" id="c-fr-0031]
31. Method according to any one of claims 13 to 30, in which the cycle is repeated from 1 to 10 times using the same gel during all the cycles or using different gels during one or more cycles ( s).
[32" id="c-fr-0032]
32. Method according to any one of claims 13 to 31, in which during step b), the gel, before total drying, is rewetted with a solvent, preferably with the solvent of the gel applied during the step at).
S62413
1/4

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US20090197790A1|2008-02-05|2009-08-06|Amcol International Corporation|Drip resistant cleaning compositions|

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FR2956517B1|2010-02-17|2012-03-09|Commissariat Energie Atomique|PROCESS FOR TREATMENT BEFORE CALCINATION OF A NITRIC AQUEOUS SOLUTION COMPRISING AT LEAST ONE RADIONUCLEID AND POSSIBLY RUTHENIUM|

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FR2957929A1|2010-03-29|2011-09-30|Lobial|PROCESS FOR TREATING A SOLID SURFACE|

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US9006417B2|2010-06-30|2015-04-14|Protiva Biotherapeutics, Inc.|Non-liposomal systems for nucleic acid delivery|

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FR2962046B1|2010-07-02|2012-08-17|Commissariat Energie Atomique|BIOLOGICAL DECONTAMINATION GEL AND METHOD OF DECONTAMINATING SURFACES USING THE GEL.|

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FR3003763B1|2013-03-29|2015-05-15|Commissariat Energie Atomique|ALKALINE OXIDIZING GEL FOR BIOLOGICAL DECONTAMINATION AND METHOD FOR BIOLOGICAL DECONTAMINATION OF SURFACES USING THE GEL.|

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FR3027310B1|2014-10-15|2017-12-15|Commissariat Energie Atomique|GEL FOR REMOVING GRAFFITI AND METHOD FOR REMOVING GRAFFITIS USING THE GEL.|FR3083712B1|2018-07-11|2022-01-21|Commissariat Energie Atomique|METHOD FOR DECONTAMINATING A GAS MEDIUM CONTAMINATED BY CONTAMINATING SPECIES IN SUSPENSION.|

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CN109402644A|2018-12-03|2019-03-01|巢湖鹏远金属焊管有限公司|A kind of degreased cleaning agent for metallic conduit|

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CN111876071A|2020-08-08|2020-11-03|百草春天大生物科技有限公司|Mint modified water-based paint and preparation method thereof|

法律状态:
2018-02-09| PLSC| Publication of the preliminary search report|Effective date: 20180209 |

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2018-04-26| PLFP| Fee payment|Year of fee payment: 2 |

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2019-04-29| PLFP| Fee payment|Year of fee payment: 3 |

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2020-04-30| PLFP| Fee payment|Year of fee payment: 4 |

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2021-04-29| PLFP| Fee payment|Year of fee payment: 5 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1657620A|FR3054839B1|2016-08-05|2016-08-05|SUCTION GEL AND METHOD FOR ELIMINATING RADIOACTIVE CONTAMINATION CONTAINED IN AN ORGANIC LAYER ON THE SURFACE OF A SOLID SUBSTRATE.|

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FR1657620|2016-08-05|JP2019506102A| JP6983224B2|2016-08-05|2017-08-02|Aspirable gels and methods for removing contaminants contained in organic layers on the surface of solid substrates|

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US16/323,095| US11081251B2|2016-08-05|2017-08-02|Suctionable gel and method for eliminating a contamination contained in a surface organic layer of a solid substrate|

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PCT/FR2017/052171| WO2018024990A1|2016-08-05|2017-08-02|Vacuumable gel and method for eliminating contamination contained in an organic layer on the surface of a solid substrate|

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EP17765221.1A| EP3494181A1|2016-08-05|2017-08-02|Vacuumable gel and method for eliminating contamination contained in an organic layer on the surface of a solid substrate|