EP1228512B1 - Organisches gel zur dekontaminierung und seine verwendung zur dekontaminierung von oberflächen - Google Patents

Organisches gel zur dekontaminierung und seine verwendung zur dekontaminierung von oberflächen Download PDF

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Publication number
EP1228512B1
EP1228512B1 EP00964318A EP00964318A EP1228512B1 EP 1228512 B1 EP1228512 B1 EP 1228512B1 EP 00964318 A EP00964318 A EP 00964318A EP 00964318 A EP00964318 A EP 00964318A EP 1228512 B1 EP1228512 B1 EP 1228512B1
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Prior art keywords
gel
mol
agent
weight
decontamination
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French (fr)
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EP1228512A1 (de
Inventor
David Résidence "Le Lauréat" CHEUNG
Philippe Rigal
Stéphane BARGUES
Frédéric FAVIER
Jean-Louis Résidence Facultés PASCAL
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Orano DS Demantelement et Services SA
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STMI Societe des Techniques en Milieu Ionisant SPL
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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions

Definitions

  • the present invention relates to an organic decontamination gel that can be used for the radioactive decontamination of surfaces, in particular metal surfaces.
  • organic gel is meant, according to the invention, a gel in which the viscosifying agents are essentially organic, that is to say free of any inorganic or mineral material.
  • the decontamination of parts contaminated with radioactive elements can be achieved either by mechanical treatments or by chemical treatments.
  • the methods using mechanical treatments have the disadvantage of causing a more or less significant modification of the surface of the part and to be, moreover, difficult to implement on parts of complicated shape.
  • Dipping treatment methods which consist essentially of entraining the radioactive elements fixed on the surface of the part by means of solutions of suitable decontamination active agents, in particular of Ce (IV) stabilized in a highly concentrated acid medium such as acid nitric or sulfuric, have the disadvantage of leading to the production of large volumes of effluents whose subsequent treatment including concentration is very expensive.
  • dipping methods employing solutions pose certain problems for the treatment of large parts which are difficult to immerse and soak completely in the reagent solution.
  • Decontamination solutions do indeed allow the treatment by soaking only dismountable metal parts of limited size, that is to say that these solutions can in practice be used only in the context of the dismantling of radioactive facilities.
  • the inorganic supports such as aluminas and silicas, available on the market, which also have a great diversity of their characteristics such as hydrophilic, hydrophobic, pH, etc., appear as the best way to viscose / gel these solutions.
  • the spraying of such gels can allow on-site decontamination of large metal surfaces that are not necessarily horizontal, but can be as inclined or even vertical.
  • the decontamination gels can therefore be described as colloidal solutions comprising a generally inorganic viscosifying agent such as alumina or silica and an active decontamination agent, for example an acid, a base, an oxidizing agent, a reducing agent or a reducing agent. mixture thereof, which is chosen in particular depending on the nature of the contamination and the surface.
  • a generally inorganic viscosifying agent such as alumina or silica
  • an active decontamination agent for example an acid, a base, an oxidizing agent, a reducing agent or a reducing agent. mixture thereof, which is chosen in particular depending on the nature of the contamination and the surface.
  • an alkaline gel for stainless and ferritic steels will have degreasing properties for the removal of unfixed contamination.
  • An oxidizing gel for stainless steels will eliminate hot and cold contamination.
  • a reducing gel will preferably be used in addition to the oxidizing gel and alternately for the dissolution of hot-formed oxides, for example in the primary circuit of pressurized water reactors (PWRs).
  • a decontaminant gel consisting of a colloidal solution of an organic or inorganic compound to which a decontaminating product such as hydrochloric acid, stannous chloride, oxine and / or sodium fluoride is optionally added.
  • Document FR-A-2 656 949 describes an oxidizing decontaminating gel which makes it possible to eliminate the radioactive elements deposited on the part as well as the radioactive elements embedded on its surface.
  • the gel further comprises 0.1 to 1 mol / l of a compound d) capable of oxidizing the reduced form of this oxidizing agent.
  • the presence of components b) and c) makes it possible respectively to eliminate the radioactive deposits formed on the surface of the part and to eliminate the encrusted radioactivity, by controlled erosion of the surface to decontaminate.
  • This oxidizing gel does not have sufficient efficiency vis-à-vis the layers of metal oxides adherent deposited on the surface of alloys such as austenitic steels, Inconel 600 and Incoloy.
  • the application of the gels to the surface, for example the metal surface, to be decontaminated is preferably carried out by spraying with a gun, for example under a pressure that may range from 50 to 160 bars and even beyond, the gel being stirred before spraying to make the gel homogeneous.
  • a gun for example under a pressure that may range from 50 to 160 bars and even beyond
  • the gel being stirred before spraying to make the gel homogeneous.
  • the gel is rinsed by spraying with water, and the effluents generated are treated, for example, by neutralization, decantation and filtration.
  • FEVDIRAD Typical gels of the prior art are marketed by FEVDI under the name "FEVDIRAD"
  • the restructuring means a return to gelation, thus adhesion to the surface, and a short recovery time characterizes a gel quickly recovering sufficient viscosity after spraying to prevent sagging.
  • the recovery times are too long.
  • the recovery times are always greater than 5 seconds, which is obviously excessive.
  • the return time to a viscosity sufficient for the gel to adhere to the wall may be reduced, but this then requires to significantly increase the mineral load.
  • the gels described above which comprise an exclusively mineral viscosing agent composed in particular of micrometric particles of fumed silica or mixtures of alumina and silica while reducing their mineral charge and without affecting their corrosive qualities.
  • the incorporation into the viscosifying agent of the decontamination gel, in addition to the mineral viscosing agent, of an organic viscosifying agent (called coviscosant) makes it possible to greatly improve the rheological properties of the gels, and to reduce significantly their mineral load and solid waste produced without the corrosive properties and other decontamination qualities of these gels are affected.
  • the gels described in this document are perfectly projectable, are easily removed by rinsing after application, filtration during the treatment of effluents is facilitated and the volume of ultimate solid waste is reduced accordingly.
  • organic covariant polymer or surfactant is easily degraded during the treatment of the effluents.
  • the inorganic filler of the gels described in document FR-A-2 746 328 is still important, since generally close to 5%, which implies in particular the need for a complex filtration system.
  • the purpose of the present invention is to provide a decontamination gel which meets, inter alia, all the needs mentioned above.
  • the object of the present invention is still to provide a decontamination gel which does not have the disadvantages, defects, limitations and disadvantages of the processes of the prior art and which solves the problems of the prior art.
  • Preferred embodiments of said gel are as defined in Claims 2 to 31.
  • the gels according to the invention therefore do not contain any mineral viscosity, such as silica or alumina. Consequently, because their mineral load, related to the viscosizer, is substantially zero, all the disadvantages due to the solid waste created by this mineral filler are eliminated, in particular a complex and expensive filtration and recovery system for this waste. is no longer necessary.
  • the only waste produced in small quantities contains only easily degradable organic products, preferably exclusively composed of carbon, nitrogen, oxygen and hydrogen without prohibited elements in the nuclear, such as sulfur or halogens.
  • the decontamination factors obtained with the gels of the invention are quite comparable or even superior to those of the analog gels of the prior art, that is to say gels comprising the same decontamination agent. but having a mineral viscosity agent alone or in combination with a viscose, as in FR-A-2 746 328.
  • the gels according to the invention retain, surprisingly, their characteristic structure, much longer than the gels comprising a mineral viscosity, and dry much less quickly, while also maintaining their corrosion properties. Their removal by rinsing is thus facilitated and the volume of rinsing effluents reduced.
  • the gels according to the invention have excellent temperature stability - for example, up to 80 ° C - or, in other words, excellent heat resistance, i.e. recycling and prolonged corrosion properties of these gels, are, among others, kept at these high temperatures. This property is particularly important in certain specific uses, where the surfaces to be treated are permanently at a high temperature, for example, greater than or equal to 40 ° C.
  • the preparation of the gels according to the invention is easy and fast and uses only readily available reagents, low cost; the gels according to the invention can therefore be used on a large scale and on an industrial scale.
  • the gels according to the invention are a totally surprising step and going against what could have been expected. Indeed, nothing could have suggested that the total suppression of the mineral viscosity in the gels of the prior art, represented in particular by FR-A-2 746 328, would lead to gels having all the required properties, in particular for regarding their rheology.
  • the invention therefore excludes over prejudice and provides a solution to the problems of the prior art.
  • the viscosing agent a) is an exclusively organic viscosifying agent which is a water-soluble organic polymer chosen from acrylic acid polymers and copolymers of acrylic acid with acrylamide.
  • polymers may be used in the gel at a content, generally from 1 to 11%, preferably from 2 to 8% by weight, more preferably from 4 to 6% by weight; at these levels, they allow in particular a significant improvement in the rheological properties of the gels and a total suppression of the mineral filler, for example, alumina and / or silica.
  • the polymer generally has a molecular weight defined by the weight average molecular weight of 200,000 to 5,000,000 g / mol.
  • polymer according to the invention is meant both homopolymers and copolymers, sequenced or statistics.
  • this polymer must fulfill a number of conditions related in particular to its use in nuclear installations.
  • the polyacrylic acid polymer is constituted by the repetition of the following monomeric unit (I): -CH 2 CH (CO 2 H) -.
  • the weight average molecular weight of the polyacrylic acid polymers is generally from 450,000 to 4,000,000. Preferably, the weight average molecular weight is 4,000,000. Indeed, it has been demonstrated that the formation of a gel requires increasing percentages of polymer with the decrease of the macromolecular chain. This is because a large weight average molecular weight corresponding to a larger chain length must promote better crosslinking and thus the formation of a more viscous gel for a smaller amount of polymer.
  • copolymers of acrylic acid with acrylamide generally have an average molecular weight by weight from 200,000 to 5,000,000; preferably from 200,000 to 4,000,000.
  • the percentage of each of monomers in the copolymer of acrylic acid and acrylamide is variable; the copolymer will generally comprise from 95 to 60% by weight of acrylic acid and from 5 to 40% by weight of acrylamide.
  • a preferred copolymer is a weight average molecular weight copolymer of 200,000 and the percentage by weight of acrylamide is 10%.
  • copolymers can be sequenced or statistical.
  • the random copolymer of formula (I): is thus constructed from two types of blocks of varying lengths consisting of one of acrylic acid monomer units and the other of acrylamide monomer units.
  • acrylic acid-acrylamide copolymers examples include the copolymers marketed by SCOTT BADER® under the name TEXIPOL®, such as TEXIPOL® 63-510. This product is in the form of a 25% aqueous solution. % of a polyacrylic acid-acrylamide copolymer (molar mass: 10 6 , percentage of acrylamide: 20 - 30%) dispersed in an organic phase composed of toluene white spirit or 20% isopar in the form of an emulsion with 5% surfactant.
  • the gels according to the invention further comprise also an organic surfactant which is included in the organic viscosity agent.
  • n defines the length of the aliphatic chain and is an integer which can vary from 6 to 18, preferably from 6 to 12
  • m controls the size of the polar head and is an integer which can vary from 1 to 23, preferably 2 to 6.
  • the compounds C 6 E 2 di (ethylene glycol) hexyl ether), C 10 E 3 and C 12 E 4 are preferred.
  • Such C n E m compounds are available from ALDRICH® and SEPPIC® companies.
  • the nature of the surfactant depends on the type of decontamination gel used, ie the nature and the content of the active decontamination agent b) and the nature and content of the agent. organic viscous polymer.
  • the compounds C n E m are they particularly suitable for use in gels comprising polyacrylic acid, in particular particularly in acidic oxidizing gels comprising polyacrylic acid.
  • the surfactant content depends on the nature of the decontamination gel as well as the concentration and nature of the organic viscosity agent.
  • This surfactant content will generally be between 0.1 and 5% by weight, preferably between 0.2 and 2% by weight, more preferably between 0.5 and 1% by weight.
  • the viscosing agent a) according to the invention can be used in any decontamination gel, whatever the type of the latter, that is to say whatever active decontamination agent b) is used in the decontamination gel.
  • FR-A-2,380,624. FR-A-2 656 949 and FR-A 2 695 839, or it may be used in place of the viscosing agent comprising the combination of a mineral viscosity agent and an organic viscosifying agent described in document FR-A-2,746,328.
  • decontamination gels are of different types depending on the active decontamination agent b) they contain; alkaline gels, acid gels, reducing gels and oxidizing gels are generally distinguished.
  • the decontamination gel according to the invention may contain as active agent for decontamination b) an acid, preferably an inorganic acid preferably chosen from acid hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and mixtures thereof.
  • an acid preferably an inorganic acid preferably chosen from acid hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and mixtures thereof.
  • the acid is generally present at a concentration of 1 to 10 mol / l, preferably 3 to 10 mol / l.
  • Such gel known as “acid gel” is particularly suitable for removing cold-fixed contamination on ferritic steels.
  • the viscosing agent is preferably a polyacrylic acid, more preferably a high weight average molecular weight, that is to say greater than or equal to 450,000, for example, close to 4,000. 000.
  • the viscosing agent is in this type of gel generally present at a concentration of 3 to 12% by weight.
  • the decontamination gel according to the invention may also contain, as active decontamination agent b), a base preferably a mineral base preferably chosen from sodium hydroxide, potassium hydroxide and mixtures thereof.
  • a base preferably a mineral base preferably chosen from sodium hydroxide, potassium hydroxide and mixtures thereof.
  • the base is generally present at a concentration of 0.1 to 14 mol / l.
  • alkaline gel has interesting degreasing properties and is particularly suitable for removing non-fixed contamination on stainless and ferritic acids.
  • the viscosing agent is preferably an acrylic acid-acrylamide copolymer, for example of TEXIPOL type, 63-510.
  • this gel does not require any heating during its synthesis.
  • the decontamination gel according to the invention may also contain, as decontamination active agent b) a reducing agent, this reducing agent may for example be a reducing agent such as that described in document FR-A-2 695 839 in which the Reducing agent used is a reducing agent having a normal redox potential E 0 of less than -600 mV / ENH (normal hydrogen electrode) in a strong base medium (pH ⁇ 13).
  • this reducing agent may for example be a reducing agent such as that described in document FR-A-2 695 839 in which the Reducing agent used is a reducing agent having a normal redox potential E 0 of less than -600 mV / ENH (normal hydrogen electrode) in a strong base medium (pH ⁇ 13).
  • reducing agents By way of example of such reducing agents, mention may be made of borohydrides, sulphites, hydrosulphites, sulphides, hypophosphites, zinc, hydrazine and their mixtures.
  • metal salts for example alkali metal salts such as sodium.
  • the pH of the colloidal solution is preferably greater than or equal to 14 so that the borohydride remains stable.
  • the reducing agents as described in document FR-A-2 695 839 are generally associated with a mineral base such as NaOH or KOH at a concentration generally of between 0.1 and 14 mol / l, the concentration of reducing agent being as for it, generally between 0.1 and 4.5 mol / l.
  • the viscosing agent is rather an acrylic acid-acrylamide copolymer, for example of TEXIPOL type, 63-510.
  • reducing gel is generally used in addition and alternately an oxidizing gel as described below.
  • Such a gel makes it possible, in particular, to weaken and displace the adherent surface metal oxide layers which have been deposited on the surface of alloys such as the austenitic stainless steels, Inconel and Incoloy which form the primary circuits of the alloys.
  • pressurized water reactors PWRs that are not sensitive to the action of oxidizing decontaminant gels.
  • This gel does not require any other heating during its synthesis.
  • the decontamination gel according to the invention may also contain, as active decontamination agent b), an oxidizing agent.
  • This oxidizing agent can be, for example, an oxidizing agent such as that described in document FR-A-2 659 949 in which the oxidizing agent used is an oxidizing agent which must have a normal redox potential greater than 1400 mV / ENH in strong acid medium (pH ⁇ 1), that is to say an oxidizing power greater than permanganate.
  • oxidizing agents are particularly suitable when the surface to be decontaminated is a metal surface, for example noble alloy, such as stainless steel 304 and 316L, Inconel and Incolloy.
  • these oxidizing agents can also oxidize some very insoluble colloidal oxides such as PuO 2 to transform them into a soluble form such as PuO 2 2+ .
  • the oxidizing agent in its reduced form, for example Ce III , Co II or Ag I may be used , provided that a compound capable of oxidizing this gel is added to the gel. reduced form, or provided to associate the gel with another gel or other colloidal solution containing a compound capable of oxidizing this reduced form of the oxidizing agent.
  • the compound capable of oxidizing the reduced form of the oxidizing agent may consist for example of an alkali metal persulfate.
  • the oxidizing agents are generally associated, with a mineral base, or for stabilization purposes, with a mineral acid such as HCl, H 3 PO 4 , H 2 SO 4 and preferably HNO 3 at a concentration generally of between 1 and 10 mol / l, preferably of 2 to 10 mol / l, more preferably of 2 to 3 mol / l, for example 2.88 mol / l, the concentration of oxidizing agent being, in turn, generally between 0.1 and 2 mol / l, preferably between 0.6 and 1.5 mol / l, more preferably this concentration is 1 mol / l.
  • an oxidizing cation such as Ce IV , Ag II or Co III
  • it may be introduced in the form of one of its salts, such as nitrate, sulphate or other, but it may also be electrogenerated. .
  • the preferred oxidizing gels contain cerium (IV) in the form of electrogenerated cerium (IV) nitrate Ce (NO 3 ) 4 or hexanitrate cerium ammonium (NH 4 ) 2 Ce (NO 3 ) 6 , the latter being preferred because of the relative instability of cerium (IV) nitrate in a concentrated nitric medium.
  • Nitric acid stabilizes cerium to the oxidation state IV, participates in corrosion and ensures, among other things, the maintenance in solution of the corroded species, namely complex oxo-nitrato transition metals constituting the metal alloy.
  • Such gels contain the organic viscosity agent, preferably the polyacrylic acid at a concentration generally of 2 to 12% by weight.
  • the viscosing agent is a polyacrylic acid, more preferably a polyacrylic acid, of relatively high weight average molecular weight, for example 4 000 000, but one can also implement TEXIPOL, for example TEXIPOL 63-510, already described above.
  • This type of gel comprises, in addition to said viscosity agent, a surfactant or surfactant as defined above, preferably C 6 E 2 or C 12 E 4 , at a concentration of 0.1 to 1.5% by weight. .
  • the decontaminant gels described above can be used in particular for the decontamination of metal surfaces and this, both as part of the periodic maintenance of existing installations, as the dismantling of nuclear facilities.
  • the gels according to the invention can be used for example for decontaminating tanks, fuel storage tanks, glove boxes, etc.
  • the subject of the invention is also a process for the decontamination of a metal surface, which comprises the application on the surface to be decontaminated of a decontaminating gel according to the invention, the maintenance of this gel on the surface for a period of time. sufficient to carry out the decontamination, this duration for example of 10 min. at 24 hours, preferably from 30 minutes to 10 hours, and more preferably from 2 to 5 hours, and the removal of this gel from the metal surface thus treated, for example by rinsing or by mechanical action.
  • the surface to be decontaminated may be a surface whose temperature is, even permanently, greater than or equal to 40 ° C, by for example, from 40 ° C to 80 ° C.
  • the amounts of gel deposited on the surface to be decontaminated are generally from 100 to 2000 g / m 2 , preferably from 100 to 1000 g / m 2 , more preferably from 200 to 800 g / m 2 .
  • the treatment can be repeated several times by using each time the same gel or gels of different natures during the different successive stages, each of these stages comprising the application of a gel, the maintenance of the gel on the surface and removal of the gel from the surface, for example by rinsing or mechanical action.
  • the treatment may be repeated over the entire surface to be treated or only a part thereof having for example a complex shape, or depending on the activity of the surface (mRad / h) in some particular points of it requiring intensive treatment.
  • the contact time may vary within wide limits and also depends on the nature of the active decontamination agent and the nature of the organic viscosity agent.
  • the contact time is preferably from 30 minutes to 5 hours, more preferably from 2 to 5 hours.
  • the contact time will preferably be from 10 minutes to 5 hours.
  • the application of the gel to the metal surface to be decontaminated may be carried out by conventional methods, for example by spraying, dipping and draining, by packaging or by means of a paintbrush.
  • the gel spray / spray gun for example under a pressure (airless compressor) at the injector from 10 to 200 kg / cm 2 for example, from 10 to 160 kg / cm 2 , for example still from 50 to 100 kg / cm 2 .
  • the gel can be removed, preferably by rinsing, from the treated surface, it can also be removed by other means, for example mechanical or by a jet of gas, for example compressed air.
  • Rinsing is usually carried out with deionized water or an aqueous solution in which the gel used can be dissolved or in which it can form a release film which is water-entrainable.
  • Rinsing can be carried out under pressure, that is to say at a pressure of, for example, 10 to 160 kg / cm 2 .
  • the gels according to the invention comprising an organic-only viscosing agent, retain for a prolonged period of time, up to 48 hours and more, their gel texture, the rinsing the surface is much easier, can be done at low pressure for example 15 kg / cm 2 , or even without pressure and requires a reduced amount of demineralized water or other, for example less than 10 liters / m 2 .
  • the number of rinsing treatments (or passes) during a decontamination operation is reduced, since the gel according to the invention does not contain any mineral filler.
  • the gels of the prior art the viscosity of which is inorganic, in part or in whole, and which comprise for example only silica, become after application, and in a relatively short time, dry and cracked, their rinsing is very difficult and requires a high amount of water under high pressure. As a result, large quantities of liquid effluents are generated.
  • the rinsing effluents are then suitably treated, for example they can be neutralized, for example with sodium hydroxide in the case where an acid gel has been used.
  • the effluents are then generally subjected to a solid-liquid separation, for example by filtration with a cartridge filter to give on the one hand liquid effluents, and on the other hand solid waste whose quantity is extremely reduced, or even zero, because of the very low mineral charge of the gels according to the invention which in fact only comes from the active decontamination agent.
  • the amount of mineral filler in the gel according to the invention is even so small that it makes it possible to transfer the rinsing effluents to an evaporator without any prior treatment.
  • the decontaminant gels of the invention can be prepared in a simple manner, for example by adding to an aqueous solution of component b), that is to say of the active agent for decontamination, the viscosifying agent a) exclusively organic .
  • the viscosifying agent a) exclusively organic .
  • a mineral acid chosen, for example, from HNO 3 , HCl, H 3 PO 4 , H 2 SO 4 and mixtures thereof, preferably HNO 3
  • the following preparation process was particularly advantageous, especially in terms of preparation time: the viscosing agent a) and a solution of mineral acid with stirring are mixed first.
  • the gels according to the invention generally have a very long storage time, however the chemical inertness of some surfactants although good is limited in time, for example in the presence of an oxidant such as Ce (IV).
  • Acidic oxidizing gels whose active agent is (NH 4 ) 2 Ce (NO 3 ) 6 in nitric acid and which comprise an acrylic acid-acrylamide copolymer, namely TEXIPOL 63 510, have been prepared as the organic viscosity agent.
  • the prepared gels comprise silica (CaS O Sil M5) and are based on the gels described in document FR-A-2 746 328.
  • These gels are prepared in the following manner: the nitric acid solution and the "TEXIPOL" are moderately heated to a temperature of about 50 ° C with stirring, the time to obtain a homogeneous mixture, this time can go from about 24 hours to about 48 hours.
  • Table I below groups together the different compositions of the samples prepared. ⁇ u> Table I ⁇ / u> No. SiO 2 (CabosilM5) in g Texipol 63510 in g (NH 4 ) 2 Ce (NO 3 ) (1M) 6 in g HNO 3 (2.88M) in g 1 4 1.5 38.4 56.1 2 3 two 38.4 56.6 3 two 3 38.4 56.6 4 1 4 38.4 56.6 5 0.5 5 38.4 56.1 6 0.5 8 38.4 53.1
  • Oxidizing gels without any mineral filler were prepared in the following manner: TEXIPOL®, whose concentration is greater than 5% by weight, is added under heating to the nitric acid solution, and forms a homogeneous solution. Then just add (NH 4 ) 2 Ce (NO 3 ) 6 .
  • Demixing occurs at the time of mixing. It is necessary to wait for a while while maintaining a moderate agitation (3 to 10 days) according to the composition of the gel in TEXIPOL® and in (NH 4 ) 2 Ce (NO 3 ) 6 before obtaining the gel.
  • Cerium low concentration gels (# 7, # 8, and # 9) are found to be less viscous than their higher concentration counterparts. Their color is also paler.
  • Table IV gives the compositions of each of the TEXIPOL constant concentration gels. ⁇ u> Table IV ⁇ / u> Number Last name Texipol 63510 in g (NH 4 ) 2 Ce (NO 3 ) 6 in g HNO 3 (2.88M) in g 18 Tg11.1 11 33.5 55.5 19 Tg11.2 11 34.5 54.5 20 Tg11.3 11 35.5 53.5 21 Tg11.4 11 36.5 52.5
  • the most important corrosion power reaches 0.3 ⁇ m for Gel No. 1, after a single treatment of two hours and a gel quantity equal to 1 kg / m 2 .
  • the corrosive power seems to be limited to a value close to 0.4 ⁇ m. it is indeed the maximum thickness eroded during the experiment on a duration of application of 14 hours (n ° 2). The gel became colorless, translucent and did not dry; it is easily cleaned with water under low pressure.
  • the gels that possess the strongest corroding powers are tg11.1 and tg11.2 which paradoxically have the lowest initial Ce (IV) titers. Furthermore, it is observed that the faster the setting time of the gel is better corrosion. In fact, the oxidation of the polymer decreases the concentration of Ce (IV) in the gel. However, the higher the initial cerium titre, the longer the gel setting time is.
  • An optimal formulation is a balance between a percentage by weight of Texipol and an ideal Ce (IV) concentration, which should not be too low, resulting in low corrosion; neither too strong, which gives a long setting time and therefore low corrosion.
  • the optimum percentage of Texipol must be both sufficient to confer a value of the viscosity necessary for the adhesion of the gel, and minimal in order to allow good corrosion.
  • the polymer and the nitric acid solution are mixed.
  • the polymer solubilizes rapidly with manual stirring for about a quarter of an hour.
  • a highly viscous and homogeneous gel of whitish appearance is thus obtained.
  • This acid gel has a long life and can be prepared several days in advance.
  • adding (NH 4 ) 2 Ce (NO 3 ) 6 ensuring that the mixture is always homogeneous.
  • the formation of (NH 4 ) 2 Ce (NO 3 ) 6 lumps is avoided.
  • the addition of diammonium hexanitrotoketate results in a fluidification of the mixture. A rest of the mixture of approximately one hour is necessary in order to obtain a projectable gel.
  • This example illustrates the influence of the nitric acid concentration on the corrosion properties of the gels.
  • the 2.88M gel in HNO 3 corrodes better than the 2M gel.
  • the loss of mass is greater than 26 mg which corresponds to an additional erosion of 32%.
  • the role played by the title in nitric acid is determining in erosion for a constant concentration of (NH 4 ) 2 Ce (NO 3 ) 6 .
  • a powerful formulation D (see below) could thus be developed.
  • Gels A and B were prepared to decrease the (NH 4 ) 2 Ce (NO 3 ) 6 titre in order to further reduce the mineral filler while maintaining a good corrosion power.
  • gel B did not flow after 4 hours of application. It rinses very easily. Erosion is 102 mg or 1.22 ⁇ m.
  • the eroded thickness values are spread in a narrow range of 0.66 to 0.77 ⁇ m for a duration of two hours. No change in the corrosion power of the gel is observed in the time considered from t 0 to t 0 + 6h.
  • the gel C is applied on a vertical wall (wall) or on an upside down horizontal wall (ceiling) for at least four hours to check the good adhesion of the freeze during the erosion process.
  • the gel is spread on a horizontal surface (ground) for two hours. Whatever the method of application (wall, ceiling or floor), the gel did not sink and rinsing was very easy.
  • the thickness eroded as a function of the duration of application of the gel was measured. Rinsing the gel is in any case very easy.
  • the erosion limit of gel C in the first pass is 120 mg (1.44 microns) for a duration of application of 12 hours.
  • the duration of application influences corrosion which is important during the first four hours of contact.
  • the amount of gel applied influences the corrosion.
  • the mass losses were 94 mg at a rate of 1 kg / m 2 and 56 mg at a rate of 0.5 kg.
  • the corrosion power does not decrease during the first hours of use of the gel (more than 24 hours). However, the corrosion experiments conducted with gels having been prepared for 24 hours have shown that the corrosion decreases slightly. In fact, a limit corrosion of 1.44 ⁇ m is passed for a gel applied immediately after it has been prepared, for 12 hours, with a limiting corrosion of 1.04 ⁇ m for an applied liquid gel. hours after its preparation.
  • a second gel pass always increases the corrosion power when the passes are made from a gel taken at the same "age" (in the first six hours the gel corrosion does not decrease). For example, there is corrosion in first class of 1.28 microns at an erosion of 1.45 microns in the second pass for two successive passes of 4 hours each of a gel C.
  • a characteristic common to all gels is a 24 hour shelf life beyond which the gel gradually loses its viscous structure.
  • This example illustrates the influence of polymer concentration on corrosion.
  • the increase in the percentage of polymers in the medium leads to a reduction in the corrosion power.
  • the viscosity of the gels increases with the polymer concentration of P1 to P4.
  • excessive viscosity of the gels leads to a non-homogeneous spread on the surface. These lumps of gels remain red during the time of application and therefore do not allow a participation in the corrosion of the entire amount of gel applied initially.
  • Table IX gathers the data on P1, P2, P3 and P4.
  • the duration of application of the gel is three hours and the amount applied is 1 kg / m 2 .
  • Table IX ⁇ / u> Gel Polymer [4] in g (NH 4 ) 2 Ce (NO 3 ) 6 in g HNO 3 2.88 M in g Mass lost in mg Thickness in ⁇ m P1 4 57.8 38.2 74 0.89 P2 4.6 57.5 37.9 72 0.86 P3 5.1 57.2 37.7 62 0.74 P4 5.7 56.8 37.5 58 0.70
  • This example illustrates the influence of cerium concentration on corrosion.
  • Samples A1, B1, C1 and D1 confirm the influence of the concentration of Ce (IV) on the corrosion power in a medium containing a polyacrylic acid polymer.
  • the significant increase in the Ce (IV) titre increases the corrosion power.
  • a second pass gives a lower erosion. For example, for Cl, with an average erosion of 0.31 ⁇ m / h when the corrosion is carried out on the same day as that of the synthesis, the limit becomes 0.26 ⁇ m / h when the corrosion is carried out the day after the synthesis. . This confirms the gradual loss of the corrosion power of the gels over time.
  • Table X collects the data for A1, B1, C1 and D1.
  • the 1.25 million polymer gives the medium a lower viscosity but it offers a more homogeneous structure (without lumps) and a more flexible structure that allows a good spreading of the gel.
  • the corrosion limit of an A8 gel is 1.54 ⁇ m for an application time of 18 hours.
  • the corrosion power of a viscose gel with a polymer of 4 million is superior to a viscose gel with a polymer of 1.25 million (B8 corrodes 0.28 microns).
  • the lifetime of all gels with 0.5% of silica is of the order of that of the gels "all polymer": is about 24 hours.
  • Table XII collects the data relating to the corrosion experiments of the viscosity gels with a polyacrylic acid polymer (4,000,000 and / or 1,250,000), and coviscosed with 0.5% silica. ⁇ u> Table XII ⁇ / u> No.
  • gels incorporating a polyacrylic acid and a polyoxyethylene surfactant were prepared.
  • ceric solution (NH 4 ) 2 Ce (NO 3 ) 6 (1.2M) + HNO 3 (2M) is mixed directly with the polymer and the surfactant. The mixture is homogenized by stirring.
  • Table XIV summarizes the data on the corroding power of these gels.
  • gels comprise sodium hydroxide or sodium borohydride in sodium hydroxide as active agents. Gels containing alumina have also been prepared for comparison.
  • Table XVI gathers the compositions of these basic gels according to the invention.

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Claims (39)

  1. Dekontaminationsgel, das aus einer Lösung besteht, die
    a) ein viskosmachendes Mittel,
    b) ein zur Dekontamination wirksames Mittel umfasst,
    wobei das viskosmachende Mittel a) ein ausschließlich organisches viskosmachendes Mittel ist, das ein wasserlösliches organisches Polymer ist, das aus Acrylsäurepolymeren und Copolymeren von Acrylsäure mit Acrylamid ausgewählt ist; wobei das Gel ferner ein organisches grenzflächenaktives Mittel umfasst, das aus den Polyoxyethylenethern der Formel (II)

            CH3-(CH2)n-1-(O-CH2-CH2)m-OH     (II)

    die auch als CnEm bezeichnet werden,
    worin n eine ganze Zahl von 6 bis 18 ist und m eine ganze Zahl von 1 bis 23 ist, ausgewählt ist.
  2. Gel nach Anspruch 1, wobei das organische Polymer mit einem Gehalt von 1 bis 11 Gew.-%, vorzugsweise 2 bis 8 Gew.-% vorhanden ist.
  3. Gel nach einem der Ansprüche 1 und 2, wobei das Polymer eine Gewichts-Molmasse von 200 000 bis 5 000 000 g/mol aufweist.
  4. Gel nach Anspruch 1, wobei das Copolymer von Acrylsäure mit Acrylamid der Formel (I) entspricht:
    Figure imgb0004
  5. Gel nach Anspruch 1, wobei das grenzflächenaktive Mittel der Formel (II) die Verbindung der Bezeichnung C6E2 (Diethylenglykol)hexylether), die Verbindung der Bezeichnung C10E3 oder die Verbindung der Bezeichnung C12E4 ist.
  6. Gel nach Anspruch 1, wobei das organische grenzflächenaktive Mittel mit einem Gehalt von 0,1 bis 5 Gew.-% vorhanden ist.
  7. Gel nach einem der Ansprüche 1 bis 6, das als "saures Gel" bezeichnet wird, das dadurch gekennzeichnet ist, dass das zur Dekontamination wirksame Mittel b) eine Mineralsäure umfasst.
  8. Gel nach Anspruch 7, das dadurch gekennzeichnet ist, dass die Mineralsäure aus Salzsäure, Salpetersäure, Schwefelsäure, Phosphorsäure und deren Gemischen ausgewählt ist.
  9. Gel nach Anspruch 7, das dadurch gekennzeichnet ist, dass die Mineralsäure in einer Konzentration von 1 bis 10 mol/l vorhanden ist.
  10. Gel nach einem der Ansprüche 1 bis 6, das dadurch gekennzeichnet ist, dass das zur Dekontamination wirksame Mittel b) eine anorganische Base umfasst.
  11. Gel nach Anspruch 10, das dadurch gekennzeichnet ist, dass die anorganische Base aus Natriumcarbonat, Kaliumcarbonat und deren Gemischen ausgewählt ist.
  12. Gel nach Anspruch 10, das dadurch gekennzeichnet ist, dass die anorganische Base in einer Konzentration von 0,1 bis 14 mol/l vorhanden ist.
  13. Gel nach einem der Ansprüche 1 bis 6, das als "reduzierendes Gel" bezeichnet wird, das dadurch gekennzeichnet ist, dass das zur Dekontamination wirksame Mittel b) ein Reduktionsmittel umfasst.
  14. Gel nach Anspruch 13, das dadurch gekennzeichnet ist, dass das Reduktionsmittel ein Redoxstandardpotential E0 von unter -600 mV/NWE (Normalwasserstoffelektrode) in stark basischer Umgebung (pH ≥ 13) hat.
  15. Gel nach Anspruch 13, das dadurch gekennzeichnet ist, dass das Reduktionsmittel in einer Konzentration von 0,1 bis 4,5 mol/l vorhanden ist.
  16. Gel nach Anspruch 14, das dadurch gekennzeichnet ist, dass das Reduktionsmittel aus Borhydriden, Sulfiten, Hydrogensulfiten, Sulfiden, Hypophosphiten, Zink, Hydrazin und deren Gemischen ausgewählt ist.
  17. Gel nach Anspruch 14, das dadurch gekennzeichnet ist, dass das wirksame Mittel b) ferner eine anorganische Base in einer Konzentration von 0,1 bis 14 mol/l umfasst.
  18. Gel nach einem der Ansprüche 1 bis 6, das als "oxidierendes Gel" bezeichnet wird, das dadurch gekennzeichnet ist, dass das zur Dekontamination wirksame Mittel b) ein Oxidationsmittel oder die reduzierte Form dieses Oxidationsmittels umfasst.
  19. Gel nach Anspruch 18, das dadurch gekennzeichnet ist, dass das Oxidationsmittel ein Redoxstandardpotential E0 von über 1400 mV/NWE (Normalwasserstoffelektrode) in stark saurer Umgebung (pH < 1) hat.
  20. Gel nach Anspruch 18, das dadurch gekennzeichnet ist, dass das Oxidationsmittel in einer Konzentration von 0,1 bis 2 mol/l vorhanden ist.
  21. Gel nach Anspruch 19, das dadurch gekennzeichnet ist, dass das Oxidationsmittel aus CeIV, AgII, CoIII und deren Gemischen ausgewählt ist.
  22. Gel nach Anspruch 21, das dadurch gekennzeichnet ist, dass CeIV in der Form von Cernitrat, Cersulfat oder Diammoniumhexanitratocerat, vorhanden ist.
  23. Gel nach Anspruch 19, das dadurch gekennzeichnet ist, dass das oxidierende Gel außer der reduzierten Form des Oxidationsmittels eine Verbindung mit der Fähigkeit zur Oxidation der reduzierten Form dieses Oxidationsmittels umfasst.
  24. Gel nach Anspruch 23, das dadurch gekennzeichnet ist, dass die Verbindung mit der Fähigkeit zur Oxidation der reduzierten Form des Oxidationsmittels ein Alkalimetallpersulfat ist.
  25. Gel nach Anspruch 19, das dadurch gekennzeichnet ist, dass das aktive Mittel b) außer dem Oxidationsmittel eine Mineralsäure oder eine anorganische Base in einer Konzentration von 1 bis 10 mol/l umfasst.
  26. Gel nach Anspruch 25, das dadurch gekennzeichnet ist, dass die Mineralsäure aus HNO3, HCl, H3PO4, H2SO4 und deren Gemischen ausgewählt ist.
  27. Alkalisches Dekontaminationsgel nach Anspruch 10, das aus einer Lösung besteht, die umfasst:
    - 9 bis 11 Gew.-% an einem Acrylsäure-Acrylamid-Copolymer eines Gewichtsmittels der Molmasse von 200 000, das 20 Gew.-% Acrylamid enthält,
    - 1 mol/l bis 12 mol/l, vorzugsweise 3 mol/l Natriumcarbonat.
  28. Reduzierendes Dekontaminationsgel nach Anspruch 17, das aus einer Lösung besteht, die umfasst:
    - 9 bis 11 Gew.-% an einem Acrylsäure-Acrylamid-Copolymer eines Gewichtsmittels der Molmasse von 200 000, das 20
    Gew.-% Acrylamid enthält;
    - 1 bis 12 mol/l, vorzugsweise 3 mol/l Natriumcarbonat;
    - 1 bis 4 mol/l, vorzugsweise 3 mol/l NaBH4.
  29. Oxidierendes Dekontaminationsgel nach Anspruch 18, das aus einer Lösung besteht, die umfasst:
    - 10 bis 13 Gew.-% an einem Acrylsäure-Acrylamid-Copolymer eines Gewichtsmittels der Molmasse von 200 000, das 20 Gew.-% Acrylamid enthält;
    - 2 bis 3 mol/l, vorzugsweise 2,88 mol/l HNO3;
    - 0,1 bis 2 mol/l (NH4)2Ce(NO3)6.
  30. Oxidierendes Dekontaminationsgel nach Anspruch 18, das aus einer Lösung besteht, die umfasst:
    - 0,6 bis 1,2 mol/l, vorzugsweise 0,9 mol/l (NH4)2Ce(NO3)6 oder Ce(NO3)4;
    - 2 bis 3 mol/l, vorzugsweise 2,88 mol/l HNO3;
    - 3 bis 4,5 Gew.-%, vorzugsweise 3,7 Gew.-% an einer Polyacrylsäure eines Gewichtsmittels der Molmasse von 4 000 000.
  31. Oxidierendes Dekontaminationsgel nach Anspruch 18, das dadurch gekennzeichnet ist, dass es aus einer Lösung besteht, die umfasst:
    - 7 bis 8 Gew.-%, an einer Polyacrylsäure eines Gewichtsmittels der Molmasse von 450 000;
    - 2 bis 3 mol/l, vorzugsweise 2,88 mol/l HNO3;
    - 0,1 bis 2 mol/l (NH4)2Ce(NO3)6;
    - bis zu 1 Gew.-% an grenzflächenaktiven Mitteln, vorzugsweise C6E2 oder C12E4.
  32. Verfahren zur Herstellung eines oxidierenden Gels nach Anspruch 25 oder 26, wobei das wirksame Mittel b) außer dem Oxidationsmittel eine Mineralsäure umfasst, wobei zuerst unter Rühren und gegebenenfalls Erhitzen das viskosmachende Mittel a) und eine Mineralsäurelösung gemischt werden, um das Polymer zu solubilisieren und um ein viskoses und homogenes saures Gel zu erhalten, und dann zu dem sauren Gel unter Rühren das Oxidationsmittel, wie (NH3)2Ce(NO3)6, gegeben wird.
  33. Verfahren zur Dekontamination einer Metalloberfläche, das die Applikation eines Gels nach einem der Ansprüche 1 bis 31 auf die zu dekontaminierende Oberfläche, das Halten dieses Gels auf der Oberfläche während einer zur Durchführung der Dekontamination ausreichenden Zeitspanne und die Entfernung des Gels von der auf diese Weise behandelten Metalloberfläche umfasst.
  34. Verfahren nach Anspruch 33, wobei die zu dekontaminierende Oberfläche eine Temperatur von höher als oder gleich 40 °C aufweist.
  35. Verfahren nach Anspruch 33, wobei das Gel durch Zerstäuben mit einer Pistole appliziert wird.
  36. Dekontaminationsverfahren nach Anspruch 33, wobei das Gel auf der Oberfläche während einer Zeitspanne, die zwischen 10 min und 24 h umfasst, gehalten wird.
  37. Dekontaminationverfahren nach Anspruch 33, wobei das Gel ein saures oxidierendes Gel ist und auf die Oberfläche während eines Zeitraums, der zwischen 2 und 5 h umfasst, appliziert wird.
  38. Verfahren nach Anspruch 33, wobei das Gel von der Oberfläche durch Abspülen entfernt wird.
  39. Verfahren nach Anspruch 33, wobei das Gel auf der Oberfläche in einer Menge von 100 g bis 2000 g/m2 appliziert wird.
EP00964318A 1999-09-20 2000-09-19 Organisches gel zur dekontaminierung und seine verwendung zur dekontaminierung von oberflächen Expired - Lifetime EP1228512B1 (de)

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FR9911741A FR2798603B1 (fr) 1999-09-20 1999-09-20 Gel organique de decontamination et son utilisation pour la decontamination de surfaces
FR9911741 1999-09-20
PCT/FR2000/002592 WO2001022431A1 (fr) 1999-09-20 2000-09-19 Gel organique de decontamination et son utilisation pour la decontamination de surfaces

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FR2827530B1 (fr) * 2001-07-17 2004-05-21 Commissariat Energie Atomique Procede de traitement d'une surface par un gel de traitement, et gel de traitement
FR2841802B1 (fr) * 2002-07-08 2005-03-04 Commissariat Energie Atomique Composition, mousse et procede de decontamination de surfaces
FR2853129B1 (fr) * 2003-03-28 2005-09-09 Salvarem Procede et produit de decontamination radioactive
CA2595837A1 (en) * 2004-12-08 2006-08-10 Armordynamics, Inc. Methods and apparatus for providing ballistic protection
FR2891470B1 (fr) * 2005-10-05 2007-11-23 Commissariat Energie Atomique Gel aspirable pour la decontamination de surfaces et utilisation
EP2056302B1 (de) 2007-10-29 2011-12-21 Atomic Energy Council - Institute of Nuclear Energy Research Dekontaminierungsverfahren für eine durch radioaktive Elemente kontaminierte Metalloberfläche
EP2970836B1 (de) 2013-03-15 2020-10-14 Klear Solutions Mehrzweckreiniger für harte oberflächen
CN109799528B (zh) * 2019-01-17 2022-08-19 中国辐射防护研究院 用于放射性污染金属浅层取样的氧化凝胶及其制备方法

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JPS4937010B1 (de) * 1968-11-26 1974-10-04
JPS4937010A (de) 1972-08-17 1974-04-06
JPS51147486A (en) * 1975-06-12 1976-12-17 Dai Ichi Kogyo Seiyaku Co Ltd Thickener for inorganic acid
FR2380624A1 (fr) * 1977-02-09 1978-09-08 Commissariat Energie Atomique Procede de decontamination radioactive d'une piece
JPS546820A (en) * 1977-06-18 1979-01-19 Nishiyama Sutenresu Kemikaru K Acidic cleaning agent for stainless steel
EP0047857A3 (de) * 1980-09-13 1982-06-23 Nukem GmbH Verfahren zur Dekontamination radioaktiv verunreinigter Oberflächen
US4529450A (en) * 1983-10-18 1985-07-16 The United States Of America As Represented By The Secretary Of The Navy Metal oxide remover and method of using
FR2656949B1 (fr) * 1990-01-09 1994-03-25 Commissariat A Energie Atomique Gel decontaminant et son utilisation pour la decontamination radioactive de surfaces.
JPH03260081A (ja) * 1990-03-09 1991-11-20 Kaiho Giken:Kk ペースト状酸洗浄剤
FR2690163A1 (fr) * 1992-04-17 1993-10-22 Commissariat Energie Atomique Procédé de décontamination de la couche superficielle d'un sol recouvert de particules polluantes et solution de décontamination.
FR2695839B1 (fr) * 1992-09-23 1994-10-14 Commissariat Energie Atomique Gel décontaminant réducteur et son utilisation pour la décontamination de surface notamment d'installations nucléaires.
FR2746328B1 (fr) * 1996-03-21 1998-05-29 Stmi Soc Tech Milieu Ionisant Gel organomineral de decontamination et son utilisation pour la decontamination de surfaces
FR2781809B1 (fr) * 1998-07-31 2002-06-07 Commissariat Energie Atomique Composition de degraissage et procedes utilisant cette composition
US6670281B2 (en) * 1998-12-30 2003-12-30 Honeywell International Inc. HF etching and oxide scale removal

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