EP0928489B1 - Organomineralgel zur dekontamination von oberflächen - Google Patents

Organomineralgel zur dekontamination von oberflächen Download PDF

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Publication number
EP0928489B1
EP0928489B1 EP97915523A EP97915523A EP0928489B1 EP 0928489 B1 EP0928489 B1 EP 0928489B1 EP 97915523 A EP97915523 A EP 97915523A EP 97915523 A EP97915523 A EP 97915523A EP 0928489 B1 EP0928489 B1 EP 0928489B1
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EP
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Prior art keywords
gel
agent
accordance
mineral
decontamination
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English (en)
French (fr)
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EP0928489A1 (de
Inventor
Stéphane BARGUES
Frédéric FAVIER
Jean-Louis Résidence es Facultés PASCAL
Jean-Pierre Lecourt
Frédérique DAMERVAL
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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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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/903—Two or more gellants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S588/00—Hazardous or toxic waste destruction or containment
    • Y10S588/901—Compositions

Definitions

  • the present invention relates to a gel organomineral decontamination usable for radioactive decontamination of surfaces, in particular of metal surfaces.
  • Decontamination of parts soiled by radioactive elements can be carried out either by mechanical treatments, either by treatments chemical.
  • Methods using mechanical treatments have the disadvantage to cause a more or less significant modification from the surface of the room and to be, moreover, difficult to implement on shaped parts complicated.
  • Soaking treatment methods which basically consist of training the elements radioactive attached to the workpiece surface using solutions of active decontamination agents suitable, in particular Ce (IV) stabilized in strong concentrated acid medium such as nitric acid or sulfuric, have the disadvantage of leading to the production of large volumes of effluent including further treatment, in particular by concentration, is very expensive.
  • dipping methods implementing solutions pose some problems for handling large parts dimensions that are difficult to immerse and soak completely in the reagent solution.
  • Decontamination solutions do not allow soaking treatment only removable metal parts of limited sizes, that is to say that these solutions cannot in practice only be used for dismantling radioactive installations.
  • mineral supports such as aluminas and commercially available silicas which also present a wide variety of their characteristics such as hydrophilicity, hydrophobic, pH Vietnamese crystals, appear to be the best means of viscosing / gelling these solutions.
  • Spraying such gels can allow decontamination on large metal surfaces that are not not necessarily horizontal, but which can be also inclined or even vertical.
  • Decontamination gels can therefore be described as colloidal solutions comprising a generally mineral viscous agent such as alumina or silica and an active agent of decontamination, for example an acid, a base, a oxidizing agent, reducing agent or mixture of these, which is chosen notably according to the nature of contamination and surface.
  • a generally mineral viscous agent such as alumina or silica
  • an active agent of decontamination for example an acid, a base, a oxidizing agent, reducing agent or mixture of these, which is chosen notably according to the nature of contamination and surface.
  • An oxidizing gel for stainless steels will allow elimination of hot fix contamination and cold.
  • a reducing gel will preferably be used in supplement of the oxidizing gel and alternately for dissolution of hot formed oxides for example in the primary circuit of water reactors pressurized (REP).
  • a gel decontaminant consisting of a colloidal solution an organic or mineral compound to which we add possibly a decontaminating product such as acid hydrochloric acid, stannous chloride, oxine and / or sodium fluoride.
  • Document FR-A-2 656 949 describes a gel oxidizing decontaminant which eliminates radioactive elements deposited on the part as well as the radioactive elements encrusted on its surface.
  • the gel includes plus 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) ensures respectively the elimination of radioactive deposits formed on the workpiece surface and removing embedded radioactivity, by controlled erosion of the surface to be decontaminated.
  • This oxidizing gel does not, however, sufficient effectiveness with regard to the layers adherent metal oxides deposited on the surface alloys such as austenitic steels, Inconel 600 and the Incoloy.
  • EP-A-0 674 323 relates to a gel for radioactive decontamination of surfaces consisting of a colloidal solution comprising a gelling agent and a fibrogenic agent based on silica. This document also mentions that an acrylic copolymer can be added to the colloidal aqueous solution.
  • FEVDIRAD Typical gels of the prior art are marketed by FEVDI under the name of "FEVDIRAD"
  • Control of this thixotropy is fundamental to allow projection and optimal adhesion of the gel to the surface to be treated.
  • the speed of resumption of freezes, or restructuring partial or total, constitutes the primordial concept for their projection.
  • restructuring means a back to gelation, therefore adhesion to the surface, and a short recovery time characterizes a gel quickly recovering sufficient viscosity after projection to avoid any sagging.
  • the factors of decontamination obtained must be at least identical to those of existing gels.
  • the object of the present invention is therefore to provide a decontamination gel that meets between others to all of the needs mentioned above.
  • viscosity agent a) decontamination gel in addition mineral viscosity agent, viscosity agent specific organic (called coviscosant) allows so surprising, in particular, to greatly improve rheological properties of gels, and decrease significantly the mineral load of these gels without that the corrosive properties and other qualities of these gels are not affected.
  • coviscosant viscosity agent specific organic
  • Decontamination factors obtained with the gels according to the invention are completely comparable or even superior to those of gels analogs of the prior art, i.e. gels comprising the same decontamination agent but without coviscosant.
  • the effectiveness of the decontamination agent implemented is absolutely not affected by the presence of a coviscosant in the gel according to the invention.
  • the gel according to the invention is obtained in adding component a) to an aqueous solution, that is to say a viscosifying / gelling agent which comprises the combination of a mineral viscosity agent and a organic viscosifier.
  • the mineral viscosity agent is generally an mineral viscosity agent which is insensitive to oxidation, resists the active decontamination constituents b), and preferably has a high specific surface, for example greater than 100 m 2 / g.
  • the gel has a viscosity of 10 -3 to 10 -1 Pa.sec, preferably 10 -2 Pa.sec at the time of use, that is to say under high shear to be able easily apply it to the surface of a part, for example by spraying with a spray gun.
  • the content of this mineral viscosity agent can generally be lowered for example to less than 20% by weight, for example still from 1 to 15% by weight, preferably from 1 to 8% by weight, more preferably from 1 to 7% by weight, for example from 4 to 6% by weight, in particular 5% in weight.
  • the content of mineral viscosity agent can be lowered for example up to 1 to 15% by weight, preferably 1 to 8% by weight, more preferably from 1 to 7% by weight, per example from 4 to 6% by weight, in particular 5% by weight of the solution.
  • the content of mineral viscosity agent can represent for example less than 8%, for example from 1 to 7% and generally 4 to 6%, for example 5% by weight of the solution.
  • the mineral load of gel according to the invention is always greatly reduced compared to the equivalent gel comprising only one agent viscous mineral.
  • the mineral viscosifier / gelling agent can be based on alumina Al 2 O 3 and it can be obtained by hydrolysis at high temperature.
  • a viscous / gelling mineral agent which can be used, mention may be made of the product sold under the trade designation "Alumina C”.
  • the mineral viscosifier / gelling agent can also be based on silica; this silica can be hydrophilic, hydrophobic, basic like silica marketed under the name "Tixosil 73" by the Company RHONE-POULENC or acid such as silicas marketed under the names of "TIXOSIL 331" and "TIXOSIL 38AB” by the company RH ⁇ NE-POULENC.
  • silicas in liquid form sold under the names of "SNOWTEX O” and “SNOWTEX OL” by the Company Nissan Chemical Industries, and silicas marketed under the general name of "Cab-O-Sil” by Degussa Company such as “Cab-O-Sil” silicas M5 "Cab-O-Sil” H5 and "Cab-O-Sil” EH5.
  • pyrogenic silica "Cab-O-Sil” hydrophilic and acidic M5 with a specific surface of 200 m 2 / g is preferred and gives the best results: that is to say maximum viscous properties for a minimum mineral charge, in particular when it is used in so-called “oxidizing gels”.
  • the viscosity agent a further comprises the mineral viscosity agent described above an agent specific organic viscosant.
  • This organic viscosity agent again called “coviscosant” is chosen from among polyoxyethyethylene ethers responding to the formula given above.
  • This coviscosant must meet a number of conditions related in particular to its use in nuclear installations.
  • the surfactants of the family of polyoxyethylene ethers of formula: CH 3 - (CH 2 ) n-1 - (O - CH 2 - CH 2 ) m - OH also called C n E m fulfilled the required criteria, that is to say among other things a great affinity for mineral particles, in particular silica, and a great chemical inertness and sufficient stability in particular in very acidic environments, very oxidizing and electrolytically strong like decontamination gels.
  • 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 from 2 to 6.
  • the compounds C 6 E 2 hexyl ether of di (ethylene glycol)
  • C 10 E 3 and C 12 E 4 are preferred.
  • Such compounds C n E m are available from the companies ALDRICH and SEPPIC.
  • the nature of the surfactant depends on the type of decontamination gel used, i.e. the nature and content of the active agent decontamination b) and the nature and content of the mineral viscosity agent.
  • the compounds C n E m are particularly suitable for use in acid oxidizing gels comprising silica.
  • the surfactant content depends on the nature of the decontamination gel as well as the concentration and nature of the viscosity agent mineral.
  • This surfactant content will be generally between 0.1 and 5% by weight, preferably between 0.2 and 2% by weight, preferably still between 0.5 and 1% by weight.
  • the viscosity agent a) according to the invention can be used in any decontamination gel whatever either the type of it, that is to say whatever the active decontamination agent b) used in decontamination gel.
  • decontamination gels are of different natures depending on the active agent of decontamination b) they contain; we distinguish in general so-called alkaline gels, acid gels, reducing gels and oxidizing salts.
  • the decontamination gel according to the invention may contain as active agent decontamination b) an acid, preferably an acid mineral preferably chosen from acid hydrochloric, nitric acid, sulfuric acid, phosphoric acid and their mixtures.
  • an acid preferably an acid mineral preferably chosen from acid hydrochloric, nitric acid, sulfuric acid, phosphoric acid and their mixtures.
  • the acid is usually present at a concentration from 1 to 10 mol / l, preferably from 3 to 10 mol / l.
  • Such a gel called “acid gel” is particularly suitable for eliminating contamination cold-set on ferritic steels.
  • the agent mineral viscosity is preferably silica and coviscosant is an ether polyoxyethylene.
  • the decontamination gel according to the invention may also contain as an active agent decontamination b), a base preferably a base mineral preferably chosen from soda, potash and their mixtures.
  • a base preferably a base mineral preferably chosen from soda, potash and their mixtures.
  • the base is usually present at a concentration from 0.1 to 14 mol / l.
  • alkaline gel presents interesting degreasing properties and is particularly suitable for eliminating contamination not fixed on stainless and ferritic acids.
  • the agent mineral viscosity is preferably alumina.
  • the decontamination gel according to the invention may also contain as active decontamination 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 less than -600 mV / ENH (normal hydrogen electrode) in a strong base medium (pH ⁇ 13).
  • 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 less than -600 mV / ENH (normal hydrogen electrode) in a strong base medium (pH ⁇ 13).
  • Such agents reducing agents there may be mentioned borohydrides, sulfites, hydrosulfites, sulfides, hypophosphites, zinc, hydrazine and their mixtures.
  • borohydrides When using borohydrides, sulfites, sulfides, hydrosulfites or hypophosphites, these are usually in the form of salts metallic, for example of 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.
  • Reducing agents as described in document FR-A-2 695 839 are generally associated with a mineral base such as NaOH or KOH to a concentration generally between 0.1 and 14 mol / l, the concentration of reducing agent being, as to it, generally between 0.1 and 4.5 mol / l.
  • the viscosity agent mineral is rather based on alumina.
  • reducing gel is in general used in addition to and alternating with a gel oxidant as described below.
  • Such a gel makes it possible in particular to weaken and move the metal oxide layers adherent superficies which have been deposited hot on the surface of alloys such as steels austenitic stainless steels, the Inconel and the Incoloy which form the primary circuits of water reactors pressurized (REP) that are not sensitive to action oxidizing decontaminating gels.
  • alloys such as steels austenitic stainless steels, the Inconel and the Incoloy which form the primary circuits of water reactors pressurized (REP) that are not sensitive to action oxidizing decontaminating gels.
  • the decontamination gel according to the invention may still contain, as an active agent of decontamination b), an oxidizing agent.
  • This oxidizing agent can for example be a oxidizing agent such as that described in document FR-A-2 659,949 in which the oxidizing agent used is a oxidizing agent which must have normal potential oxidation-reduction higher than 1400 mV / ENH in medium strong acid (pH ⁇ 1), i.e. an oxidizing power higher than that of permanganate.
  • a oxidizing agent such as that described in document FR-A-2 659,949 in which the oxidizing agent used is a oxidizing agent which must have normal potential oxidation-reduction higher than 1400 mV / ENH in medium strong acid (pH ⁇ 1), i.e. an oxidizing power higher than that of permanganate.
  • oxidizing agents powerful particularly suitable when the surface to be decontaminate is a metallic surface, for example by noble alloy, such as stainless steel 304 and 316L, the Inconel and the Incolloy.
  • these oxidizing agents can also oxidize certain poorly soluble 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 one can use Ce III , Co II , Ag I , on condition of adding to the gel a compound capable of oxidizing this reduced form, or on condition that the gel is combined with another gel or with another colloidal solution containing a compound capable of oxidizing this reduced form of the oxidizing agent.
  • the compound capable of oxidizing the form reduced oxidizing agent can consist of for example with an alkali metal persulfate.
  • Oxidizing agents of which Cerium (IV) is preferred, 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 between 1 and 10 mol / l, preferably from 3 to 10 mol / l, more preferably from 2 to 3 mol / l, for example 2.88 mol / l, the concentration of oxidizing agent being, for its part, 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.
  • a mineral acid such as HCl, H 3 PO 4 , H 2 SO 4 and preferably HNO 3
  • the concentration of oxidizing agent being, for its part, 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
  • this can be introduced in the form of one of its salts such as nitrate, sulfate or the like, but it can also be electrogenerated .
  • Preferred oxidizing gels contain cerium (IV) in the form of electrogenerated cerium (IV) nitrate Ce (NO 3 ) 4 or hexanitrato diammonium cerate (NH 4 ) 2 Ce (NO 3 ) 6 , the latter being preferred due to the relative instability of cerium (IV) nitrate in concentrated nitric medium.
  • Nitric acid stabilizes the cerium at oxidation state IV, participates in corrosion and ensures, among other things, the maintenance in solution of corroded species, namely complex oxo-nitrato transition metals constituting the alloy metallic.
  • Such gels contain, for example, the mineral viscous agent, preferably silica such as "Cab-O-Sil” M5 at a concentration preferably of between 4 and 6% by weight, for example 5% by weight, and l organic viscosifying agent, which is a polyoxyethylene ether, for example of the C 6 E 2 , C 10 E 3 or C 12 E 4 type at a concentration preferably between 0.2 and 2% by weight, for example 1% by weight .
  • the mineral viscous agent preferably silica such as "Cab-O-Sil” M5 at a concentration preferably of between 4 and 6% by weight, for example 5% by weight
  • l organic viscosifying agent which is a polyoxyethylene ether, for example of the C 6 E 2 , C 10 E 3 or C 12 E 4 type at a concentration preferably between 0.2 and 2% by weight, for example 1% by weight.
  • the decontaminating gels described above can be used especially for the decontamination of metal surfaces and this, too well as part of periodic maintenance existing installations, only dismantling nuclear facilities.
  • the gels according to the invention can be used for example to decontaminate tanks, fuel storage pools, glove boxes etc.
  • the subject of the invention is also a method for decontaminating a metal surface, which includes applying it to the surface to decontaminate a decontaminating gel according to the invention, maintaining this gel on the surface for a period sufficient to carry out the decontamination, this duration ranging for example from 10 min. at 24 hrs, from preferably from 30 min to 10 h, and more preferably from 2 to 5 hours, and removing this gel from the surface metallic thus treated for example by rinsing or by mechanical action.
  • 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 on the entire surface to be treated or on a part only of it having for example a form complex, or depending on the activity of the surface (mRad / h) at certain particular points thereof requiring intensive treatment.
  • Contact time can vary between wide limits and also depends on the nature of the active decontamination agent and the nature of the "coviscosing" agent.
  • the contact time is preferably 30 min to 5 hours, more preferably 2 to 5 hours.
  • the contact time will preferably be 10 minutes to 5 hours.
  • the application of the gel to the metal surface to be decontaminated can be carried out by conventional methods, for example by spraying with a spray gun, by soaking and draining, by packaging or even by means of a brush.
  • the gel is applied by spraying / spraying with a spray gun, for example under a pressure (Airless compressor) at the level of the injector ranging from 10 to 200 kg / cm 2 for example, from 10 to 160 kg / cm 2 , again for example from 50 to 100 kg / cm 2 .
  • the gel can be removed, preferably by rinsing of the treated surface, you can also eliminate it by other means, for example mechanical or by a jet of gas, for example compressed air.
  • the rinsing can be carried out under pressure, that is to say at a pressure for example from 10 to 160 kg / cm 2 .
  • the gels according to the invention comprising the combination of an inorganic viscous agent such as silica, and an organic viscous agent described above, keep for a period prolonged, up to 48 hours or more, their gel texture, 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 demineralized or other water, 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 contains less mineral filler.
  • gels without coviscosants organic, without surfactant, art including only for example silica become after application, and in a while relatively short, dry and cracked, their rinsing is very difficult and requires a high amount of water under strong pressure. Therefore large quantities liquid effluents are generated.
  • the rinsing effluents are then treated adequately for example they can be neutralized, for example by soda in the case where an acid gel has been used.
  • the effluents are then generally subjected to 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 of which the quantity is extremely reduced due to the low mineral load of the gels according to the invention.
  • the amount of charge mineral in the gel according to the invention is even if low, that it makes it possible to transfer the effluents from rinsing to an evaporator without any treatment prior.
  • the decontaminating gels of the invention can be prepared in a simple way, for example by adding to an aqueous solution of component b), that is to say the active decontamination agent, viscosity agent a). Generally, we add the agent mineral viscosity agent such as silica before the agent organic viscosant (coviscosant).
  • the gels according to the invention generally have a very long storage period, however the inertia chemical of some surfactants although good is limited in time, for example in the presence of a oxidant such as Ce (IV).
  • the rheological properties of gels according to the invention by measuring their viscosity at different times, time 0 corresponding to the moment the frost is projected.
  • FIG. 2 represents the curves giving the viscosity as a function of the recovery time for gels of which the viscosity agent comprises the combination of an inorganic viscosity agent (silica "Cab-O-Sil”) and a surfactant according to the invention ("C 6 E 2 ", “C 10 E 3 “ or “C 12 E 4 "); or of a polymer (“Texipol”) each time at 1% by weight.
  • Gels prepared with combinations viscosifiers according to the invention are therefore, under agitation, and like the gels of the prior art, sufficiently liquid to allow projection.
  • the viscosity at rest of a gel according to the invention such as the gel, prepared with a viscosifying agent comprising 5% by weight of "Cab-O-Sil” and 1% by weight of surfactant C 6 E 2 is multiplied by up to 50 to reach 20 to 25 Pa.s.
  • the gels according to the invention therefore generate makes their mineral load significantly less large, less waste.
  • This example relates to the implementation oxidizing gels which include title of active decontamination agent, an agent oxidant which is Cerium (IV) and as an agent organic viscosant (coviscosant) of ethers polyoxyethylene according to the invention; or a water-soluble polymer.
  • the gels prepared are applied to the steel plates to be treated over a thickness of 1 mm, ie 1 kg of gel per m 2 of surface to be treated.
  • the effect of corrosion is checked by weighing.
  • the amount of cerium used in this example i.e. 1 mol / liter, removes steel plate on average 1 micron in one hour for a gel thickness of approximately 1 mm.
  • the amount of alloy corroded depends essentially the amount of cerium (IV) in the frost, so it's completely normal that all of these values are comparable.
  • the thickness of gel applied is approximately 1mm, i.e. 1kg of gel per m 2 of surface to be treated.
  • the effect of corrosion is checked by weighing.
  • Table II specifies the quantities of material removed from a naturally passivated commercial type 316L stainless steel plate.
  • This example relates to the use of oxidizing gels according to the invention comprising, as mineral viscosifying agent, silica "Cab-O-Sil” at 5 or 6% by weight; as an organic viscosifying agent (coviscosant) of C 6 E 2 at 0.7 or 1% by weight, and as an oxidizing agent for hexa nitrato diammonium cerate at 1 mol / l and HNO 3 to 2 , 88 mol / l.
  • Conditions for applying gels are the same as for examples 3 and 4 above, but the corrosion tests are carried out on oxidized 316L type plates.
  • This heat treatment generates on the surface stainless alloys a layer of oxide of composition, thickness and morphology comparable to that likely to be on the surface of steels to decontaminate.
  • Table III specifies the quantities of material removed from 316L stainless steel plates with different gels. The plates having been oxidized by 4 days of heating at 600 ° C. (the oxide layer is uniform).
  • Ech. coviscosant Cab-O-Sil mineral filler % in weight Amount of gel kg / m 2 duration h Corrosion microns 20 without surfactant 8 1.11 2 1.6 21 without surfactant 8 1.11 5 2.2 22 without surfactant 8 1.11 24 2.6 23 C 6 E 2 1% 5 1.07 2 0.6 24 C 6 E 2 1% 5 1.09 5 1.4 25 C 6 E 2 1% 5 1.11 24 2.3
  • Table IV specifies the quantities of material removed from 316L stainless steel plates.
  • Examples 3 to 5 above show that besides the unexpected improvement of .properties rheological and the reduction of the mineral load obtained by using a co-viscous agent in a gel oxidant according to the invention, the presence of surfactant does not very moderately limits the corrosive power of gels, only a small part of Ce (IV) is indeed consumed by the surfactant.
  • decontamination is carried out by the method according to the invention of a 316 m stainless steel tank of 50 m 3 , that is to say which has a surface to be decontaminated of 120 m 2 .
  • the initial dose rate of the surface was 557 mRad / h and its final dose rate was 4 mRad / h.
  • the steps and conditions of the decontamination treatment are the same as in Example 6, except that it was necessary during the rinses for the removal of the gel, to implement a very high pressure 150 to 300 kg / cm 2 at place of low pressure.
  • the initial dose rate of the surface was 3 rad / h and its final dose rate was 2 to 20 mRad / h.
  • the decontamination factor is approximately 150.
  • the steps and conditions of the decontamination treatment are the same as in Example 8, except that it was necessary during the rinses for the removal of the gel, to apply a very high pressure (150 to 300 kg / cm 2 instead of low pressure.

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Claims (32)

  1. Organomineralgel zur Dekontamination, das aus einer kolloidalen Lösung, die
    a) ein viskosmachendes Mittel,
    b) ein dekontaminierend wirkendes Mittel
    umfasst, besteht, dadurch gekennzeichnet, dass das viskosmachende Mittel a) eine Kombination aus einem mineralischen viskosmachenden Mittel und einem organischen viskosmachenden Mittel (Coviskositätsmittel), das aus den Polyoxyethylenethern der Formel: CH3-(CH2)n-1-(O-CH2-CH2)m-OH, wobei n eine ganze Zahl von 6 - 18 und m eine ganze Zahl von 1 - 23 ist, ausgewählt ist, umfasst.
  2. Gel gemäß Anspruch 1, dadurch gekennzeichnet, dass das mineralische viskosmachende Mittel aus Siliciumdioxiden und Aluminiumoxiden ausgewählt ist.
  3. Gel gemäß Anspruch 1, dadurch gekennzeichnet, dass das mineralische viskosmachende Mittel ein in einer Menge von 1 - 7 Gew.-% vorliegendes Siliciumdioxid ist.
  4. Gel gemäß Anspruch 2, dadurch gekennzeichnet, dass das mineralische viskosmachende Mittel ein in einer Menge von 1 - 15 Gew.-% vorliegendes Aluminiumoxid ist.
  5. Gel gemäß Anspruch 1, dadurch gekennzeichnet, dass das Coviskositätsmittel in einer Menge von 0,1 - 5 Gew.-% vorhanden ist.
  6. Gel gemäß Anspruch 1 mit der Bezeichnung "saures Gel", dadurch gekennzeichnet, dass das dekontaminierend wirkende Mittel b) eine Mineralsäure umfasst.
  7. Gel gemäß Anspruch 6, dadurch gekennzeichnet, dass die Mineralsäure aus Salzsäure, Salpetersäure, Schwefelsäure, Phosphorsäure und deren Mischungen ausgewählt ist.
  8. Gel gemäß Anspruch 6, dadurch gekennzeichnet, dass die Mineralsäure in einer Konzentration von 1 - 10 mol/l vorliegt.
  9. Gel gemäß Anspruch 1, dadurch gekennzeichnet, dass das dekontaminierend wirkende Mittel b) eine anorganische Base umfasst.
  10. Gel gemäß Anspruch 9, dadurch gekennzeichnet, dass die anorganische Base aus Natron, Kali und deren Mischungen ausgewählt ist.
  11. Gel gemäß Anspruch 9, dadurch gekennzeichnet, dass die anorganische Base in einer Konzentration von 0,1 - 14 mol/l vorliegt.
  12. Gel gemäß Anspruch 1 mit der Bezeichnung "reduzierendes Gel", dadurch gekennzeichnet, dass das dekontaminierend wirkende Mittel b) ein Reduktionsmittel umfasst.
  13. Gel gemäß Anspruch 12, dadurch gekennzeichnet, dass das Reduktionsmittel in stark basischer Umgebung (pH-Wert ≥ 13) ein Normalredoxpotential E0 unter -600 mV/NWE (Normalwasserstoffelektrode) besitzt.
  14. Gel gemäß Anspruch 12, dadurch gekennzeichnet, dass das Reduktionsmittel in einer Konzentration von 0,1 - 4,5 mol/l vorliegt.
  15. Gel gemäß Anspruch 13, dadurch gekennzeichnet, dass das Reduktionsmittel aus Borhydriden, Sulfiten, Hydrogensulfiten, Sulfiden, Hypophosphiten, Zink, Hydrazin und deren Gemischen ausgewählt ist.
  16. Gel gemäß Anspruch 13, dadurch gekennzeichnet, dass das dekontaminierend wirkende Mittel b) außerdem eine anorganische Base in einer Konzentration von 0,1 - 14 mol/l umfasst.
  17. Gel gemäß Anspruch 1 mit der Bezeichnung "oxidierendes Gel", dadurch gekennzeichnet, dass das dekontaminierend wirkende Mittel b) ein Oxidationsmittel oder die reduzierte Form dieses Oxidationsmittels umfasst.
  18. Gel gemäß Anspruch 17, dadurch gekennzeichnet, dass das Oxidationsmittel in stark saurer Umgebung (pH-Wert < 1) ein Normalredoxpotential E0 über 1400 mV/NWE (Normalwasserstoffelektrode) besitzt.
  19. Gel gemäß Anspruch 17, dadurch gekennzeichnet, dass das Oxidationsmittel in einer Konzentration von 0,1 - 2 mol/l vorliegt.
  20. Gel gemäß Anspruch 18, dadurch gekennzeichnet, dass das Oxidationsmittel aus CeIV, AgII, CoIII und Gemischen derselben ausgewählt ist.
  21. Gel gemäß Anspruch 20, dadurch gekennzeichnet, dass das CeIV in der Form von Cernitrat, Cersulfat oder Diammoniumhexanitratocerat vorliegt.
  22. Gel gemäß Anspruch 18, dadurch gekennzeichnet, dass das oxidierende Gel zusätzlich zur reduzierten Form des Oxidationsmittels eine Verbindung mit der Fähigkeit zur Oxidation der reduzierten Form dieses Oxidationsmittels umfasst.
  23. Gel gemäß Anspruch 22, dadurch gekennzeichnet, dass die Verbindung mit der Fähigkeit zur Oxidation der reduzierten Form des Oxidationsmittels ein Alkalimetallpersulfat ist.
  24. Gel gemäß Anspruch 18, dadurch gekennzeichnet, dass das kontaminierend wirkende Mittel b) zusätzlich zum Oxidationsmittel eine Mineralsäure oder eine anorganische Base in einer Konzentration von 1 - 10 mol/l umfasst.
  25. Gel gemäß Anspruch 24, dadurch gekennzeichnet, dass die Mineralsäure aus HNO3, HCl, H3PO4, H2SO4 und Gemischen derselben ausgewählt ist.
  26. Oxidierendes Gel zur Dekontamination gemäß Anspruch 18, dadurch gekennzeichnet, dass es aus einer kolloidalen Lösung, die
    0,6 - 1 mol/l, vorzugsweise 1 mol/l (NH4)2Ce(NO3)6 oder Ce(NO3)4,
    2 - 3 mol/l, vorzugsweise 2,88 mol/l HNO3,
    4 - 6 Gew.-%, vorzugsweise 5 Gew.-% Siliciumdioxid,
    0,2 - 2 Gew.-%, vorzugsweise 1 Gew.-% eines Polyoxyethylenethers umfasst,
    besteht.
  27. Verfahren zur Dekontamination einer Metalloberfläche, dadurch gekennzeichnet, dass es die Applikation eines Gels nach einem der Ansprüche 1 - 26 auf die zu dekontaminierende Oberfläche, das Halten dieses Gels auf der Oberfläche während einer zum Durchführen der Dekontamination ausreichenden Zeitspanne und das Beseitigen des Gels von der auf diese Weise behandelten Metalloberfläche umfasst.
  28. Verfahren gemäß Anspruch 27, dadurch gekennzeichnet, dass das Gel durch Zerstäuben mit einer Spritzpistole appliziert wird.
  29. Verfahren zur Dekontamination gemäß Anspruch 27, dadurch gekennzeichnet, dass das Gel auf der Oberfläche während einer Zeitspanne zwischen 10 min und 24 h gehalten wird.
  30. Verfahren zur Dekontamination gemäß Anspruch 27, dadurch gekennzeichnet, dass das Gel ein saures oxidierendes Gel ist und dass es auf die Oberfläche während einer Zeitspanne zwischen 2 und 5 h appliziert wird.
  31. Verfahren gemäß Anspruch 27, dadurch gekennzeichnet, dass das Gel durch Spülen von der Oberfläche entfernt wird.
  32. Verfahren gemäß Anspruch 27, dadurch gekennzeichnet, dass das Gel auf die Oberfläche in einer Menge von 100 - 2000 g/m2 appliziert wird.
EP97915523A 1996-03-21 1997-03-20 Organomineralgel zur dekontamination von oberflächen Expired - Lifetime EP0928489B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9603517A FR2746328B1 (fr) 1996-03-21 1996-03-21 Gel organomineral de decontamination et son utilisation pour la decontamination de surfaces
FR9603517 1996-03-21
PCT/FR1997/000491 WO1997035323A1 (fr) 1996-03-21 1997-03-20 Gel organomineral de decontamination et son utilisation pour la decontamination de surfaces

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EP0928489A1 EP0928489A1 (de) 1999-07-14
EP0928489B1 true EP0928489B1 (de) 2002-02-13

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EP (1) EP0928489B1 (de)
JP (1) JP2001500608A (de)
CN (1) CN1135568C (de)
CA (1) CA2249633A1 (de)
DE (1) DE69710479T2 (de)
ES (1) ES2172777T3 (de)
FR (1) FR2746328B1 (de)
UA (1) UA44355C2 (de)
WO (1) WO1997035323A1 (de)

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US7514493B1 (en) 2004-10-27 2009-04-07 Sandia Corporation Strippable containment and decontamination coating composition and method of use
FR2879490B1 (fr) 2004-12-21 2007-03-23 Tech En Milieu Ionisant Stmi S Dispositif d'intervention motorise pour boite a gant et boite a gant equipee d'un tel dispositif
US7166758B2 (en) * 2005-03-26 2007-01-23 Luis Nunez Foam and gel methods for the decontamination of metallic surfaces
US20070065587A1 (en) * 2005-08-26 2007-03-22 Hatle Loren L Method for removal of surface contaminants from substrates
FR2891470B1 (fr) * 2005-10-05 2007-11-23 Commissariat Energie Atomique Gel aspirable pour la decontamination de surfaces et utilisation
CN101100286B (zh) * 2006-07-05 2011-11-16 罗门哈斯公司 稳定的高温硼氢化物制剂
FR2962046B1 (fr) * 2010-07-02 2012-08-17 Commissariat Energie Atomique Gel de decontamination biologique et procede de decontamination de surfaces utilisant ce gel.
FR2984170B1 (fr) * 2011-12-19 2014-01-17 Commissariat Energie Atomique Gel de decontamination et procede de decontamination de surfaces par trempage utilisant ce gel.
KR101278212B1 (ko) * 2011-12-22 2013-07-01 한국수력원자력 주식회사 방사성 오염 제거용 환원제 함유 겔 화학제염제, 이의 제조방법 및 이를 이용한 제염방법
JP5936121B2 (ja) * 2012-05-23 2016-06-15 株式会社ダイアテック 放射性物質の除染方法
JP2014041100A (ja) * 2012-08-23 2014-03-06 Shimizu Corp コンクリート構造体の表層除染方法
CN105210151B (zh) 2013-03-15 2017-07-14 赛瑞丹公司 使核反应堆冷却的方法以及包含多面体硼烷阴离子或碳硼烷阴离子的核反应堆
JP6338835B2 (ja) * 2013-08-27 2018-06-06 株式会社ネオス 放射性物質の除染用酸性ゲルおよび除染方法
KR101657529B1 (ko) 2013-10-25 2016-09-20 한국원자력연구원 고제염능 및 저부식성을 갖는 화학제염제, 이의 제조방법 및 이를 이용한 제염방법
CN106463190B (zh) * 2014-04-25 2019-02-15 赛瑞丹公司 包含多面体硼烷阴离子或碳硼烷阴离子的水性溶液的池及其使用方法
CN104900285B (zh) * 2015-04-08 2017-11-07 武汉网绿环境技术咨询有限公司 一种含放射性核素污染物的治理方法
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KR102273062B1 (ko) * 2019-10-30 2021-07-06 한국원자력연구원 계통 제염용 제염제 및 이를 이용한 제염방법
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CN1135568C (zh) 2004-01-21
JP2001500608A (ja) 2001-01-16
DE69710479D1 (de) 2002-03-21
UA44355C2 (uk) 2002-02-15
ES2172777T3 (es) 2002-10-01
CN1224527A (zh) 1999-07-28
WO1997035323A1 (fr) 1997-09-25
EP0928489A1 (de) 1999-07-14
FR2746328B1 (fr) 1998-05-29
CA2249633A1 (fr) 1997-09-25
FR2746328A1 (fr) 1997-09-26
US6203624B1 (en) 2001-03-20
DE69710479T2 (de) 2002-10-31

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