EP1062006B1 - Oxidationsmittel wie cerium (iv) enthaltender schaum zur dekontamination - Google Patents

Oxidationsmittel wie cerium (iv) enthaltender schaum zur dekontamination Download PDF

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Publication number
EP1062006B1
EP1062006B1 EP99907664A EP99907664A EP1062006B1 EP 1062006 B1 EP1062006 B1 EP 1062006B1 EP 99907664 A EP99907664 A EP 99907664A EP 99907664 A EP99907664 A EP 99907664A EP 1062006 B1 EP1062006 B1 EP 1062006B1
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Prior art keywords
cerium
foam
mol
foam according
oxide
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French (fr)
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EP1062006A1 (de
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Bruno Fournel
Maria Faury
Jean-Luc Alcaraz
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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

Definitions

  • the present invention relates to foams decontamination, usable for decontamination large volume industrial equipment, in particular nuclear facilities.
  • the volume of the liquid phase may be weak because the foam contains usually 5 to 50 times more gas than liquid. In Consequently, liquid active effluents from decontamination with foam are significantly reduced.
  • the document EP-A-0 526 305 [1] describes a decontamination foam in which the phase liquid includes at least one decontamination reagent and two surfactants to promote training foam.
  • Decontamination reagents can consist of sulfuric acid, acid phosphoric and cerium (IV).
  • the cerium (IV) acts as a powerful oxidizing agent, this which allows in the case of decontamination stainless steel equipment, ensuring chemical attack on the steel surface in order to dissolve it superficially and eliminate the contamination fixed.
  • EP-A-727 243 [2] also illustrates decontamination foam using Ce (IV) with an acid such as HNO3 or H2SO4 and surfactants from sulfobetaine and / or alkyl ether type oligosaccharides.
  • the main difficulty raised by a formulation comprising Ce (IV) consists in finding foaming surfactants capable of resisting strongly oxidizing mixture associating a strong acid and the cerium IV.
  • the normal potential oxidation-reduction of the Ce (IV) / Ce (III) couple amounts to 1.72 V.
  • the second difficulty consists in formulating, on the base of the retained surfactants, a foam having good rheological and hydrodynamic properties allowing its implementation in installations with closed loop recirculation like the one described in [1].
  • the present invention has precisely for object a foam composition containing an agent oxidant such as Ce (IV), which makes it possible to avoid this disadvantage thanks to the use of a surfactant suitable, while having good properties of runoff and being compatible with a setting work with closed loop recirculation.
  • an agent oxidant such as Ce (IV)
  • the use of a surfactant consisting of at least one amine oxide avoids the reduction of oxidizing agents mentioned and thus obtain a foam of decontamination with chemical resistance significant and compatible with the duration of a decontamination operation, which is usually 1 to 10 hours. Furthermore, the choice of this surfactant allows to obtain a foam having rheological properties suitable for the decontamination of nuclear installations.
  • the amine oxides used in the invention can correspond to the following formula: in which R 1 , R 2 and R 3 which may be identical or different, are hydrocarbon groups of 1 to 20 carbon atoms, optionally substituted, at least one of R 1 , R 2 and R 3 being a hydrocarbon group at least 8 carbon atoms, so that the amine oxide can play the role of surfactant.
  • the hydrocarbon groups used for R 1 , R 2 and R 3 may be aliphatic groups, linear or branched, saturated or unsaturated.
  • saturated groups mention may be made of linear or branched alkyl groups.
  • Substitutes usable in groups hydrocarbons can for example be atoms halogens, amido groups, hydroxyls, esters, ...
  • the groups R 1 , R 2 and R 3 have at most 16 carbon atoms.
  • the amine oxide used corresponds to the formula given above in which R 1 and R 3 are lower alkyl groups of 1 to 4 carbon atoms such as methyl, ethyl and propyl groups, and R 2 is an alkyl group of 10 to 16 carbon atoms.
  • Aromox® or cocodimethylamine oxide
  • R 1 and R 3 representing the methyl group
  • R 2 being a C 16 alkyl group, C 14 or C 12 .
  • the amine oxide with R 2 at C 12 predominates before the amine oxide where R 2 is at C 14 , then before the amine oxide with R 1 at C 16 .
  • Ninox FCA or cocamidopropylamine oxide
  • R 1 represents the propyl group
  • R 2 represents an aliphatic chain
  • R 3 is an alkyl group.
  • the agent oxidant can consist of silver (II), cobalt (III), potassium permanganate or cerium (IV).
  • cerium (IV) is used.
  • the acid used in the liquid phase of the foam can be nitric acid, sulfuric acid or mixtures thereof.
  • the acid concentration of the aqueous solution is 0.3 N to 4 N.
  • the acid concentration nitric in the liquid phase is low, for example from 0.3 to 2 mol / l, and preferably 0.3 to 0.35 mol / l, in because of the problems of partial insolubility of this amine oxide in nitric medium. Too much acidity low, for example less than 0.3 N, is not desirable because it leads to the insolubilization of the cerium. Conversely, significant acidity leads to slower solubilization kinetics of cerium and does not increase the efficiency of the process in a significative way.
  • An acidity of the order of 2N is suitable for particularly for the decontamination of surfaces in stainless steel.
  • Cerium (IV) may be present in the liquid phase of the foam in the form of cerium or double nitrate of ammonium and cerium.
  • the inorganic acid is nitric acid
  • cerium we prefer to add cerium to the liquid phase under the form of nitrate by generating it in a electrolysis cell from nitrate of cerium (III). Indeed, this avoids introduction into the sulfate ion foam or ammonium which could be troublesome.
  • the cerium (IV) concentration of the phase foam liquid is preferably 0.01 to 0.2 mol / l.
  • the optimal value is around 0.05 mol / l.
  • the total concentration of oxide-based surfactant amine is generally in the range of 5 to 50 g / l.
  • This concentration is chosen according to of the amine oxide used.
  • a concentration is advantageously used in Aromox® of about 10 to 40 g / l, and preferably of 25 to 30 g / l.
  • Ninox® we can also use concentrations of 10 to 40 g / l, but preferably 20 to 30 g / l.
  • Ninox® leads to drier foams and more stable therefore having a longer lifespan while Aromox® tends to moisten the foam and decrease its stability.
  • the surfactant consists of a mixture of amine oxides
  • a concentration is chosen adapted according to the proportions of the amine oxides in the mixture.
  • cerium (IV) is added in the form of cerium sulfate, cerium double nitrate and ammonium or cerium (IV) electrogenerated from cerium (III) nitrate, and add the or amine oxide surfactants. This order is chosen to facilitate the solubilization of cerium (IV) because it decreases in presence of surfactants.
  • the foam generator in which the pressurized gas phase in a diffuser within the liquid phase introduced into the generator.
  • the size of the gas bubbles depends on the flow of gas phase, its distribution through the pores of the sintered plate constituting the diffuser and above all the pressure drop caused by the packing porous.
  • the foam gas content by choosing so appropriate flow rates and inlet pressures of the liquid phase and the gas phase in the generator.
  • the gas phase can be a gas or a mixture of gases, for example oxygen, dioxide nitrogen, argon and most often air. Debits of gas and liquid are chosen so as to obtain a foam with an abundance in the range ranging from 5 to 40 and preferably from 10 to 20.
  • V gas + V liquid V foam V liquid in which V represents the volume of gas (V gas ), liquid (V liq ) or foam (V foam ).
  • the foams of the invention can be used in a range of temperatures from 15 to 65 ° C. At high temperature, the kinetics are accelerated attack of the metal surface to be decontaminated, but at the same time the reduction of cerium (IV) in cerium (III) by surfactants is favored. The foams obtained are of lower quality because more dry and less stable. If the temperature is too weak, the kinetics of chemical attack of the surface to decontaminate will be slow. For use optimal cerium (IV) foams, temperature should be in the range of 20 to 50 ° C.
  • the foams of the invention can be destabilized by mechanical means, for example by ultrasound, in order to separate quickly the liquid phase of the foam at the end of operation.
  • the single figure represents the device used for foam foam testing decontamination.
  • cerium (IV) Preliminary resistance tests at cerium (IV) of these surfactants were made in using a 1M nitric acid solution containing 0.03 mol / l of cerium (IV) and a mass proportion Aromox® from 2.8 to 3% or NinoxFCA from 2.5 to 3%. In table 1 which follows, the proportion is indicated. cerium (IV) molar not consumed after 24 hours and 60 hours in the presence of an excess of these surfactants, as well as the appearance of the liquid phase.
  • Tables 1 and 5 show a exceptional stability of AROMOX amine oxides by compared to that of any other surfactant and a good behavior of NINOX amine oxides from the point of view foamability. So it's on the basis of these molecules that the amine formulation study has been carried out.
  • a liquid foam phase is prepared, formed from an aqueous solution of cerium (IV) and Aromox® containing 1 mol / l of nitric acid, 2.8% by weight of Aromox® and 0 , 03 mol / l of cerium (IV), then the evolution of the concentration of cerium (IV) of this solution is determined as a function of time.
  • Table 6 which follows. Time (h) Cerium (IV) concentration (mol.l -1 ) % of cerium (IV) remaining 0 0.03 100 12 0.027 90 24 0.023 77 36 0.019 63 48 0.016 53
  • phase foam liquid consisting of an acid solution sulfuric at 1 mol / l including 0.06 mol / l of cerium (IV) and 2.8% by weight of Aromox®.
  • phase foam liquid consisting of an acid solution 1 mol / l nitric containing 0.03 mol / l of cerium (IV) and 2.5% by weight of surfactant consisting of Ninox FCA.
  • Example 1 We determine as in Example 1 the evolution of the cerium concentration of the solution as a function of time.
  • a foam is generated according to a given laboratory protocol and the liquid which has drained over time is recovered.
  • the quality criteria closely depend on the desired application. In decontamination, some qualitative criteria can be set, this is the first stage. In a second step, it is possible, using a representative model of the intended application, here the decontamination of large components, to quantify certain properties.
  • the drainage rate qualifies the proportion of liquid present in the foam at the high level and at the low level. It is defined as the ratio of the flow of liquid on the wall on the liquid flow introduced to the entry at the bottom of the vertical column multiplied by The test is carried out at 20 ⁇ 2 ° C.
  • cerium (IV) is preferably introduced in the form of sulfate, it is possible introduce it all at once or add it gradually in the form of metered additions. We prefer do not exceed a molar concentration of 0.15 mol / l cerium (IV).
  • Aromox® In nitric medium, the function is better with Ninox®, but given its durability weaker chemical vis-à-vis cerium (IV), Aromox® may be preferred for long duration. With Aromox®, however, preferably nitric acid concentration solutions around 0.35 mol / l and a concentration of cerium (IV) less than 0.03 mol / l due to problems of partial insolubility of Aromox® in nitric medium.
  • Amonyl® is a sulfobetaine corresponding to the following formula: in which R 1 is an alkyl group and X represents COO - or SO - 3 .
  • Oramix® is an alkyl oligosaccharide ether corresponding to the following formula: in which n is an integer from 1 to 5 and R 2 is a C 8 to C 10 alkyl group.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Food Science & Technology (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (17)

  1. Dekontaminationsschaum, umfassend:
    a) eine flüssige Phase, die von einer wässrigen Lösung, die
    mindestens eine anorganische Säure,
    mindestens ein Oxidationsmittel, das aus Silber (II), Cobalt (III), Kaliumpermanganat und Cer (IV) ausgewählt ist, und
    ein tensioaktives Mittel, das mindestens ein Aminoxid umfasst,
    umfasst, gebildet wird; und
    b) eine gasförmige Phase, die in der flüssigen Phase verteilt ist.
  2. Schaum gemäß Anspruch 1, in dem die anorganische Säure aus HNO3, H2SO4 und Gemischen derselben ausgewählt ist.
  3. Schaum gemäß Anspruch 2, in dem die Säurekonzentration der wässrigen Lösung 0,3 N bis 4 N beträgt.
  4. Schaum gemäß einem der Ansprüche 1-3, in dem das Oxidationsmittel Cer (IV) ist.
  5. Schaum gemäß Anspruch 4, in dem die Konzentration der wässrigen Lösung an Cer (IV) 0,01-0,2 mol/l beträgt.
  6. Schaum gemäß einem der Ansprüche 1-5, in dem das Aminoxid der Formel:
    Figure 00350001
    worin R1, R2 und R3, die identisch oder verschieden sein können, Kohlenwasserstoffgruppen mit 1-20 Kohlenstoffatomen, die ggf. substituiert sind, sind, wobei mindestens einer der Reste R1, R2 und R3 eine Kohlenwasserstoffgruppe mit mindestens 8 Kohlenstoffatomen ist, entspricht.
  7. Schaum gemäß Anspruch 6, in dem die Konzentration der wässrigen Lösung an Aminoxid 5-50 g/l beträgt.
  8. Schaum gemäß einem der Ansprüche 1-5, in dem das Aminoxid Cocodimethylaminoxid ist.
  9. Schaum gemäß Anspruch 8, in dem die Konzentration der wässrigen Lösung an Aminoxid etwa 10-40 g/l beträgt.
  10. Schaum gemäß einem der Ansprüche 1-5, in dem das Aminoxid Cocamidopropylaminoxid ist.
  11. Schaum gemäß Anspruch 10, in dem die Konzentration der wässrigen Lösung an Aminoxid 10-40 g/l beträgt.
  12. Schaum gemäß einem der Ansprüche 1-5, in dem das Aminoxid Lauraminoxid oder Myristaminoxid ist.
  13. Schaum gemäß Anspruch 1, in dem die flüssige Phase eine wässrige Lösung ist, die 0,3-2 mol/l HNO3, 0,01-0,1 mol/l Cer (IV) und 25-30 g/l Cocodimethylaminoxid umfasst.
  14. Schaum gemäß Anspruch 1, in dem die flüssige Phase eine wässrige Lösung ist, die 0,2-3 mol/l H2SO4, 0,01-0,2 mol/l Cer (IV) und 25-30 g/l Cocodimethylaminoxid umfasst.
  15. Schaum gemäß Anspruch 1, in dem die flüssige Phase eine wässrige Lösung ist, die 0,3-2 mol/l HNO3, 0,01-0,1 mol/l Cer (IV) und 20-30 g/l Cocamidopropylaminoxid umfasst.
  16. Verwendung eines Schaums gemäß einem der Ansprüche 1-14 in einem Temperaturbereich von 15 °C bis 65 °C.
  17. Verwendung eines Schaums gemäß einem der Ansprüche 1-15 zur Dekontamination von metallischen Einrichtungen.
EP99907664A 1998-03-09 1999-03-08 Oxidationsmittel wie cerium (iv) enthaltender schaum zur dekontamination Expired - Lifetime EP1062006B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9802836A FR2775606B1 (fr) 1998-03-09 1998-03-09 Mousse de decontamination comprenant un agent oxydant tel que le cerium (iv)
FR9802836 1998-03-09
PCT/FR1999/000514 WO1999046010A1 (fr) 1998-03-09 1999-03-08 Mousse de decontamination comprenant un agent oxydant tel que le cerium (iv)

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EP1062006A1 EP1062006A1 (de) 2000-12-27
EP1062006B1 true EP1062006B1 (de) 2001-12-12

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EP (1) EP1062006B1 (de)
AU (1) AU2732199A (de)
DE (1) DE69900595T2 (de)
ES (1) ES2169946T3 (de)
FR (1) FR2775606B1 (de)
WO (1) WO1999046010A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6566574B1 (en) * 1998-06-30 2003-05-20 Sandia Corporation Formulations for neutralization of chemical and biological toxants
US7390432B2 (en) 1998-06-30 2008-06-24 Sandia Corporation Enhanced formulations for neutralization of chemical, biological and industrial toxants
FR2841802B1 (fr) * 2002-07-08 2005-03-04 Commissariat Energie Atomique Composition, mousse et procede de decontamination de surfaces
EP3464708B1 (de) 2016-06-07 2021-10-06 Battelle Memorial Institute Beschichtungsmaterialien und mit den beschichtungsmaterialien beschichtete persönliche schutzkleidung
CN111655343A (zh) * 2017-12-05 2020-09-11 巴特尔纪念研究院 净化组合物和净化方法
US11266865B2 (en) 2017-12-05 2022-03-08 Battelle Memorial Institute Decontamination compositions and methods of decontamination

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3219670C1 (de) * 1982-05-26 1983-10-27 Kaercher Gmbh & Co Alfred Entgiftungsfluessigkeit
JPS63172799A (ja) * 1987-01-12 1988-07-16 日本パ−カライジング株式会社 アルミニウムの表面洗浄剤
FR2679458A1 (fr) * 1991-07-23 1993-01-29 Commissariat Energie Atomique Mousse de decontamination a duree de vie controlee et installation de decontamination d'objets utilisant une telle mousse.
DE4331942C2 (de) * 1993-09-21 1996-02-22 Loeffler Karl Gmbh & Co Kg Verwendung einer Zusammensetzung zur Reinigung und Desinfektion von Gegenständen in der Brauindustrie
FR2730641B1 (fr) * 1995-02-20 1997-03-14 Commissariat Energie Atomique Mousse de decontamination a l'ozone, et procede de decontamination utilisant cette mousse

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DE69900595D1 (de) 2002-01-24
AU2732199A (en) 1999-09-27
WO1999046010A1 (fr) 1999-09-16
EP1062006A1 (de) 2000-12-27
ES2169946T3 (es) 2002-07-16
FR2775606B1 (fr) 2000-03-31
FR2775606A1 (fr) 1999-09-10
DE69900595T2 (de) 2002-07-18

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