EP3870686A1 - Decontamination paste and method for decontaminating a substrate made of a solid material using said paste - Google Patents
Decontamination paste and method for decontaminating a substrate made of a solid material using said pasteInfo
- Publication number
- EP3870686A1 EP3870686A1 EP19868217.1A EP19868217A EP3870686A1 EP 3870686 A1 EP3870686 A1 EP 3870686A1 EP 19868217 A EP19868217 A EP 19868217A EP 3870686 A1 EP3870686 A1 EP 3870686A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paste
- mass
- dough
- decontamination
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005202 decontamination Methods 0.000 title claims abstract description 128
- 230000003588 decontaminative effect Effects 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000000758 substrate Substances 0.000 title claims abstract description 62
- 239000011343 solid material Substances 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 241000894007 species Species 0.000 claims description 99
- 239000003795 chemical substances by application Substances 0.000 claims description 91
- 239000000203 mixture Substances 0.000 claims description 58
- 238000001035 drying Methods 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 24
- 239000011707 mineral Substances 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000002739 metals Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- -1 cellulose fibers Chemical class 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000002285 radioactive effect Effects 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 229910052752 metalloid Inorganic materials 0.000 claims description 7
- 150000002738 metalloids Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 238000010297 mechanical methods and process Methods 0.000 claims description 5
- 230000005226 mechanical processes and functions Effects 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229920003043 Cellulose fiber Polymers 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- 241000700605 Viruses Species 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- RIAJLMJRHLGNMZ-UHFFFAOYSA-N triazanium;trioxomolybdenum;phosphate Chemical compound [NH4+].[NH4+].[NH4+].O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.[O-]P([O-])([O-])=O RIAJLMJRHLGNMZ-UHFFFAOYSA-N 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000002969 artificial stone Substances 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
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- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 235000015927 pasta Nutrition 0.000 claims description 3
- 239000012994 photoredox catalyst Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
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- 239000003053 toxin Substances 0.000 claims description 3
- 231100000765 toxin Toxicity 0.000 claims description 3
- 108700012359 toxins Proteins 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- LWIDHXZHWZWROR-UHFFFAOYSA-N 1-hexadecylpyridin-1-ium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1.CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 LWIDHXZHWZWROR-UHFFFAOYSA-N 0.000 claims description 2
- 101100046775 Arabidopsis thaliana TPPA gene Proteins 0.000 claims description 2
- BNQVPMZPVQZGNI-UHFFFAOYSA-N CC(CCCCP(O)=O)(C)C Chemical compound CC(CCCCP(O)=O)(C)C BNQVPMZPVQZGNI-UHFFFAOYSA-N 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 2
- 241000233866 Fungi Species 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 102000029797 Prion Human genes 0.000 claims description 2
- 108091000054 Prion Proteins 0.000 claims description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 2
- 229960004830 cetylpyridinium Drugs 0.000 claims description 2
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000011491 glass wool Substances 0.000 claims description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 claims description 2
- 239000011490 mineral wool Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- UJRAXLUXHBUNDO-UHFFFAOYSA-M sodium;hydron;oxalate Chemical compound [Na+].OC(=O)C([O-])=O UJRAXLUXHBUNDO-UHFFFAOYSA-M 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
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- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 9
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- GIKLTQKNOXNBNY-OWOJBTEDSA-N lewisite Chemical compound Cl\C=C\[As](Cl)Cl GIKLTQKNOXNBNY-OWOJBTEDSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 231100000189 neurotoxic Toxicity 0.000 description 1
- 230000002887 neurotoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000003608 radiolysis reaction Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000012776 robust process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000935 short-term exposure limit Toxicity 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- 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
- G21F9/28—Treating solids
- G21F9/30—Processing
-
- 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
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
-
- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
Definitions
- the present invention relates to a decontamination paste usable for the decontamination of substrates made of solid, contaminated materials.
- the present invention further relates to a decontamination process using this decontamination paste.
- decontamination or depollution of a substrate means the elimination of pollutants, contaminants of this substrate.
- contaminants or contaminating species, we generally mean substances, compounds, which are not normally part of the substrate material and whose presence is not desired.
- the process and the paste according to the invention allow the decontamination of all kinds of materials, such as metallic materials, plastics, minerals such as vitreous materials.
- the process and the paste according to the invention apply as well to the decontamination of substrates made of dense materials as to the decontamination of substrates made of porous materials such as cementitious materials such as mortars and concretes; the bricks ; plasters; and natural stone.
- the process and the paste according to the invention also allow the elimination of all kinds of contaminants and in particular chemical, biological, or nuclear, radioactive contaminants.
- the process and the paste according to the invention can therefore be qualified in particular as a NRBC decontamination process and paste (Nuclear, Radiological, Biological, Chemical).
- the technical field of the invention can thus, in general, be defined as that of the decontamination of contaminated substrates with a view to eliminating pollutants, contaminants, contaminating species which are on their surface, just below their surface (in subsurface), or deep into the substrate.
- the decontamination or decontamination of solid materials is a problem which arises in many fields, in particular in the nuclear industry, for example for sanitation operations or maintenance of installations, in certain industries using toxic chemicals. , but also, for example, in the context of decontamination operations that may be necessary following an NRBC (Nuclear, Radiological, Biological and Chemical) type accident.
- NRBC Nuclear, Radiological, Biological and Chemical
- labile contamination in particular in the form of dust, not adhering to the surface to be decontaminated.
- surface contamination the contaminants are present and adhere to the surface of the substrate in a solid material (within a layer of grease for example).
- the contamination is embedded in the first (ie) microns from the surface of the solid substrate (within an oxide layer of a metal for example).
- Contaminants have diffused within the porous network and are found embedded in the material a few millimeters, even centimeters, deep.
- the process used is generally adapted to the type of contamination targeted and to the outlets for the final waste generated.
- labile contamination can be eliminated by using methods implementing a simple aspiration of this contamination.
- Labile contamination can also be eliminated by applying a peelable gel to the surface to be decontaminated, which will then act as an adhesive tape and remove the labile contamination from the support [1].
- peelable gels are organic and are only effective for labile contamination. They therefore generate organic waste. In addition, their application with an excessively large thickness (for example greater than 2 mm) may cause gel drips which will weaken the mechanical properties of the peelable gel formed.
- the methods using gels generate solid waste of millimeter size which can be aspirated, if their implementation by spraying is controlled.
- controlling the thickness of the deposited gel is essential in these processes in order to avoid the formation of a waste of a thickness that is too thin and too adherent to the substrate (in the event of deposit of a thickness of gel that is too fine) or the appearance of streaks on non-horizontal surfaces (in the event of depositing a thickness of gel that is too thick).
- These gels do not allow the treatment of porous materials and generally do not contain contaminating species well.
- Deep decontamination of porous materials is much more complex than labile, surface or sub-surface decontamination because contaminants tend to be incorporated deep into the porous network.
- Document [6] presents a process for decontaminating porous materials deeply contaminated by radionuclides.
- the process described is dedicated to ionic nuclear contamination, and no indication is given as to the possibility of modifying it for use in fields other than nuclear.
- This document presents a two-step process.
- a first step the porous material is soaked in an ionic solution capable of dissolving the radionuclides present in the porosity.
- This first step can cause sagging and the production of liquid effluents that are difficult to recover and treat.
- the porous material may be inhomogeneously imbibed, consequently reducing the efficiency of the process.
- an organic hydrogel containing radionuclide chelating agents is brought into contact with the soaked porous material in order to extract the solubilized contaminants.
- Document [7] presents a dry composition for a compress to be used for cleaning or desalination of porous materials, more particularly for the treatment of polluted stones in the context of the restoration of monuments.
- This dry composition comprises a binder, a filler and a mineral fiber. Due to the intended application which is very restrictive, namely the desalination and cleaning of historic monuments, very specific criteria must be met (mainly safety criterion), giving rise to dry compositions of fairly complex compresses with at least minus 3 components.
- This document also relates to a cleaning or desalination pad ready for use which comprises the dry composition, from 50% to 80% by weight of a solvent, and optionally a solubilization reagent. The compress is then deposited on the surface to be treated.
- the compress is then allowed to dry and the salts dissolved in the solvent which has penetrated into the material to be treated are extracted by migration to the compress. After drying, the remains of the compress are removed by a final rinse, producing liquid effluents, and by simultaneous aspiration.
- composition of the gels and compresses described respectively in documents [2] and [7] does not allow these gels and compresses "to hold" on a vertical wall, to hang on this wall, without sagging, to flow, when 'They are applied to this vertical wall with a significant thickness, in particular a centimeter thickness.
- the maximum thickness of these gels and compresses that can be applied without sagging is a few millimeters.
- aspirable gels do not generally confine contaminating species which are only adsorbed on the surface of the final waste or mechanically trapped within the flakes of dry gel.
- the aspirable gels used for surface or sub-surface decontamination generate non-pulverulent waste of millimeter size. It would therefore be desirable to obtain larger waste to avoid resuspension in the air.
- a decontamination paste comprising, preferably consisting of:
- inorganic viscosifier chosen from clays, said inorganic viscosifier representing from 20% to 70% by mass, preferably from 35% to 70% by mass, more preferably from 40% to 65% by mass, better still 45 to 55% by mass of the total mass of the dough, and said inorganic viscosifying agent being in the form of particles of micron and / or nanometric size;
- component (s) chosen from the following components:
- At least one active decontamination agent at least one active decontamination agent
- At least one agent chelating contaminating species at least one agent chelating contaminating species
- the said component (s) is (are) present in the following proportions: 0.1 to 8 or 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, better 1 to 5% by mass, better still 1 to 3% by mass relative to the mass of the dough, of the at least one compound in the form of fibers;
- 0.1 to 10 mol / L of dough optionally, 0.1 to 10 mol / L of dough, preferably 0.5 to 10 mol / L of dough, more preferably 1 to 10 mol / L of dough, and better still 3 to 6 mol / L of dough, at least one active decontamination agent;
- solvent residue is meant that the solvent is always present in the paste, and that the amount of solvent is such that when added to the amounts of the components of the paste other than the solvent (that these components are mandatory or possible components mentioned above, or other optional additional components mentioned or not mentioned), the total amount of all the components of the dough is 100% by mass.
- particles of micron size it is meant that these particles have an average size, generally defined by their largest dimension of more than 0.1 ⁇ m to 100 ⁇ m, preferably from 1 to 100 ⁇ m, for example more than 0.1 pm to 4, 5 or 10 pm.
- said inorganic viscosity agent is present only in the form of particles of micron size.
- nanometric size particles it is meant that these particles have an average size, generally defined by their largest dimension of 1 to 100 nm.
- the dough according to the invention comprises a specific amount of a specific clayey inorganic viscosifying agent giving the dough a viscosity suitable for its use, at least one compound in the form of fibers, and a solution comprising a solvent, and optionally one or more optional components which are generally chosen according to the particular application which is made of the dough.
- paste is well known to those skilled in the art, who know that a paste is intrinsically different from a gel constituted by a colloidal solution.
- the dough according to the invention generally has a viscosity greater than or equal to 100 Pa.s at 20 ° C for a shear less than 1 s 1 .
- the solution allows attack of the substrate, solubilization of the contaminating species, or fixation of the contaminating species during the decontamination step (see below).
- the decontamination paste according to the invention differs fundamentally from the decontamination compositions according to the prior art and in particular from the aspirable gels of the prior art in that it contains a specific inorganic viscosifying agent chosen from clays and not from silicas and aluminas, and in that the amount of this inorganic viscosity agent in the dough is greater than the amount of inorganic viscosity agent in the aspirable gels.
- the amount of this inorganic viscosifying agent in the dough is from 20% to 70% by mass, preferably from 35% to 70% by mass, more preferably from 40% to 65% by mass, better still from 45 to 55%
- the decontamination paste according to the invention also differs fundamentally from decontamination compositions according to the prior art and in particular from the aspirable gels of the prior art in that it contains at least one compound in the form of fibers.
- the inorganic viscosifier is present only in the form of particles of micron size.
- the paste according to the invention meets all the needs listed above, achieves the goals mentioned above and solves the problems of the decontamination compositions of the prior art.
- the paste according to the invention makes it possible, surprisingly, to eliminate both labile contamination, sub-surface contamination, and deep contamination (for example contamination embedded in a porous network of a substrate made of a porous material).
- the paste according to the invention can, surprisingly hold, without flowing, without sagging on vertical walls even when applied to these walls with a thickness much greater than that with which the gels are applied. aspirable. This thickness is in particular from 2 to 5 mm.
- this thickness can be greater than 5 mm.
- the decontamination effect in particular the corrosive effect, is greater, which thus allows deeper and sub-surface decontamination.
- the paste according to the invention nevertheless retains a handy consistency allowing its easy application on any surface.
- the number of fractures which appear during the drying of the dough according to the invention is considerably reduced compared to aspirable gels and a solid waste consisting of pieces, non-pulverulent particles, and of much larger sizes than the waste obtained. after drying vacuum gels is obtained.
- the waste obtained after drying the gel according to the invention generally has a size (the size being defined by their largest dimension) greater than or equal to one cm, or even greater than or equal to 10 cm. Often, the final dry waste presents little fractures (one, two, for example), or even no fracture, and it is then the same size as the “wet” gel deposit initially deposited (see examples).
- waste which is large, contaminating species can be chemically adsorbed.
- the compound in the form of fibers ensures that an even greater thickness of dough, for example greater than or equal to 5 mm, preferably greater than or equal to 6, 7, 8 or 9 mm, more preferably at least 10 mm -and up to 50 mm, for example, on a vertical wall without sagging, and after drying a solid non-pulverulent waste is always obtained. This is demonstrated in Example 4.
- a paste comprising only the solvent, the viscosifying agent, and the compound in the form of fibers, makes it possible to successfully implement the method according to the invention by trapping, capturing, capturing contaminating species, and allows to obtain the effects and advantages listed above.
- the clays play both the role of viscous agent and the role of "trapper", "fixer”.
- optional components are required to trap these contaminating species. These optional components can be extracting agents from contaminating species and / or chelating agents from contaminating species.
- a surfactant in the paste according to the invention has a favorable and significant influence on the rheological properties of the paste.
- This surfactant in particular promotes the recovery of viscosity of the paste after its application and prevents risk of spreading or sagging when the paste is deposited on vertical surfaces and ceilings.
- the presence in the dough of at least one active decontamination agent makes it possible to eliminate, destroy, inactivate, kill, extract the contaminating species whether they are labile, surface, sub-surface or deep below the surface of the substrate of the solid substrate.
- the presence in the paste of at least one extracting and fixing agent for the contaminating species, such as an inorganic adsorbent makes it possible to facilitate the capture and the fixing of the contaminating species, and also makes it possible to avoid a release of the contaminating species in the case of a possible leaching, in particular of an undesired leaching, of the final dry and solid residue.
- the treatment of the waste resulting from the decontamination operation using the paste according to the invention is greatly facilitated.
- the clays can possibly, in certain cases play both the role of viscous agent and the role of “trapper”, “fixative”.
- the presence in the paste of at least one agent chelating contaminating species also makes it possible to facilitate the capture and the fixation of the contaminating species.
- the presence of extracting and / or chelating agents in the paste, or more exactly in the solution forming part of the paste makes it possible to promote the recovery of contaminants chemically linked within the porosity of a material, such as, for example a cementitious material.
- the organic matter content of the pulp according to the invention is generally less than 4% by mass, preferably less than 2% in mass, which constitutes an advantage of the dough according to the invention.
- the inorganic viscosity agent can be chosen from smectites, kaolinites, perlites, vermiculites, and their mixtures.
- the nature of the mineral, inorganic viscosifying agent unexpectedly influences the drying of the paste according to the invention and the particle size of the residue obtained.
- the decontamination paste according to the invention contains a compound in the form of fibers.
- the fibers can be chosen from fibers of organic compounds such as cellulose fibers, and fibers of mineral compounds such as rock wool and glass wool.
- the fibers can have a diameter of 2 ⁇ m to 10 ⁇ m.
- the fibers can have a length of 50 ⁇ m to 10 mm.
- the paste according to the invention may contain an active decontamination agent.
- This active decontamination agent can be any active decontamination agent making it possible to eliminate a contaminating species whatever the nature of this contaminating species: whether this contaminating species is chemical, biological or even nuclear, radioactive - in other words, this decontamination agent can be any “NRBC” (Nuclear, Biological, Radiological, Chemical) decontamination agent, or whether this contaminating species is organic or mineral, liquid or solid.
- NRBC Nuclear, Biological, Radiological, Chemical
- the paste according to the invention can thus contain an active agent for biological, chemical or nuclear, radioactive decontamination.
- the active decontamination agent can also be a degreasing agent, pickling in order to eliminate any contaminating species found on the surface and possibly below the surface and into the depth of the substrate.
- Certain active decontamination agents can simultaneously play several decontamination functions.
- biological decontamination agent which can also be described as a biocidal agent, or a disinfecting agent, is meant any agent which, when brought into contact with a biological species and in particular a toxic biological species, is capable of inactivate or destroy it.
- biological species is meant any type of microorganism such as bacteria, fungi, yeasts, viruses, toxins, spores, in particular spores of Bacillus anthracis, prions, and protozoa.
- the biological species which are eliminated, destroyed, inactivated by the paste according to the invention are essentially biotoxic species such as pathogenic spores, for example spores of Bacillus anthracis, toxins such as, for example, botulinum toxin or ricin, bacteria such as Yersinia pestis bacteria and viruses such as vaccinia virus or haemorrhagic fever viruses, for example of the Ebola type.
- pathogenic spores for example spores of Bacillus anthracis
- toxins such as, for example, botulinum toxin or ricin
- bacteria such as Yersinia pestis bacteria
- viruses such as vaccinia virus or haemorrhagic fever viruses, for example of the Ebola type.
- chemical decontamination agent any agent which, when it is brought into contact with a chemical species and in particular a toxic chemical species, is capable of destroying or inactivating it.
- the chemical species which are eliminated by the paste according to the invention are in particular toxic chemical species such as toxic gases, in particular neurotoxic or vesicants.
- toxic gases are in particular organophosphorus compounds, among which mention may be made of Sarin or GB agent, VX, Tabun or GA agent, Soman, Cyclosarin, diisopropyl fluoro phosphonate (DFP), Amiton or VG agent, the Parathion.
- Other toxic gases are mustard gas or agent H or agent HD, Lewisite or agent L, agent T.
- the nuclear, radioactive species which can be eliminated by the paste according to the invention can be chosen, for example, from metal oxides and hydroxides, in particular in the form of solid precipitates.
- the active decontamination agent for example the active biological or chemical decontamination agent can be chosen from bases such as sodium hydroxide, potassium hydroxide, and mixtures thereof; acids such as nitric acid, acid phosphoric, hydrochloric acid, sulfuric acid, hydrogen oxalates such as sodium hydrogen oxalate, and mixtures thereof; oxidizing agents such as peroxides, permanganates, persulfates, ozone, hypochlorites such as sodium hypochlorite, IV cerium salts, and mixtures thereof; quaternary ammonium salts such as hexadecylpyridinium (cetylpyridinium) salts, such as hexadecylpyridinium chloride (cetylpyridinium); reducing agents; and their mixtures.
- bases such as sodium hydroxide, potassium hydroxide, and mixtures thereof
- acids such as nitric acid, acid phosphoric, hydrochloric acid, sulfuric acid, hydrogen oxalates
- the active decontamination agent can be a disinfecting agent such as bleach, which provides the dough with decontamination, biological and / or chemical depollution properties.
- Certain active decontamination agents can be classified among several of the categories defined above.
- Nitric acid is therefore an acid, but also an oxidizing agent.
- the active decontamination agent such as a biocidal agent
- a concentration of 0.1 to 10 mol / L of pulp preferably of 0.5 to 10 mol / L of pulp, more preferably of 1 to 10 mol / L, and better still 3 to 6 mol / L of dough in order to guarantee a decontamination power, for example a power of inhibition of biological species, in particular biotoxic, compatible with the drying time of the dough, and to ensure, for example, a drying of the dough at a temperature between 20 ° C and 50 ° C and at a relative humidity between 20% and 60% on average in 30 minutes to 5 hours.
- the formulation of the paste supports different concentrations of active agent. It can be noted, in fact, that the increase in the concentration of decontamination agent more particularly in acid or basic decontamination agent considerably increases the drying time of the paste and therefore the efficiency of the process.
- the active decontamination agent can be an acid or a mixture of acids. These acids are generally chosen from mineral acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.
- a decontaminating agent in particular a particularly preferred biological decontaminating agent is nitric acid. Indeed, it turned out in a completely surprising way that nitric acid destroyed, inactivated, biological species, in particular biotoxic ones.
- nitric acid destroys and inactivates spores such as the spores of Bacillus thuringiensis which are particularly resistant species.
- the acid or acids is (are) preferably present at a concentration of 0.5 to 10 mol / L, more preferably from 1 to 10 mol / L, better still from 3 to 6 mol / L to ensure drying of the dough generally at a temperature between 20 ° C and 50 ° C and at a relative humidity between 20% and 60% on average in 30 minutes to 5 hours.
- the paste according to the invention can then be constituted by a clay, such as kaolinite, and by an acidic aqueous solution of nitric acid, for example IM, and phosphoric acid for example IM, the clay representing for example 40% to 60% by mass of the mass of the dough, and the acidic aqueous solution representing for example from 60% to 40% by mass of the mass of the dough.
- a clay such as kaolinite
- an acidic aqueous solution of nitric acid for example IM
- phosphoric acid for example IM
- the active decontamination agent for example the active biological decontamination agent, may be a base, preferably an inorganic base, preferably chosen from soda, potash, and mixtures thereof.
- the paste according to the invention has, in addition to the decontamination action, a degreasing action which also makes it possible to eliminate any contaminating species on the surface of the substrate.
- the dough according to the invention can have a large concentration range of basic decontamination agent (s).
- the base is advantageously present at a concentration of less than 10 mol / L, preferably between 0.5 and 7 mol / L, more preferably between 1 and 5 mol / L, better still between 3 and 6 mol / L, to ensure a drying of the dough at a temperature between 20 ° C and 50 ° C and at a relative humidity between 20% and 60% on average in 30 minutes to 5 hours.
- the decontamination agent in particular when it is a biological decontamination agent, is preferably sodium hydroxide or potassium hydroxide.
- the active decontamination agent in particular when it is a biocidal agent, will preferably be hydroxide. sodium at a concentration between 1 and 5 mol / L.
- the paste according to the invention may optionally also contain a surfactant or a mixture of surfactants, preferably chosen from the family of nonionic surfactants such as block copolymers, block copolymers such as block copolymers of 'ethylene oxide and propylene oxide, and ethoxylated fatty acids; and their mixtures.
- a surfactant or a mixture of surfactants preferably chosen from the family of nonionic surfactants such as block copolymers, block copolymers such as block copolymers of 'ethylene oxide and propylene oxide, and ethoxylated fatty acids; and their mixtures.
- the surfactants are preferably block copolymers marketed by BASF under the name PLURONIC ®.
- Pluronics ® are block copolymers of ethylene oxide and propylene oxide.
- the agent extracting contaminating species is chosen from inorganic adsorbents such as zeolites, clays, phosphates such as apatites, titanates such as sodium titanates, and ferrocyanides and ferricyanides.
- inorganic adsorbents such as zeolites, clays, phosphates such as apatites, titanates such as sodium titanates, and ferrocyanides and ferricyanides.
- This optional extracting agent such as a zeolite or a clay can be used in the case where the contaminating species is a radionuclide, but this optional extracting agent can also be used in the case of contaminating species other than radionuclides, such as for example metals, such as toxic metals or heavy metals.
- the chelating agent of the contaminating species is chosen from n-octylphenyl-N oxide, N-diisobutylcarbamoyl methylphosphine (CMPO), tributyl phosphate (TBP), l-hydroxyethane-1,1 diphosphonic acid ( HEDPA), di-2-ethylhexylphosphoric acid (DHEPA), trioctylphosphine oxide (TOPO), diethylenetriamine pentaacetate (DTPA), primary, secondary and tertiary organic amines, cobalt dicarbollide, calixarenes, niobates , ammonium molybdophosphate (AMP), (trimethylpentyl) phosphinic acid (TPPA), and mixtures thereof.
- CMPO N-diisobutylcarbamoyl methylphosphine
- TBP tributyl phosphate
- HEDPA tributyl phosphate
- the extracting agent can sometimes act as a chelating agent and vice versa.
- the coloring agent is chosen from dyes, preferably organic dyes, and pigments, preferably mineral dyes.
- the pigment is a mineral pigment.
- the mineral pigment is chosen from mineral pigments which are stable in the paste.
- stable pigment is generally understood to mean that the pigment does not exhibit a stable change in color over time, when the paste is stored for a minimum of 6 months.
- This pigment is usually the color it will impart to the paste.
- This pigment can be black, red, blue, green, yellow, orange, purple, brown, etc., and even white.
- the paste therefore has a color identical to the color of the pigment it contains. It is however possible that the paste has a color which differs from the color of the pigment it contains, but this is not sought.
- the pigment especially when it is white, is generally different from the inorganic viscosity agent.
- the mineral pigment is chosen so that it gives the paste after drying a color different from the color of the surface on which the paste is deposited.
- the mineral pigment is a micronized pigment, and the average particle size of the mineral pigment can be from 0.05 to 5 ⁇ m, preferably from 0.1 to 1 ⁇ m.
- the mineral pigment is chosen from oxides of metal (metals) and / or metalloid (s), hydroxides of metal (metals) and / or metalloid (s), oxyhydroxides of metal (metals) and / or of metalloid (s), ferrocyanides and ferricyanides of metal (metals), metal aluminates (metals), and mixtures thereof.
- the mineral pigment is chosen from iron oxides, preferably micronized, and their mixtures.
- the iron oxides can have different colors, they can be for example yellow, red, purple, orange, brown, or black.
- iron oxide pigments are known to have good hiding power and great resistance to acids and bases.
- iron oxides For incorporation into a decontamination paste, iron oxides have the best performance in terms of stability and coloring power. Thus, an iron oxide content of 0.1%, or even 0.01% by mass is sufficient to strongly color the dough without modifying its properties.
- Micronized iron oxides are available from the company Rockwood ® under the Ferroxide ® trade name.
- Ferroxide ® 212M which is a micronised red iron oxide with an average particle size of 0.1 pm
- Ferroxide ® M 228 which is a micronised red iron oxide with an average particle size of 0.5 pm.
- iron oxides In addition and / or instead of iron oxides, other oxides or hydroxides of colored metals or metalloids can be incorporated into the paste according to the invention, depending on the pH of the paste, mention may in particular be made of the vanadium oxide (V2O5) which is orange, manganese oxide (Mn02) which is black, cobalt oxide which is blue or green, and rare earth oxides.
- V2O5 vanadium oxide
- Mn02 manganese oxide
- cobalt oxide which is blue or green
- rare earth oxides rare earth oxides.
- iron oxides are preferred for the reasons stated above.
- the oxyhydroxides there may be mentioned goethite, that is to say iron oxyhydroxide FeOOH, which is very colored.
- metal ferrocyanide By way of example of metal ferrocyanide, mention may be made of Prussian blue, that is to say ferric ferrocyanide, and by way of example of aluminate, mention may be made of cobalt blue, it that is, cobalt aluminate.
- the solvent for the paste according to the invention is generally chosen from water, organic solvents, and their mixtures.
- a preferred solvent is water, and in this case, the solvent therefore consists of water, comprises 100% water.
- the paste according to the invention can in certain cases be defined as a paste called “reabsorbing” paste, in which case the paste is then specifically formulated to be supersaturated in solution, in solvent.
- a “reabsorbing”, “supersaturated” paste makes it possible in particular to decontaminate porous materials that are deeply contaminated.
- part of the solvent of the paste then spontaneously soaks the pores of the material and solubilizes the contaminating species (contaminants).
- the supersaturation therefore essentially depends on the composition of the dough, namely the type of materials included in the dough and their concentrations.
- the solution can be formulated so as to specifically react with the porous material to promote the solubilization of contaminating species, contaminants, for example by chemical attack, chelation of the contaminant etc.
- the paste is first brought into contact with the surface of the porous solid substrate to be decontaminated. Once the equilibrium has been reached between saturation of the paste in solution and imbibition of the porous material, the paste begins to dry, because the solvent evaporates at the paste-air interface. The solution soaked in the material is then reabsorbed within the paste under the effect of capillary rebalancing, causing at the same time the contaminants solubilized by advection and thereby allowing the decontamination of the porous material.
- the invention further relates to a method for decontaminating a substrate made of a solid material, said substrate being contaminated by at least one contaminating species called labile contaminating species and / or by at least one contaminating species known as surface contaminating species. on one of its surfaces, and / or by at least one contaminating species known as the subsurface contaminating species located just below said surface, and / or by at least one contaminating species located under said surface in the depth of the substrate, in which one carries out at least one cycle comprising the following successive steps:
- the dough is kept on the surface at least for a sufficient time for the dough to destroy and / or inactivate and / or absorb and / or dissolve the contaminating species, and for the dough to dry and forms a dry and solid residue containing said contaminating species;
- the decontamination process implements the paste according to the invention as described above and it therefore has all the advantageous effects inherent in this paste which have been described above in particular with regard to the thickness applied and the size of the residue. dry and solid obtained.
- the compound in the form of fibers ensures that an even greater thickness of dough, for example greater than or equal to 5 mm, preferably greater than or equal to equal to 6, 7, 8 or 9 mm, more preferably at least 10 mm -and up to for example up to 50 mm- hold on a vertical wall without sagging, and after drying a solid non-pulverulent waste is always obtained. This is demonstrated in Example 4.
- the pulp decontamination mechanism involved in the process according to the invention differs according to the type of decontamination.
- the paste is deposited on the contaminated surface and the viscosifying agent allows prolonged contact between the decontaminating solution (solvent for the paste) and the contaminated substrate.
- the paste can dissolve the labile and surface contamination but also corrode the substrate over several ⁇ m to dissolve the sub-surface contamination.
- the paste finally dries to produce a dry and solid residue at least centimeter containing the contaminating species.
- the paste according to the invention used in the process according to the invention, contains a specific inorganic viscosity agent chosen from clays and a compound in the form of fibers, and can be applied with a thickness much greater than that with which the gels are applied.
- the truly synergistic combination of these characteristics namely inorganic viscosity agent chosen from clays, composed in the form of fibers, and high applied thickness, makes it possible, surprisingly, to obtain a dry and solid residue comprising, on the contrary aspirable gels, little or no fractures, and therefore made up of one or more pieces (s) of a much larger size than the glitter of aspirable gel.
- the method according to the invention it is sought to avoid fractures, unlike methods which use aspirable gels in which it is sought to produce fractures.
- the method according to the invention makes it possible to fix, immobilize the contaminating species securely within the dry paste, of the dry and solid residue, which makes it possible to avoid any release in the event of leaching of the dry and solid residue.
- the process according to the invention is a reliable and reproducible process which can be described as a robust process and the efficiency of the process depends little on the way in which the dough is deposited.
- the pastes according to the invention can be spread manually on contaminated surfaces with a float. for example, or preferably, using a spraying machine in the manner of a mortar or a plaster.
- the substrate made of a solid material can be a porous substrate, preferably a porous mineral substrate.
- the efficiency of the paste and of the process according to the invention is just as good in the presence of a dense, non-porous and / or non-mineral surface.
- the substrate is made of at least one solid material chosen from metals and metal alloys such as stainless steel, painted steels, aluminum, and lead; polymers such as plastics or rubbers such as poly (vinyl chloride or PVC, polypropylenes or PP, polyethylenes or PE, in particular high density polyethylenes or HDPE, poly (methyl methacrylate or PMMA, poly ( vinylidene fluoride or PVDF, polycarbonates or PC; glasses; cements and cement materials; mortars and concretes; plasters; bricks; natural or artificial stone; ceramics.
- metals and metal alloys such as stainless steel, painted steels, aluminum, and lead
- polymers such as plastics or rubbers such as poly (vinyl chloride or PVC, polypropylenes or PP, polyethylenes or PE, in particular high density polyethylenes or HDPE, poly (methyl methacrylate or PMMA, poly ( vinylidene fluoride or PVDF, polycarbonates or PC; glasses; cements and cement materials; mortars and concretes; plaster
- the contaminating species is chosen from the chemical, biological, nuclear or radioactive contaminating species already listed above and in particular from the toxic biological species already listed above.
- the paste is applied to the surface to be decontaminated at the rate of 2000 g to 50,000 g of paste per m 2 of surface, preferably from 5,000 g to 10,000 g of paste per m 2 of surface, which corresponds approximately to a thickness of dough from 2 to 50 mm per m 2 of surface, preferably from 5 to 10 mm of dough per m 2 of surface.
- the paste can be applied to the surface manually, with a float for example, or using a spraying machine.
- the drying is carried out at a temperature of 1 ° C to 50 ° C, preferably from 15 ° C to 25 ° C, and under a relative humidity of 20% to 80%, preferably from 20% to 70%.
- the dough is kept on the surface for a period of 2 to 72 hours, preferably from 2 to 48 hours.
- the dry and solid residue is in the form of one or more pieces (x), each of said pieces having a size (defined by their largest dimension) greater than or equal to 1 cm, preferably greater than or equal to 2 cm, preferably still greater than or equal to 5 cm.
- the dry and solid residue is removed from the solid surface by a mechanical process such as brushing.
- the cycle described above can be repeated for example from 1 to 10 times using the same paste during all the cycles or by using different pastes during one or more cycle (s).
- step b) the dough, before total drying, is rewetted with a solution, for example with a solution of a decontamination agent, preferably with a solution of the active decontamination agent for the dough.
- a solution for example with a solution of a decontamination agent, preferably with a solution of the active decontamination agent for the dough.
- This rewetting operation can be repeated for example from 1 to 10 times.
- the paste applied during step a) may be a paste supersaturated with solvent (see above), in particular in the case where the substrate is made of a porous solid material.
- the process according to the invention can be qualified as a “regenerative” process because it uses a paste giving a waste, residue, dry and solid which, advantageously, can be regenerated to form a new paste according to the invention, which, if if necessary, can be used again in the process according to the invention.
- the waste, residue, dry and solid in order to be regenerated, can be brought into contact with a solution, comprising a solvent, and optionally one or more optional components mentioned above to thereby obtain a paste according to the invention as described above, for example, the waste, residue, dry and solid can be brought into contact with a solution of a decontamination agent.
- the process for decontaminating a substrate made of a solid material according to the invention in particular in the case where this substrate is made of a porous solid material does not require prior imbibition of the substrate, in particular thanks to effective control of the supersaturation ( see above) of the dough according to the invention.
- the process and the paste according to the invention exhibit, among other things, in addition to the advantageous properties already mentioned above, the following other advantageous properties:
- drying time is greater than or equal to the time necessary for inactivation.
- a rewetting can be used.
- the applications of the paste and of the surface, sub-surface and in-depth decontamination process, in particular of porous materials according to the invention are diverse and varied.
- a particularly targeted application concerns the nuclear decontamination of cementitious materials in order to minimize the waste generated by the clean-up and dismantling of nuclear installations at the end of their life.
- Figure 1 is a photograph of Dough-1 prepared in Example 1, in a container.
- Figure 2 is a photograph of Dough-2 prepared in Example 1, in a container.
- Figures 3A, 3B, and 3C show photographs showing a layer, deposit, of Dough-3 (Figure 3A), a layer, deposit, of Dough-1 ( Figure 3B), and a layer, deposit, of Dough-4 ( Figure 3C) deposited on a surface of a vertical mortar wall.
- the thickness of the layers of pasta deposited is 10 mm.
- the dough according to the invention can be easily prepared at room temperature.
- the dough according to the invention can be prepared by preferably adding gradually, (successively in any order, and / or simultaneously) the or inorganic viscosifying agent (s), and the compound in the form of fibers in solvent such as water, preferably deionized water, or in a mixture of the solvent and one or more several components chosen from the components already listed above, namely: a surfactant, an active decontamination agent, an agent extracting contaminant species, a chelating agent contaminant species, and a coloring agent.
- solvent such as water, preferably deionized water, or in a mixture of the solvent and one or more several components chosen from the components already listed above, namely: a surfactant, an active decontamination agent, an agent extracting contaminant species, a chelating agent contaminant species, and a coloring agent.
- This mixing can be carried out by mechanical stirring, for example by means of a mechanical stirrer equipped with a three-blade propeller.
- the rotation speed is for example 200 revolutions / minute, and the duration of the stirring is for example from 3 to 5 minutes.
- the addition of the inorganic viscous agent (s) and the compound in the form of fibers to the solvent or to the mixture of the solvent and of the component (s) mentioned above can be carried out. by simply pouring the viscosifying agent (s) and the compound in the form of fibers into the said mixture, successively in any order or simultaneously.
- the mixture containing the solvent, this or these inorganic viscosity agent (s) ( s), and / or the compound in the form of fibers and optionally the or component (s) mentioned above is generally kept under mechanical stirring.
- This stirring can be, for example, carried out by means of a mechanical stirrer equipped with a three-blade propeller.
- the stirring speed is generally gradually increased as the viscosity of the solution increases, finally reaching a stirring speed of for example between 400 and 600 revolutions / minute when all of the agent (s) inorganic viscosant (s) and compound in the form of fibers was added, without any splashes.
- the dough thus prepared is then left to stand for at least one hour before using it
- the optional surface-active agent of the paste according to the invention favorably and notably influences the rheological properties of the paste according to the invention.
- This surfactant in particular avoids the risks of spreading or sagging during the treatment of vertical surfaces and ceilings.
- the paste according to the invention thus prepared is then applied to the solid surface to be decontaminated from a substrate made of a solid material, in other words to the surface having been exposed to contamination, for example to biological contamination.
- contamination has already been described above.
- biological contamination can consist of one or more of the biological species already defined above.
- the active decontamination agent for example the active biological decontamination agent
- the active biological decontamination agent is chosen according to the contaminating species, for example the biological species to be eliminated, destroyed, or inactivate.
- the paste according to the invention allows to treat without any damage, all kinds of materials even fragile.
- the paste according to the invention generally does not generate any alteration, erosion, attack, chemical, mechanical or physical of the treated substrate.
- the paste according to the invention is therefore in no way detrimental to the integrity of the treated substrates and even allows their reuse.
- sensitive materials such as military equipment are preserved and can be reused after their decontamination, while the monuments treated with the paste according to the invention are absolutely not degraded and have their visual and structural integrity preserved.
- This substrate material can therefore be chosen from, for example, metals and alloys such as stainless steel, aluminum, and lead; polymers such as plastics or rubbers among which mention may be made of PVC, PP, PE in particular HDPE, PMMA, PVDF, PC; the glasses ; cements and cementitious materials; mortars and concretes; plasters; the bricks ; natural or artificial stone; ceramics.
- metals and alloys such as stainless steel, aluminum, and lead
- polymers such as plastics or rubbers among which mention may be made of PVC, PP, PE in particular HDPE, PMMA, PVDF, PC
- the glasses cements and cementitious materials; mortars and concretes; plasters; the bricks ; natural or artificial stone; ceramics.
- the treated surface can be painted or unpainted.
- the effectiveness of the treatment with the paste according to the invention is generally effective, including on contaminated substrates over several millimeters in depth.
- the paste according to the invention and the process implementing it allow the treatment of large surfaces, of geometries complex, for example with hollows, angles, recesses.
- the paste according to the invention ensures the effective treatment not only of substrates with horizontal surfaces such as floors, but also of substrates with vertical surfaces such as walls, or inclined or overhanging surfaces such as ceilings.
- the decontamination process according to the invention which uses a paste is particularly advantageous for the treatment of large surface materials , not transportable and installed outside. Indeed, the method according to the invention due to the implementation of a paste, allows in situ decontamination avoiding the spreading of chemical solutions in the environment and the dispersion of contaminating species.
- the paste according to the invention can be applied, spread over the surface to be treated by all the application methods known to those skilled in the art.
- Conventional methods are manual application, for example with a float, or application using a spraying machine in the manner of a mortar or a plaster.
- the sufficiently short viscosity recovery time of the pastes according to the invention allows the applied pastes to adhere to all surfaces, for example to walls.
- the quantity of paste deposited on the surface to be treated is generally from 2000 to 50,000 g / m 2 , preferably from 5,000 to 10,000 g / m 2 .
- the quantity of dough deposited per unit of surface and, consequently, the thickness of paste deposited influences the speed of drying.
- the effective contact time between the paste and the materials is then equivalent to its drying time. , period during which the active ingredient contained in the paste will interact with the contamination.
- the quantity of paste deposited - this paste containing, in addition, a specific viscosifying agent chosen from clays - when it is within the ranges mentioned above and in particular when it is greater or equal to 2000 g / m 2 and in particular in the range from 5000 to 10000 g / m 2 , which corresponds to a minimum thickness of paste deposited, for example greater than or equal to 2000 pm (2 mm) for a quantity of paste deposited greater than or equal to 2000 g / m 2 , allowed after drying of the dough to obtain a dry and solid residue in the form of one or more large piece (s) (the size being defined by the largest dimension or pieces), each of the pieces having a size greater than or equal to 1 cm, preferably greater than or equal to 2 cm, more preferably still greater than or equal to 5 cm.
- a specific viscosifying agent chosen from clays - when it is within the ranges mentioned above and in particular when it is greater or equal to 2000 g / m 2 and in particular in the range from
- the quantity of paste deposited, and therefore the thickness of paste deposited, preferably greater than or equal to 2000 g / m 2, ie 2000 ⁇ m, is, with the specific nature of the viscosifying agent used in the paste according to the invention (see above), the fundamental parameter which influences the size of the dry residues formed after drying of the dough and which thus ensures a dry and solid residue in the form of one or more large pieces, each of the pieces having a size greater than or equal to 1 cm, and not dry residues of millimeter size or pulverulent residues are formed.
- the dry and solid residue in the form of one or more large pieces obtained is easily removed by a mechanical process.
- the paste contains a surfactant at low concentration, generally from 0.1% to 2% of the total mass of the paste, then the drying of the paste is improved and leads to a increased ability of dry residue to detach from the support.
- the paste is then kept on the surface to be treated for the entire time necessary for its drying.
- the solvent contained in the paste namely generally the water contained in the paste evaporates until obtaining a dry and solid residue.
- the drying time depends on the composition of the dough in the concentration ranges of its constituents given above, but also, as has already been specified, on the quantity of dough deposited per unit of area, that is to say say the thickness of the dough deposited.
- the drying time also depends on climatic conditions, namely the temperature and the relative humidity of the atmosphere in which the surface of the substrate made of a solid material is found.
- the process according to the invention can be implemented under extremely wide climatic conditions, namely at a temperature T of 1 ° C to 50 ° C and at a relative humidity RH of 20% to 80%.
- the drying time of the dough according to the invention is therefore generally from 1 hour to 48 hours at a temperature T of 1 ° C to 50 ° C and at a relative humidity RH of 20% to 80%.
- the formulation of the paste according to the invention in particular when it contains surfactants such as "Pluronics ® " generally provides a drying time which is substantially equivalent to the contact time (between the decontamination, such as a biocidal agent, and contaminating species, for example biological species, in particular biotoxic to be eliminated) which is necessary, required to inactivate and / or absorb the contaminating species polluting the material of the substrate, and / or to achieve sufficient the surface erosion reactions of the material.
- the formulation of the paste ensures a drying time which is none other than the inactivation time of the contaminating species, for example biological species, which is compatible with the kinetics of inhibition of the contamination, for example biological contamination. Or else the formulation of the paste ensures a drying time which is none other than the time necessary for the erosion reactions to remove a contaminated surface layer from the material.
- the specific surface area of the generally used mineral filler which is generally from 50 m 2 / g to 300 m 2 / g, preferably from 100 m 2 / g and the absorption capacity of the paste according to the invention make it possible to trap the labile (surface) and fixed contamination of the material constituting the surface to be treated.
- the contaminating species for example the contaminating biological species are inactivated in the pasty phase. After the pulp has dried, the contamination, for example the inactivated biological contamination, is eliminated during the recovery of the dry pulp residue described below.
- the dry dough forms a dry residue which fractures little or not unlike the dry residue of the aspirable gels.
- This dry residue comprises one or more large pieces.
- the dry residue may contain the inactivated contaminant species.
- the dry residue obtained after drying the paste has poor adhesion to the surface of the decontaminated material. Therefore, the dry residue obtained after drying the dough can be easily recovered by simple mechanical processes such as brushing. However, dry residues can also be removed by gas jet, for example by compressed air jet.
- the process according to the invention therefore therefore firstly achieves a significant saving in chemical reagents compared to a process of decontamination by washing with a solution. Then the fact that a waste in the form of a dry residue easily recoverable mechanically is obtained, a rinsing operation with water or with a liquid, generally necessary for the removal of traces of chemical agents from the part , is generally avoided. This obviously results in a reduction in the quantity of effluents produced but also a significant simplification in terms of waste treatment and outlet channel.
- the dry waste can be stored or directed to an evacuation system ("outlet") without prior treatment.
- a solid waste is recovered in the form of one or more piece (s) of large dry paste, which can be packaged as it is, directly packaged, it results as a significant reduction in the quantity of effluents produced has already indicated above, as well as a significant simplification in terms of waste treatment and outlet channels.
- the paste may therefore contain powerful oxidizing agents such as cerium IV which can very easily be regenerated from the electrolysis of cerium III.
- the mass of dry waste produced is less than 1400 grams per m 2 .
- Dough-1 is a dough whose composition is as follows: 0.8% by weight (based on the total weight of the paste) of cellulose BC 1000 (fiber size of about 700 pm) marketed by Arbocel ®;
- Dough-2 is a dough whose composition is as follows:
- Deionized water is first weighed in a suitable container.
- the kaolinite and the cellulose are then gradually added to the water with stirring using a mechanical stirrer with three blades, until a homogeneous mixture presenting no lumps is obtained.
- the pastes thus formed are finally kept stirring for a few minutes.
- Figure 1 is a photograph of the prepared Dough-1.
- Figure 2 is a photograph of the prepared Dough-2.
- Each of the two pastes has a malleable structure which can be deposited on a surface, such as a wall of an installation for example, manually or using a projection machine, in the manner of a mortar or a coating.
- the effectiveness of a paste according to the invention is demonstrated, namely the paste-1 prepared in example 1 for decontaminating a porous material at the surface, subsurface and in depth. More precisely, in this example, we study decontamination using a decontaminating paste according to the invention, of a porous material constituted by a stack of glass beads, which is contaminated in depth by 133 Cs.
- the decontaminating paste according to the invention used in this example is Paste-1 prepared in Example 1.
- the porous material used is a stack of glass beads, of sizes between 45 ⁇ m and 90 ⁇ m, which is prepared in a round crystallizer with a diameter of 9.1 cm.
- the stack of glass beads produced which has a height of 2 cm, is soaked and saturated with 43.42 mL of an aqueous solution of CsNÜ3 with a CSNO3 concentration of 0.016 M. 93 mg of 133 They are present in the stack of glass beads.
- a 2 cm layer of Paste-1 is then placed on the stack of glass beads saturated with the solution. The whole is then left to dry under ambient conditions. After one week of drying, the residual solid waste resulting from the drying of Pulp-1 is separated from the stack of glass beads. The glass beads are then collected and washed using a 0.1 M NaOH solution. The washing solution is finally analyzed by atomic absorption spectroscopy in order to determine the amount of Cs remaining in the stack. glass beads, and thus study the effectiveness of the process. Analysis of the washing solution reveals the presence of 63.2 mg of Cs. The decontamination step thus made it possible to recover 68% of the contaminants - that is to say 133 Cs - present in the stack of glass beads.
- Paste-1 dried and absorbed the aqueous solution by capillary action.
- the contaminants - that is to say 133 Cs - were thus absorbed from the porous material towards the Paste-1 by advection.
- the “re-absorbent” pastes according to the invention have the capacity to decontaminate porous materials contaminated both at the surface, subsurface and in depth.
- the percentage of Cs retained by the clay depends on the initial amount of Cs added, which can be explained by the saturation of the binding sites.
- the pastes according to the invention can hold on a vertical wall even if they are applied with a significant thickness and this thanks to the presence of a compound in the form of fibers.
- a "paste-4" according to the invention whose composition is: 2.4% by mass of cellulose Arbocel BC 1000 ® sold by; 48.8% by mass of kaolinite sold by Sigma-Aldrich; and 48.8% by mass of deionized water.
- Figures 3A, 3B, and 3C show a layer, deposition, of Paste-3 (Figure 3A), a layer, deposition, of Paste-1 (described in Example 1) ( Figure 3B) and a layer, deposit, of Dough-4 ( Figure 3C) deposited on a surface of a vertical mortar wall.
- the thickness of the layers of pasta deposited is 10 mm.
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Abstract
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FR1872500A FR3089520B1 (en) | 2018-12-07 | 2018-12-07 | DECONTAMINATION PULP AND PROCESS FOR DECONTAMINATION OF A SUBSTRATE INTO A SOLID MATERIAL USING THIS Paste |
PCT/FR2019/052945 WO2020115443A1 (en) | 2018-12-07 | 2019-12-05 | Decontamination paste and method for decontaminating a substrate made of a solid material using said paste |
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KR100274703B1 (en) * | 1997-08-26 | 2000-12-15 | 김성년 | Gel-type decontamination material based on clay mineral for radioactive-contaminated surface and production method thereof |
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-
2018
- 2018-12-07 FR FR1872500A patent/FR3089520B1/en active Active
-
2019
- 2019-12-05 KR KR1020217021232A patent/KR20210110607A/en unknown
- 2019-12-05 CN CN201980080995.8A patent/CN113166685A/en active Pending
- 2019-12-05 WO PCT/FR2019/052945 patent/WO2020115443A1/en unknown
- 2019-12-05 US US17/298,715 patent/US20220049189A1/en active Pending
- 2019-12-05 EP EP19868217.1A patent/EP3870686A1/en active Pending
- 2019-12-05 JP JP2021530894A patent/JP2022510938A/en active Pending
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FR3089520A1 (en) | 2020-06-12 |
JP2022510938A (en) | 2022-01-28 |
WO2020115443A1 (en) | 2020-06-11 |
KR20210110607A (en) | 2021-09-08 |
US20220049189A1 (en) | 2022-02-17 |
FR3089520B1 (en) | 2021-09-17 |
CN113166685A (en) | 2021-07-23 |
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