CN111417744A - 用于除去含有冰晶石的沉积物的无硼酸组合物 - Google Patents
用于除去含有冰晶石的沉积物的无硼酸组合物 Download PDFInfo
- Publication number
- CN111417744A CN111417744A CN201880076195.4A CN201880076195A CN111417744A CN 111417744 A CN111417744 A CN 111417744A CN 201880076195 A CN201880076195 A CN 201880076195A CN 111417744 A CN111417744 A CN 111417744A
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- Prior art keywords
- acid
- aqueous composition
- cryolite
- total
- formula
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229910001610 cryolite Inorganic materials 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 239000011707 mineral Substances 0.000 claims abstract description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000004090 dissolution Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- -1 galvanized steel Chemical compound 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical group CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
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- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
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- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
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- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
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- 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
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- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
- C11D3/048—Nitrates or nitrites
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- 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
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- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
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- 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
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- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
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- 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
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- 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
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- C11D7/08—Acids
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- 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
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- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/007—Heating the liquid
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- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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Abstract
本发明涉及一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的水性组合物,所述组合物包含:a)至少一种无机酸,和b)至少一种式HOOC‑(CH2)x‑COOH的二羧酸,其中x=0‑3,且不向组合物中加入含硼酸根的化合物,还涉及相应的除去冰晶石沉积物的方法。
Description
本发明涉及一种组合物以及一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的方法。
已知的做法是将转化涂层施加到铝和钢(包括镀锌钢)的金属表面上,例如作为随后的有机涂层的合适表面涂覆基底。在磷化溶液的情况下,用于这些目的溶液可包含例如锌和磷酸根离子以及镍、锰、镁、钙、铜、钴、碱金属和/或铵的离子。
同样常见的是存在促进助剂如亚硝酸盐、氯酸盐、过氧化物或其组合,阴离子如氯离子和硫酸根以保持电中性,和任选的涂层改善助剂如羟基羧酸、氨基羧酸或缩合磷酸盐,以及络合或简单氟化物。
此外,还用于处理特别是铝和锌的是含有氟化物和任选的硝酸盐和/或磷酸盐的处理溶液。在处理铝的情况下,含有钛和/或锆离子、氟离子和任选的单宁的溶液也是常见的。
就上述溶液用于处理全部或部分由铝或其合金组成的金属表面而言,铝离子进入溶液中,并且通过存在于浴液中的钠离子和氟离子,根据以下反应方程式以冰晶石的形式沉淀:
3Na+(aq)+Al3+(aq)+6F–(aq)→Na3AlF6(s)↓
冰晶石具有非常低的溶解度。在这种情况下,一部分沉淀的冰晶石保持悬浮在浴液中或作为可泵送和可流动的沉淀物落到浴容器的底部。另一部分以非常牢固地粘附在浴容器壁上以及管线、泵、热交换器、喷嘴组件和喷嘴内部的结壳的形式生长,并且不利地影响装置的功能。因此,必须以规整的时间间隔在可达性受到限制的位置处机械地或化学地、化学地去除沉积物。
取决于所用的构建材料,使用基于硫酸、酰胺基硫酸、盐酸、硝酸或氢氧化钠/络合剂的溶剂,实施装置或装置的部分中的沉积物的化学去除。这些适用于除去在钢(包括镀锌钢)的磷化中产生的由磷酸锌和磷酸铁组成的结壳。
相反,在所讨论的沉积物在很大程度上由非常难溶的冰晶石组成的情况下,出现的困难是上述溶剂的侵蚀非常慢,而且只能溶解少量的结壳。这意味着维护时间不希望地长,并且化学品消耗的水平不成比例地高。
为了除去冰晶石沉积物,DE4128107A1教导了使装置或装置的部分与包含无机酸和含硼酸根化合物的溶液接触。
然而,从那时起,由于环境保护以及毒理学的原因,应尽可能避免使用含硼酸根的化合物如硼酸。在不久的将来,由于REACH法规,硼酸可能根本无法再用。至少,由于所述原因,硼酸的可用性在未来数年中将越来越多地下降。
本发明的目的是提供一种组合物以及一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的方法,所述组合物和方法分别不再具有已知组合物或方法的缺点,并且特别允许耗时较少、经济的清洁方法,同时还基本上、更特别完全不使用含硼酸根的化合物进行操作。
此外,冰晶石沉积物完全分解/分散所需的时间(溶解时间)以及每单位量溶剂所溶解的冰晶石沉积物的量与由无机酸和含硼酸根化合物的组合所获得的那些相当。
该目的首先通过本发明的从装置或装置的部分除去冰晶石沉积物的方法实现,所述方法包括使装置或装置的部分与水性组合物接触,所述水性组合物包含:
a)至少一种无机酸,和
b)至少一种式HOOC-(CH2)x-COOH的二羧酸,其中x为0-3,
并且不向所述组合物中加入含硼酸根的化合物。
尽管所述至少一种无机酸以其高酸性有助于分解冰晶石沉积物,但在这方面所述至少一种二羧酸的作用可归因于其是Al3+的有效络合剂,并且通过络合,从冰晶石的溶解度平衡中除去这些离子。
定义:
术语“冰晶石沉积物”在本文中是指由优选大于50重量%,更优选大于90重量%的冰晶石(干重)组成的固体沉积物,即结壳。
“除去冰晶石沉积物”旨在不仅应理解为所述沉积物从相应的装置或装置的部分上脱离,而且还应理解为至少90重量%发生溶解和/或分散,更特别是沉积物完全溶解/分散。
“水性组合物”在本文中应理解为主要包含,即超过50重量%的水作为溶剂或分散介质的组合物。水性组合物优选为溶液,更优选为仅含有水作为其溶剂的溶液。
“不向所述组合物中加入含硼酸根的化合物”的陈述并非旨在排除在组合物中可能存在可忽略比例的含硼酸根的化合物,在这种情况下,这可归因于所用原料的污染。“含硼酸根的化合物”特别是指硼砂和硼酸。
酸的“当量浓度”与可从酸释放出的质子的摩尔浓度同义。例如,在硫酸的情况下,每分子酸释放出两个质子。因此,摩尔浓度为1mol/l的硫酸具有2mol/l的当量浓度。
所述至少一种二羧酸也可作为盐加入到溶液中,换言之,作为二羧酸盐或二羧酸一氢盐加入到水性组合物中。
根据一个优选的实施方案,使装置和/或装置的部分与水性组合物接触,所述水性组合物包含:
a)至少一种(总)当量浓度为1.0-10mol/l的无机酸,和
b)至少一种总浓度为0.07-1.7mol/l的式HOOC-(CH2)x-COOH的二羧酸,其中x为0-3,
并且不向所述组合物中加入含硼酸根的化合物。
该至少一种无机酸优选以2.0-8.0mol/l,更优选3.0-6.0mol/l,非常优选3.5-4.5mol/l的(总)当量浓度存在,而该至少一种二羧酸以0.07-1.5mol/l,更优选0.35-1.5mol/l,非常优选0.35-1.0mol/l,尤其优选0.5-0.8mol/l的总浓度存在。
同样包括的是所述至少一种无机酸的前述浓度范围与所述至少一种二羧酸的前述浓度范围的所有组合。
所述水性组合物优选包含摩尔比为2.4:1至60:1,更优选为2.6:1至60:1,更优选为2.6:1至12:1,非常优选为4.0:1至12:1,尤其优选为5.0:1至8.0:1的所述至少一种无机酸和所述至少一种二羧酸(所述至少一种无机酸的(总)当量浓度mol/l相对于所述至少一种二羧酸的总浓度mol/l)。
特别有利的是,使装置或装置的部分与水性组合物接触,所述水性组合物包含盐酸、硫酸和/或硝酸作为所述至少一种无机酸。
所述至少一种无机酸特别优选为硫酸。
从技术应用的观点且基于其功能性,硫酸优于盐酸和硝酸。因此,使用盐酸的问题是,冰晶石沉积物只能缓慢溶解,因为不可能为了加速溶解过程而加热装置。否则形成的蒸汽将腐蚀装置。另一方面,在硝酸的情况下,危险是通过与磷化残留物反应可能形成亚硝气。
所述至少一种式HOOC-(CH2)x-COOH的二羧酸可为戊二酸(x=3)、琥珀酸(x=2)、丙二酸(x=1)和/或草酸(x=0)。
相反,x>3的二羧酸,例如x=4的己二酸在水性介质中的溶解度过低,因此不再能作为Al3+的络合剂。
所述至少一种二羧酸优选为丙二酸(x=1)和/或草酸(x=0),更优选为草酸(x=0)。
所述水性组合物有利地进一步包含至少一种非离子表面活性剂。原因是这有利于水性组合物润湿冰晶石沉积物。在这种情况下,特别有利的是所述至少一种非离子表面活性剂选自乙氧基化的脂肪醇聚乙二醇醚。
所述水性组合物可优选进一步包含至少一种腐蚀抑制剂,以便在装置或装置的部分与水性组合物接触期间保护其免受腐蚀。
该至少一种腐蚀抑制剂优选包括至少一种选自脲衍生物和二醇(包括烷氧基化二醇)的化合物。
根据第一个特别优选的实施方案,所述至少一种腐蚀抑制剂为N,N'-二乙基硫脲,或者为N,N'-二(邻甲苯基)硫脲、N,N'-二丁基硫脲和六亚甲基四胺的混合物。
根据第二个特别优选的实施方案,所述至少一种腐蚀抑制剂是其中R1和R2均为H的式I化合物与其中R1和R2彼此独立地各自为HO-(CH2)w基团(w≥2),优选均为HO-CH2)2基团的式I化合物的混合物:
R1O-(CH2)x-C≡C-(CH2)y-OR2 (I),
其中对于两种式I化合物的每一种,x和y在每种情况下彼此独立地为1-4。这种混合物比上述脲衍生物毒性有害程度低,对环境的危害也小。
特别有利的是,根据本发明,上述类型的方法以这样的方式配置,使得装置和/或装置的部分与水性组合物接触,所述组合物包含:
a)(总)当量浓度为1.0-10mol/l的硫酸,和
b)总浓度为0.07-1.7mol/l的草酸,
其中不向所述组合物中加入含硼酸根的化合物。
该硫酸优选以2.0-8.0mol/l,更优选3.0-6.0mol/l,非常优选3.5-4.5mol/l的(总)当量浓度存在,而草酸以0.07-1.5mol/l,更优选0.35-1.5mol/l,非常优选0.35-1.0mol/l,尤其优选0.5-0.8mol/l的总浓度存在。
同样包括的是硫酸的前述浓度范围与草酸的前述浓度范围的所有组合。
所述水性组合物优选包含摩尔比为2.4:1至60:1,更优选为2.6:1至60:1,更优选为2.6:1至12:1,非常优选为4.0:1至12:1,尤其优选为5.0:1至8.0:1的硫酸和草酸(硫酸的(总)当量浓度mol/l相对于草酸的总浓度mol/l)。
在使用硫酸作为所述至少一种无机酸的情况下,根据本发明的一个有利的实施方案,使装置或装置的部分与额外包含硝酸盐的水性组合物接触。在含有硫酸的水性组合物中存在硝酸盐确保了由不锈钢制成的装置或装置的部分的钝化。
在用包含硫酸和草酸和硝酸盐的水性组合物处理装置和/或装置的部分中,如果根据本发明的另一个有利的实施方案,使所述装置和/或装置的部分与其中硫酸(以H2SO4计算)与硝酸盐(以NO3 –计算)的重量比为5:1至50:1,优选15:1至25:1的水性组合物接触,则获得特别有利的结果。
待除去冰晶石沉积物的装置可例如为喷雾磷化装置或浸没磷化装置。
优选通过将所述水性组合物导入装置中至一定高度,使得装置的所有带有冰晶石沉积物的部分被该水性组合物覆盖,从而使待除去冰晶石沉积物的装置与所述组合物接触。
或者,也可将受影响的装置的部分拆卸并置于所述水性组合物的相应处理浴中,从而使得装置的所有部分都被水性组合物覆盖。
为了加速冰晶石沉积物的溶解,在这种情况下,有利的是在与相应装置或装置的相应部分接触的同时搅拌该水性组合物。
或者,所述水性组合物可特别有利地通过装置—槽、管、喷嘴等循环。
所述水性组合物的使用温度原则上可介于室温和约95℃之间。然而,特别有利的是40-80℃,更特别是50-70℃的温度,因为此时冰晶石沉积物的溶解是特别快的,但是不必经受相当高的能量消耗。例如,可通过加热相应的装置和/或相应的处理浴来建立所需的温度。
如果使所述水性组合物在装置中循环,则除去时间,更特别是所有冰晶石沉积物完全溶解/分散的时间(溶解时间)优选为2-6小时。
每100g水性组合物溶解的冰晶石沉积物的量优选为至少4g,更优选为至少5g。
在这种情况下,优选地,当冷却水性组合物时,尤其是冷却至室温时,几乎没有沉降物形成。这使得水性组合物在从装置或装置的部分中泵出之后,更容易循环。
除了将其应用于由耐酸金属材料制成的装置或装置的部分之外,本发明的组合物/方法还特别适于由塑料制成的那些。
其次,所述目的通过一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的水性组合物实现,所述组合物包含:
a)至少一种无机酸,和
b)至少一种式HOOC-(CH2)x-COOH的二羧酸,其中x为0-3,
并且不向所述组合物中加入含硼酸根的化合物。
本发明的该组合物的有利配置已经在上文结合本发明的方法进行了阐述。
此外,本发明涉及一种浓缩物,通过用合适的溶剂和/或分散介质,优选用水稀释,可由该浓缩物获得本发明的水性组合物。
本发明的组合物/方法通过以下实施例更详细地阐明,其不应被理解为施加任何限制。
实施例:
在用于处理由80重量%铝、15重量%镀锌钢和5重量%钢组成的金属表面的喷雾磷化装置中,在喷嘴组件中观察到微溶性沉积物,这些沉积物的组成如下(所有数字以重量%计):
因此,所述沉积物由约95重量%的冰晶石(Na3AIF6)组成。
在每种情况下,在玻璃容器中用确定量的溶剂覆盖一块冰晶石结壳。然后在温和搅拌(250转/分钟)和下表1中报告的温度下,首先用肉眼确定结壳完全溶解/分散所用的时间。在表1中报告的时间(所需的溶解时间)之后,将溶剂与明显溶解/分散的结壳一起转移到离心管中。在约1小时后,观察离心管的圆柱体尖端以确定是否形成了沉降物。关于表1中的结果,对于所报告的结壳的可溶量和所需的溶解时间,没有测量到沉降物。
表1:
表中汇总的结果表明,使用基于各种浓度的盐酸、硫酸、氢氧化钠(含或不含络合剂),氯化铝和酰胺基硫酸(除了60℃的硫酸和硫酸/硼酸组合)的溶剂,在结壳完全溶解/分散之前需要相对长的溶解时间。
相反,当使用本发明的方法时,所需的溶解时间相对较短。然而,特别引人注目的是,当使用本发明的方法时,100g溶剂所吸收的冰晶石沉积物的量显著高于使用除硫酸/硼酸组合以外的其他溶剂时的量。
相对于大多数对比试验(不含硼酸根的方案)测量,溶解量大4-6倍,结果是显著节约了溶剂。当使用本发明的方法时,溶解的量与用硫酸/硼酸组合溶解的量相当。
己二酸不溶于20%的硫酸,因此不能用作Al3+的络合剂。因此,结果与单独使用20%硫酸的结果相同。因此,此时结壳的可溶量也显著低于硫酸/硼酸组合的情况下的可溶量。
另一方面,戊二酸可溶于20%的硫酸—尽管溶解过程可能需要30分钟。相应地,此时结壳的可溶量已经与硫酸/硼酸组合的可溶量相当。
就所需的溶解时间而言,用6%和11%草酸(与20%硫酸组合)可获得最好的结果。然而,使用6%草酸的优点还在于,与11%草酸的情况相比,冷却后存在较少的沉降物。
Claims (13)
1.一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的水性组合物,所述组合物包含:
a)至少一种无机酸,和
b)至少一种式HOOC-(CH2)x-COOH的二羧酸,其中x为0-3,
并且不向所述组合物中加入含硼酸根的化合物。
2.根据权利要求1所述的水性组合物,其包含:
a)至少一种(总)当量浓度为1.0-10mol/l,优选为3.0-6.0mol/l的无机酸,和
b)至少一种总浓度为0.07-1.7mol/l,优选为0.35-1.5mol/l的通式HOOC-(CH2)x-COOH的二羧酸。
3.根据权利要求1或2所述的水性组合物,其包含摩尔比为2.4:1至60:1,优选为2.6:1至12:1的所述至少一种无机酸和所述至少一种二羧酸(所述至少一种无机酸的(总)当量浓度mol/l相对于所述至少一种二羧酸的总浓度mol/l)。
4.根据前述权利要求中任一项所述的水性组合物,其中所述至少一种无机酸包括硫酸。
5.根据权利要求4所述的水性组合物,其进一步包含硝酸盐。
6.根据前述权利要求中任一项所述的水性组合物,其中所述至少一种二羧酸包括丙二酸和/或草酸,优选草酸。
7.根据权利要求4-6中任一项所述的水性组合物,所述组合物包含:
a)(总)当量浓度为3.0-6.0mol/l,优选为3.5-4.5mol/l的硫酸,和
b)总浓度为0.35-1.0mol/l,优选为0.5-0.8mol/l的草酸,
且以4.0:1至12:1,优选5.0:1至8.0:1的摩尔比包含硫酸和草酸(硫酸的(总)当量浓度mol/l相对于草酸的总浓度mol/l)。
8.根据前述权利要求中任一项所述的水性组合物,其额外包含至少一种非离子表面活性剂,优选至少一种选自乙氧基化脂肪醇聚乙二醇醚的非离子表面活性剂。
9.根据前述权利要求中任一项所述的水性组合物,其额外包含至少一种腐蚀抑制剂,所述腐蚀抑制剂优选包括至少一种选自脲衍生物和二醇的化合物,所述二醇包括烷氧基化二醇。
10.根据权利要求9所述的水性组合物,其中所述至少一种腐蚀抑制剂是其中R1和R2均为H的式I化合物与其中R1和R2彼此独立地各自为HO-(CH2)w且w≥2基团,优选均为HO-CH2)2基团的式I化合物的混合物:
R1O-(CH2)x-C≡C-(CH2)y-OR2 (I),
其中对于两种式I化合物的每一种,x和y在每种情况下彼此独立地为1-4。
11.一种浓缩物,通过用合适的溶剂和/或分散介质稀释,可由其获得根据前述权利要求中任一项所述的水性组合物。
12.一种从用于金属表面转化处理的装置或装置的部分除去冰晶石沉积物的方法,其包括使所述装置和/或装置的部分与根据权利要求1-10中任一项所述的水性组合物接触。
13.根据权利要求12所述的方法,其中所述水性组合物具有40-80℃、优选50-70℃的温度。
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CN111417744B (zh) | 2023-03-17 |
JP7394761B2 (ja) | 2023-12-08 |
KR20200097258A (ko) | 2020-08-18 |
EP3724371A1 (de) | 2020-10-21 |
US20200385872A1 (en) | 2020-12-10 |
JP2021505774A (ja) | 2021-02-18 |
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BR112020009513A2 (pt) | 2020-10-13 |
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