CN1981402A - 清洗和钝化燃料电池系统的方法和组合物 - Google Patents
清洗和钝化燃料电池系统的方法和组合物 Download PDFInfo
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- CN1981402A CN1981402A CNA2005800222152A CN200580022215A CN1981402A CN 1981402 A CN1981402 A CN 1981402A CN A2005800222152 A CNA2005800222152 A CN A2005800222152A CN 200580022215 A CN200580022215 A CN 200580022215A CN 1981402 A CN1981402 A CN 1981402A
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- Prior art keywords
- acid
- passivator
- acrylate
- cleaning agent
- copolymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000000446 fuel Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004140 cleaning Methods 0.000 title claims description 77
- 230000007797 corrosion Effects 0.000 claims abstract description 81
- 238000005260 corrosion Methods 0.000 claims abstract description 81
- 239000003112 inhibitor Substances 0.000 claims abstract description 62
- 239000002826 coolant Substances 0.000 claims abstract description 54
- 239000008139 complexing agent Substances 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- -1 methylene phosphonic acids Chemical class 0.000 claims description 67
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000012459 cleaning agent Substances 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
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- 229920001897 terpolymer Polymers 0.000 claims description 18
- 239000013530 defoamer Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 11
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003139 biocide Substances 0.000 claims description 10
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 9
- 230000003115 biocidal effect Effects 0.000 claims description 9
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 8
- RXDAPJJFRLSRPX-UHFFFAOYSA-N 2,3-dimethoxypropan-1-ol Chemical compound COCC(CO)OC RXDAPJJFRLSRPX-UHFFFAOYSA-N 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 8
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- 229940035423 ethyl ether Drugs 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 108010064470 polyaspartate Proteins 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000003704 aspartic acid Nutrition 0.000 claims description 7
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 7
- 101000598921 Homo sapiens Orexin Proteins 0.000 claims description 6
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 claims description 6
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 5
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 5
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- BGOVVUPZKMHFQZ-BTJKTKAUSA-N (z)-but-2-enedioic acid;2-phenylethenesulfonic acid Chemical compound OC(=O)\C=C/C(O)=O.OS(=O)(=O)C=CC1=CC=CC=C1 BGOVVUPZKMHFQZ-BTJKTKAUSA-N 0.000 claims description 4
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 4
- UCNUAGQCOCSQMY-UHFFFAOYSA-N 2-phosphanylbutanedioic acid Chemical compound OC(=O)CC(P)C(O)=O UCNUAGQCOCSQMY-UHFFFAOYSA-N 0.000 claims description 4
- KMDMOMDSEVTJTI-UHFFFAOYSA-N 2-phosphonobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)P(O)(O)=O KMDMOMDSEVTJTI-UHFFFAOYSA-N 0.000 claims description 4
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 239000004698 Polyethylene Chemical group 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
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- 150000002461 imidazolidines Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Chemical group 0.000 claims description 4
- UBYZGUWQNIEQMH-SBBOJQDXSA-M potassium;(2s,3s,4s,5r)-2,3,4,5,6-pentahydroxy-6-oxohexanoate Chemical compound [K+].OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UBYZGUWQNIEQMH-SBBOJQDXSA-M 0.000 claims description 4
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 4
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 4
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 3
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- YTSACTNRGUJEGO-UHFFFAOYSA-N oxirane prop-1-ene Chemical group CC=C.C1CO1 YTSACTNRGUJEGO-UHFFFAOYSA-N 0.000 claims 1
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- B08B9/027—Cleaning the internal surfaces; Removal of blockages
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- 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
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- 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
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- 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
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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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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- 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
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Abstract
本发明描述了清洁剂-钝化剂组合物及处理燃料电池冷却系统的方法。清洁剂-钝化剂包含络合剂、表面活性剂、腐蚀抑制剂和溶剂。清洁剂-钝化剂减少在燃料电池冷却剂系统中循环并导致燃料电池冷却剂电导率增大的污染物。此外,钝化剂减少燃料电池系统的表面腐蚀。
Description
背景
[0001]燃料电池是用于多种应用之中的清洁高效电力源,其应用包括替代或补充目前在汽车中使用的内燃机。燃料电池组件包括阳极(即在其中发生氧化反应的带负电荷的电极)、阴极(即在其中发生还原反应的带正电荷的电极)和位于两电极之间的电解质。为了产生用作车辆发动机的充足电力,燃料电池发动机通常使用包含串联连接的多个燃料电池组件(例如约100或更多的燃料电池)的燃料电池堆。单一燃料电池的工作DC电压为约0.6伏至约1.0伏,汽车燃料电池堆的工作DC电压可以为125伏至450伏。
[0002]在燃料电池系统中,单个燃料电池的部件(例如阳极、阴极和/或双极板)包含冷却剂通道。冷却剂通道使冷却剂在燃料电池堆之内的每一个燃料电池组件周围循环。在冷却剂通过冷却剂通道循环时,可以通过调节冷却剂流及温度来控制燃料电池堆的温度。
[0003]然而,围绕燃料电池堆的冷却系统与燃料电池堆本身均处于相同的电压之下。为了减少在燃料电池堆之内发生电击的可能性,冷却剂应该具有低的电导率,例如低于约5microseamens/cm(μS/cm)。在燃料电池系统的正常工作期间,冷却剂系统部件的腐蚀、浸析和分解会导致生成能增大冷却剂电导率的离子性物质。为了阻止冷却剂的电导率超限,可以使用混合床离子交换树脂过滤器除去生成的离子性物质。由于低电导率的要求及预计使用的混合床离子交换树脂的原因,在这些系统中使用腐蚀抑制剂则不是切实可行的。至少部分的原因是由于许多腐蚀抑制剂包含离子性物质。在用于提供有效腐蚀保护的抑制剂浓度,包含抑制剂的冷却剂具有的电导率可能超过低于约5μS/cm的可接受限度。此外,这些离子性腐蚀抑制剂可能会被混合床离子交换树脂脱除。
[0004]因此,仍然需要有在燃料电池系统的使用和寿命期间保持冷却剂电导率在期望的水平和/或在使用期间阻止燃料电池系统腐蚀的组合物及方法。
概述
[0005]一方面,用于燃料电池冷却剂系统处理的清洁剂-钝化剂组合物包含络合剂;表面活性剂;腐蚀抑制剂;和溶剂;其中清洁剂-钝化剂组合物中没有附加的不可生物降解的氨基羧酸盐。
[0006]另一方面,用于燃料电池冷却剂系统处理的清洁剂-钝化剂组合物包含络合剂;表面活性剂;硅酸盐,包含一个或多个硅-碳键的基于有机硅烷的化合物,四烷基原硅酸酯,或它们的组合;吡咯;焦磷酸盐;和溶剂。
[0007]处理燃料电池冷却剂系统的方法包括将燃料电池冷却剂系统与清洁剂-钝化剂组合物接触,用冲洗溶剂来冲洗燃料电池冷却剂系统。
附图简述
[0008]图1为显示不同清洁剂-钝化剂对Al 3003(一种类型的铝)腐蚀保护的处理效果的电流(I)-电势极化曲线。
[0009]从下面的详细描述、附图以及附带的权利要求中,本领域的技术人员可以意识和明了上述以及其它的特点。
详细描述
[0010]在冷却剂电导率的研究中发现,可以将要与燃料电池冷却剂系统接触的新部件在与冷却剂接触之前进行清洗,从而减少不期望的冷却剂电导率的增加。此外,在燃料电池系统的正常工作期间,冷却剂系统部件的腐蚀、浸析和分解也可能导致生成增加冷却剂电导率的离子性物质。因此可能需要进行燃料电池系统的定期清洗。为了减少系统腐蚀和延长系统使用寿命,还期望在加入新的冷却剂之前和/或在冷却剂系统中安装新部件之后钝化燃料电池冷却剂系统。钝化作用可以在燃料电池冷却剂系统部件的表面上生成保护膜,保护部件免受腐蚀。
[0011]发明者在此已经发现,使用组合清洁剂-钝化剂组合物,既可以清洗又能钝化燃料电池冷却剂系统中的金属及非金属表面。清洁剂清洗燃料电池冷却剂系统的内部,清除燃料电池冷却剂系统表面上的油类、淤泥、腐蚀产物及其它不期望的污染物和/或沉积物。清洁剂可以使这些物质分散和/或溶解至清洁剂溶液中。钝化剂促进在燃料电池冷却剂系统的金属表面上的持久保护膜的形成。该保护膜可以减小系统在后续正常工作期间的金属表面腐蚀倾向。在使用组合清洁剂-钝化剂组合物进行处理之后,可以将系统排空并用冲洗溶剂冲洗,即使用去离子水。当冲洗溶液的电导率降低至指定的低水平时,将系统排空。然后加入用于系统正常工作的冷却剂。
[0012]用于燃料电池冷却剂系统的组合清洁剂-钝化剂组合物可以是单处理包装形式或两包装形式,其中一个包含清洁剂组合物,另一个包含钝化剂组合物。为了简化应用方法,可以采用单处理包装。为了在处理之后达到更好的钝化效果和形成更持久的保护膜,可以采用两包装处理。清洗和/或钝化方法可以在10℃至100℃的温度下进行。为了增大沉积物清除速率、加快钝化过程和促进更好的保护层的形成,可以在高于环境温度的温度下进行清洗和钝化过程中的任意一个或这两个过程,例如约30℃至约100℃。
[0013]清洁剂-钝化剂组合物包含络合剂、表面活性剂、腐蚀抑制剂、溶剂、任选的消泡剂、任选的pH调节剂、任选的杀生物剂和任选的着色剂和/或染料。清洁剂组合物包含络合剂、表面活性剂、腐蚀抑制剂、溶剂、任选的消泡剂、任选的pH调节剂、任选的杀生物剂和任选的着色剂和/或染料。钝化剂组合物包含腐蚀抑制剂、溶剂、任选的消泡剂、任选的pH调节剂、任选的杀生物剂和任选的着色剂和/或染料。个别的清洁剂和/或钝化剂组分可以具有多于一种功能。例如某些pH调节剂还可以起腐蚀抑制剂的作用(例如硼砂和硝酸),某些腐蚀抑制剂还可以起络合剂的作用(例如焦磷酸钾)。
[0014]此处使用的术语络合剂包括螯合剂。络合剂可以包括羟基羧酸盐(例如柠檬酸、酒石酸、葡糖酸、葡糖二酸、葡庚糖酸、乙醇酸和它们的异构体及盐);膦酸盐和次磷酸盐[例如HEDP(1-1-羟基亚乙基-1,1-二膦酸)、PBTC(2-膦酰基丁烷-1,2,4-三羧酸)、AMP(氨基三(亚甲基膦酸))、HPA(羟基膦酰基乙酸)、HMDTMP(六亚甲基二胺四(亚甲基膦酸))、DTPA二亚乙基三胺五(亚甲基膦酸)、Bricorr 288(膦酰基丁二酸及其单、双和多聚加合物)、PSO(膦基丁二酸及其单、双和低聚加合物)以及它们的异构体和盐];不可生物降解的氨基羧酸盐[例如EDTA(乙二胺四乙酸)和NTA(次氨基三乙酸)];可生物降解的氨基羧酸盐[例如EDDS{(S,S)-乙二胺二丁二酸}、IDSA(亚氨基二丁二酸)、MGDA(亚甲基二乙酸)、乙二胺-N,N′-二戊二酸、2-羟基亚丙基二胺-N,N′-二丁二酸、羟基亚乙基二胺三乙酸以及它们的异构体和盐];羧酸盐和二羧酸盐(例如草酸、苯甲酸、甲酸、乙酸、氨基磺酸、己二酸、丁二酸和过乙酸);基于丙烯酸酯的聚合物、共聚物及三元共聚物,[例如聚丙烯酸酯、丙烯酸酯-丙烯酰胺共聚物、丙烯酸酯-AMPS(丙烯酰胺基亚甲基磺酸)共聚物、丙烯酸酯-马来酸酯共聚物、丙烯酸酯-羟基丙基丙烯酸酯(hydroxypropolyacrylate)共聚物、丙烯酸酯-磺酸共聚物、丙烯酸酯-丙烯酰胺-磺酸三元共聚物、磺烷基化丙烯酰胺丙烯酸酯三元共聚物、胺取代磺甲基化丙烯酰胺丙烯酸酯三元共聚物、聚甲基丙烯酸、丙烯酸酯-甲基丙烯酸酯共聚物、次磷酸酯-丙烯酸酯共聚物、丙烯酸酯-AMPS-苯乙烯磺酸酯三元共聚物、丙烯酸酯-AMPS-次磷酸酯三元共聚物];基于马来酸的聚合物(例如聚马来酸、聚马来酸酐、苯乙烯磺酸酯-马来酸共聚物、磺化苯乙烯马来酸酐);基于聚天冬氨酸和天冬氨酸的共聚物等;以及包含一种或多种前述络合剂的组合。在一个实施方案中,络合剂为柠檬酸。在另一实施方案中,清洁剂和/或钝化剂可以不含不可生物降解的氨基羧酸盐,例如EDTA和NTA。还在另一实施方案中,清洁剂和/或钝化剂可以不含可生物降解的氨基羧酸盐以及不可生物降解的氨基羧酸盐,即不含附加的氨基羧酸盐。
[0015]使用表面活性剂清除油和油脂。表面活性剂可以包括非离子型表面活性剂[例如(a)EO-PO(环氧乙烷-环氧丙烷)嵌段共聚物,如BASF Corp.的Pluronic L61、L62、L63、L64、L65、L81和L101,以及商标名为Tetronic和Tetronic R、Pluronic L和R以及Alkatronic的其它EP-PO、EO-PO-EO、PO-EO-PO嵌段共聚物;(b)壬基苯氧基乙氧基化物(NPE),例如Igepal CO(CDN)、Tergitol NP系列、Makron系列、AlkasurfNP、Sulfonic N系列等;(c)辛基酚乙氧基化物(OPE),例如TritonX系列、Surfonic NP、Sulfonic OP系列、Igepal CA(CDN);(d)伯和仲乙氧基化醇,例如Alfonic、DeSonic和Tergitol15-S系列、Neodol牌,(e)聚乙烯脂肪酸,如妥尔油,以及(f)聚环氧丙烷或聚丙二醇(PPG)和聚环氧乙烷或聚乙二醇等];阴离子型表面活性剂,例如二辛基磺基丁二酸钠、十二烷基苯磺酸钠、磺化二苯醚等;阳离子型表面活性剂,例如乙氧基化醚胺;两性表面活性剂,例如脂肪酸的胺和咪唑啉衍生物等;水溶助剂表面活性剂,例如烷基萘磺酸钠、芳族或脂族磷酸酯和二甲苯磺酸钠;醇表面活性剂(例如ShellChemicals的Neodol牌醇表面活性剂);以及包含一种或多种前述表面活性剂的组合。在某些实施方案中,表面活性剂包括EO-PO嵌段共聚物和/或烷氧基化醇,如Tomah的乙氧基化线形醇Tomadol 25-12。
[0016]使用腐蚀抑制剂以减少燃料电池冷却剂系统中的腐蚀。腐蚀抑制剂可以包括铝腐蚀抑制剂(例如硅酸盐;带有包含1至20个碳原子的烷基基团的四烷基原硅酸酯(例如原硅酸四甲基酯、原硅酸四乙基酯等);和/或包含硅-碳键的基于有机硅烷的化合物[即在水存在下能水解形成甲硅烷醇(即带有Si-OH基团的化合物)的化合物],例如(三羟基甲硅烷基)-丙基甲基膦酸钠或Dow Corning的Q1-6083,和烷氧基硅烷,例如SilquestY-5560硅烷(即聚氧化亚烷基烷氧基硅烷)、SilquestA-186[2-(3,4-环氧环己基)乙基三甲氧基硅烷]、SilquestA-187(3-缩水甘油氧基丙基三甲氧基硅烷)、3-氨基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、辛基三乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、甲基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、异丁基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三甲氧基硅烷、氯丙基三乙氧基硅烷、氯丙基三甲氧基硅烷、3-(三甲氧基甲硅烷基)丙基二甲基十八烷基氯化铵、双三乙氧基甲硅烷基丙基四硫化物、双三乙氧基甲硅烷基丙基二硫化物,或可以从OSi Specialties或GE Silicones获得的其它Silquest类型的硅烷,以及可以从Dow Corning及其它供应商处获得的基于硅烷的偶联剂;羧酸盐,例如苯甲酸盐;C5-C16二羧酸盐;C5-C16单羧酸;新羧酸;烷基(C1-C14)环己烯酸及其盐;硝酸盐;亚硝酸盐;磷酸盐;以及包含一种或多种前述铝腐蚀抑制剂的组合;黄色金属腐蚀抑制剂(例如烃基三唑例如苯并三唑和甲苯基三唑,噻唑例如巯基苯并噻唑,咪唑例如苯并咪唑,以及其它吡咯);黑色金属腐蚀抑制剂(例如正磷酸盐、焦磷酸盐、六偏磷酸盐、多磷酸盐、膦酸盐、次磷酸盐、钼酸盐、钒酸盐、钨酸盐、硼酸盐、硅酸盐、锌化合物、羧酸盐等);以及包含一种或多种前述腐蚀抑制剂的组合。在一个实施方案中,腐蚀抑制剂包含铝腐蚀抑制剂、黄色金属腐蚀抑制剂和黑色金属腐蚀抑制剂。在另一实施方案中,腐蚀抑制剂包含硅酸盐、四烷基原硅酸酯、含有硅-碳键的基于有机硅烷的化合物或包含一种或多种前述化合物的组合;吡咯;及焦磷酸盐。
[0017]任选的消泡剂可以包括硅酮,例如可以从OSI Specialties,Dow Corning或其它供应商获得的SAG10或类似产品;环氧乙烷-环氧丙烷(EO-PO)嵌段共聚物和环氧丙烷-环氧乙烷-环氧丙烷(PO-EP-PO)嵌段共聚物(例如Pluronic L61、Pluronic L81或其它Pluronic和Pluronic C产品);聚环氧乙烷或聚环氧丙烷,例如PPG2000(即平均分子量为2000的聚环氧丙烷);疏水无定形二氧化硅;基于聚二有机硅氧烷的产品(例如包含聚二甲基硅氧烷(PDMS)的产品等);脂肪酸或脂肪酸酯(例如硬脂酸等);脂肪醇,烷氧基化醇及聚二醇;聚醚多元醇乙酸酯、聚醚乙氧基化山梨醇(sorbital)六油酸酯和聚(环氧乙烷-环氧丙烷)单烯丙基醚乙酸酯;蜡、石脑油、煤油和芳族油;和包含一种或多种前述消泡剂的组合。某些表面活性剂可以起到表面活性剂和消泡剂组合的作用。
[0018]此处任选的pH调节剂包括缓冲和调节清洗溶液pH值的试剂。pH调节剂可以包括硼酸盐、磷酸盐、碳酸盐、碱(例如NaOH、KOH)、酸(例如H2SO4、H3PO4和HNO3)等;和包含一种或多种前述pH调节剂的组合。
[0019]任选的杀生物剂可以包括一种或多种非氧化性杀生物剂,例如戊二醛、异噻唑啉酮(isothiazolones)(例如5-氯-2-甲基-4-异噻唑啉-5-酮和2-甲基-4-异噻唑啉-3-酮)、2-溴-2-硝基丙烷-1,3-二醇、2,2-二溴-3-次氨基丙酰胺、十二烷基胍盐酸盐、二硫代氨基甲酸酯、亚甲基二硫氰酸酯、季胺、2-(硫氰基甲基硫代)苯并噻唑、硫酸四羟基甲基、2-硝基-2-羟基甲基-1,3-丙二醇以及包含一种或多种前述杀生物剂的组合。使用足够量的杀生物剂以产生期望水平的杀生物活性。
[0020]任选的着色剂和/或染料包括例如Abbey Color Inc.的“Alizarine Green”、“Uranine Yellow”或“Green AGS-liquid”,Crompton& Knowles Corp.的“Orange II(Acid Orange 7)”或“Intracid RhodamineWT(Acid Red 388)”等,以及包含一种或多种前述着色剂和染料的组合。使用足够量的着色剂和/或染料以提供期望的颜色。
[0021]清洁剂和/或钝化剂组合物的合适溶剂包括例如水;二醇;如乙二醇、1,2-丙二醇、二乙二醇、三乙二醇、二丙二醇和1,3-丙二醇、丁二醇;醇,例如甲醇、乙醇、丙醇、异丙醇、丁醇、糠醛、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇,以及包含一种或多种前述溶剂的组合。
[0022]基于清洁剂-钝化剂系统总重量而言,单组分(one part)清洁剂-钝化剂系统包含:络合剂为约0.1%重量至约50%重量,优选约0.2%重量至约30%重量,更优选约0.4%重量至约20%重量;表面活性剂为约0.003%重量至约10%重量,优选约0.006%重量至约5%重量,更优选约0.008%重量至约2.5%重量;消泡剂为约0%重量至约1%重量,优选约0.002%重量至约0.5%重量,更优选约0.003%重量至约0.2%重量;腐蚀抑制剂为约0.001%重量至约10%重量,优选约0.003%重量至约5%重量,更优选约0.005%重量至约3%重量;足够量的缓冲及pH调节剂,用以调节pH值为约pH4至约pH13,优选约pH5至约pH12.5,更优选约pH6至约pH12;溶剂为约20%重量至约99.7%重量,优选约40%重量至约99.5%重量,更优选约60%重量至约99.4%重量。
[0023]基于清洁剂的总重量而言,优选清洁剂包含:络合剂为约0.2%重量至约50%重量,优选约0.3%重量至约40%重量,更优选约0.4%重量至约30%重量;表面活性剂为约0.003%重量至约10%重量,优选约0.006%重量至约5%重量,更优选约0.008%重量至约2.5%重量;消泡剂为约0%重量至约1%重量,优选约0.002%重量至约0.5%重量,更优选约0.002%重量至约0.2%重量;腐蚀抑制剂为约0.001%重量至约10%重量,优选约0.003%重量至约5%重量,更优选约0.005%重量至约3%重量;足够量的缓冲及pH调节剂,用以调节pH值为约pH1至约pH13,优选约pH2至约pH11,更优选约pH3至约9;溶剂为约20%重量至约99.8%重量,优选约40%重量至约99.7%重量。
[0024]基于钝化剂的总重量而言,优选钝化剂包含:消泡剂为约0%重量至约2%重量,优选约0.002%重量至约1%重量,更优选约0.003%重量至约0.5%重量;腐蚀抑制剂为约0.001%重量至约10%重量,优选约0.002%重量至约6%重量,更优选约0.003%重量至约5%重量;足够量的缓冲及pH调节剂,用以调节pH值为约pH6至约pH13,优选约pH7至约pH12.5,更优选约pH7.5至约pH11.5;溶剂为约80%重量至约99.5%重量,优选约90%重量至约99%重量。
[0025]在一个实施方案中,清洁剂-钝化剂组合物中的腐蚀抑制剂包括硅酸盐、四烷基原硅酸酯、含有硅-碳键的基于有机硅烷的化合物,或包含一种或多种前述化合物的组合;吡咯类化合物;及焦磷酸盐化合物。当存在硅酸盐和/或四烷基原硅酸酯时,其占清洁剂和/或钝化剂组合物总重量的约0.005%重量至约1%重量,优选约0.01%重量至约0.7%重量,更优选约0.02%重量至约0.5%重量。当存在含有硅-碳键的基于有机硅烷的化合物时,其占清洁剂和/或钝化剂组合物总重量的约0.001%重量至约1%重量,优选约0.005%重量至约0.5%重量,更优选约0.01%重量至约0.2%重量。吡咯类化合物占清洁剂和/或钝化剂组合物总重量的约0.0002%重量至约2%重量,优选约0.001%重量至约1%重量,更优选约0.002%重量至约0.6%重量。焦磷酸盐占清洁剂和/或钝化剂组合物总重量的约0.001%重量至约1%重量,优选约0.002%重量至约0.8%重量,更优选约0.0025%重量至约0.5%重量。
[0026]如果清洁剂-钝化剂组合物为单包装清洁剂-钝化剂组合物的形式,则组合物的pH可以为约pH4至约pH13,或约pH7至约pH12.5。如果清洁剂和钝化剂组合物分开为两包装,则清洁剂的pH可以为约pH1至约pH13,或约pH3至约pH11。钝化剂组合物具有的pH可以为约pH6至约pH13,或约pH7至约pH12.5。如果清洁剂组合物的pH低于约7,可以加入一种或多种氧清除剂和铁离子还原剂,例如异抗坏血酸盐、亚硫酸盐、亚硫酸氢盐等,以使在清洗期间的腐蚀程度最小。
[0027]清洗和钝化燃料电池系统的方法包括将燃料电池系统与上述的单组分或两组分形式的清洁剂-钝化剂组合物接触。在与清洁剂-钝化剂组合物接触之后,优选将燃料电池系统用冲洗溶剂进行冲洗,例如水、甲醇、乙醇、丙醇、丁醇、糠醛、乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、丁二醇、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述溶剂的组合。优选的是接触和冲洗进行的方式应使得后续与燃料电池系统接触的冷却剂的电导率在约1小时的暴露于冷却剂之后充分保持低于约5microseamens/cm。用于该测试的冷却剂包含约10%重量至约100%重量的水和约10%重量至约90%重量的醇。醇包括例如甲醇、乙醇、丙醇、丁醇、糠醛、乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、丁二醇、丙三醇(glycrol)、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇和包含一种或多种前述醇的组合。用于该测试的冷却剂不应该包含明显改变冷却剂电导率的添加剂。
[0028]清洁剂-钝化剂可以用于处理燃料电池系统,例如PEMFC(质子交换膜或聚合物电解质膜燃料电池)、PAFC(磷酸燃料电池)、MCFC(熔融碳酸盐燃料电池)、SOFC(固体氧化物燃料电池)和AFC(碱性燃料电池)。
[0029]通过下面非限制性实施例进一步举例说明本发明。
实施例1.清洁剂-钝化剂组合物
表1:实施例1的清洁剂-钝化剂组合物
组分 | 功能 | %重量 |
DI水 | 溶剂 | 88.843% |
柠檬酸 | 络合剂 | 4.625% |
NaOH,50% | pH调节剂 | 5.842% |
SilquestY-5560硅烷 | 腐蚀抑制剂 | 0.08% |
硅酸钠 | 腐蚀抑制剂 | 0.21% |
焦磷酸钾 | 络合剂和腐蚀抑制剂 | 0.05% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.05% |
硝酸钠 | 腐蚀抑制剂 | 0.2% |
Pluronic L-61 | 表面活性剂和消泡剂 | 0.1% |
总计 | 100% |
[0030]在该实施例中,将浓清洁剂-钝化剂稀释10倍(270ml去离子(DI)水+30ml清洁剂-钝化剂)。用于模拟燃料电池冷却剂系统中通常使用的部件的样品为两个铸铝试片、两个黄铜试片、两个不锈钢(SS316)试片、一个钎焊铝试片、一个硅酮密封垫和两个Viton O形环。样品的总表面积为194平方厘米,样品之间互相电连接。将Teflon块体放入玻璃罐底部,把金属试片置于罐中Teflon块体的顶部。将清洁剂-钝化剂溶液加入至玻璃罐中,并在溶液达到80℃之后加热20分钟。为了清除清洁剂-钝化剂溶液,使用300ml DI水将带有样品的玻璃罐用DI水冲洗2次并弃去冲洗溶液。然后将300ml DI水加入到罐中,将溶液电导率记录为时间的函数。作为比较,将同样的样品浸没于300ml DI水中,不进行清洁剂-钝化剂处理,通过记录溶液电导率进行空白测试。在下面给出得到的结果。
表2:实施例1中清洁剂-钝化剂的电导率数据
时间 | 空白测试电导率(μS/cm) | 实施例1清洁剂-钝化剂处理的电导率(μS/cm) |
0分钟 | 1.80 | 0.36 |
20分钟 | 10.12 | 0.77 |
60分钟 | 16.65 | 1.17 |
120分钟 | 21.20 | 1.55 |
18小时 | 38.00 | 3.21 |
[0031]从表2中可以看出,空白测试样品显示暴露于样品的水的电导率显著增加,从0分钟时的1.8μS/cm变化到18小时时的38μS/cm。暴露于用清洁剂-钝化剂处理过的样品的水的初始电导率仅为0.36μS/cm,在18小时之后增加至3.21μS/cm。因此,在该实施例中,清洁剂-钝化剂处理减少了暴露于样品的水的电导率的发展。
实施例2:可选的清洁剂-钝化剂系统
表3:清洁剂-钝化剂组合物
组分 | 功能 | %重量 |
DI水 | 溶剂 | 88.743% |
柠檬酸 | 络合剂 | 4.625% |
NaOH,50% | pH调节剂 | 5.842% |
SilquestY-5560硅烷 | 腐蚀抑制剂 | 0.08% |
硅酸钠 | 腐蚀抑制别 | 0.21% |
焦磷酸钾 | 络合剂和腐蚀抑制剂 | 0.05% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.05% |
硝酸钠 | 腐蚀抑制剂 | 0.2% |
Pluronic L-61 | 表面活性剂和消泡剂 | 0.2% |
总计 | 100% |
[0032]除了表面活性剂/消泡剂的量加倍之外,实施例2的清洁剂-钝化剂处理与实施例1的相同。使用的样品包括一个铸铝试片、一个黄铜管部分、一个不锈钢(SS316)试片、一个钎焊铝试片、一个硅酮密封垫和两个Viton O形环。样品的总表面积为120平方厘米。样品之间互相电连接。将两套样品放入到分开的装有300ml自来水的玻璃罐中。样品预先在自来水中腐蚀五天,之后用DI水冲洗,用纸巾干燥。然后将样品放入到清洁玻璃罐中。
[0033]将浓清洁剂-钝化剂稀释10倍(270ml DI水+30ml清洁剂-钝化剂)。将清洁剂-钝化剂溶液加入至玻璃罐中,并在溶液达到80℃之后加热20分钟。为了清除清洁剂-钝化剂溶液,然后使用300ml DI水将带有样品的玻璃罐用DI水冲洗2次并弃去冲洗溶液。然后将300ml DI水加入到罐中,将溶液电导率记录为时间的函数。作为比较,将同样的样品浸没于300ml DI水中,不进行清洁剂-钝化剂处理,通过记录溶液电导率进行空白测试。在下面给出得到的结果。
表4:实施例2中清洁剂-钝化剂的电导率数据
时间 | 空白试验电导率(μS/cm) | 实施例1清洁剂-钝化剂处理的电导率(μS/cm) |
0分钟 | 1.80 | 0.34 |
20分钟 | 2.64 | 1.50 |
120分钟 | 5.56 | 3.62 |
22小时 | 22.1 | 6.88 |
[0034]从表4中可以看出,空白测试样品显示暴露于样品的水的电导率显著增加,从0分钟时的1.8μS/cm变化到22小时时的22.1μS/cm。暴露于用清洁剂-钝化剂处理的样品的水的初始电导率仅为0.34μS/cm,在22小时之后增加至6.88μS/cm。因此,在该实施例中,清洁剂-钝化剂处理减少了暴露于样品的水的电导率的发展。
实施例3:可选的清洁剂-钝化剂
表5:清洁剂-钝化剂组合物
组分 | 功能 | %重量 |
DI水 | 溶剂 | 88.773% |
柠檬酸 | 络合剂 | 4.624% |
NaOH,50% | pH调节剂 | 5.813% |
PPG-2000(聚丙二醇) | 消泡剂 | 0.002% |
硅酸钠 | 腐蚀抑制剂 | 0.07% |
n-丙醇 | 溶剂 | 0.018% |
焦磷酸钾 | 络合剂和腐蚀抑制剂 | 0.05% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.05% |
Tomadol 25-12(乙氧基化醇) | 表面活性剂 | 0.6% |
总计 | 100% |
[0035]采用的测试方法类似于实施例1。一个区别为在这些测试中清洗-钝化步骤在室温下进行,例如约22℃。测试样品与实施例2中使用的相同(数量上和种类上)。
表6:实施例3中清洁剂-钝化剂的结果
时间 | 冲洗编号-空白 | 冲洗编号-试验 | 空白电导率 | 试验电导率 | 温度 |
0分钟 | 0 | 0 | 9.31μS/cm | 11.08mS/c | 21.5℃ |
20分钟 | 0 | 0 | 13.46μS/cm | 11.16mS/cm | 20.7℃ |
40分钟 | 0 | 0 | 14.53μS/cm | 10.95mS/cm | 22.7℃ |
60分钟 | 0 | 0 | 18.86μS/cm | 10.83μS/cm | 23.3℃ |
0分钟 | 1 | 1 | 2.33μS/cm | 158.6μS/cm | 21.2℃ |
0分钟 | 2 | 2 | 0.85μS/cm | 7.61μS/cm | 21.6℃ |
0分钟 | 3 | 3 | 0.60μS/cm | 2.83μS/cm | 22.0℃ |
0分钟 | 4 | 4 | 0.72μS/cm | 2.75μS/cm | 22.5℃ |
0分钟 | 5 | 5 | 0.67μS/cm | 1.47μS/cm | 21.6℃ |
20分钟 | 5 | 5 | 2.54μS/cm | 5.86μS/cm | 22.0℃ |
40分钟 | 5 | 5 | 3.52μS/cm | 7.06μS/cm | 22.1℃ |
60分钟 | 5 | 5 | 4.52μS/cm | 8.44μS/cm | 22.5℃ |
80分钟 | 5 | 5 | 5.45μS/cm | 8.97μS/cm | 22.4℃ |
100分钟 | 5 | 5 | 6.33μS/cm | 9.67μS/cm | 21.9℃ |
20小时 | 5 | 5 | 26.8μS/cm | 27.6μS/cm | 22.8℃ |
[0036]结果表明当使用实施例3制剂时,由于泡沫情况的原因,需要更多冲洗步骤。在实施例3中在暴露于清洗-钝化处理后,采用3次DI水冲洗以将包含测试样品的溶液电导率降低至1.47μS/cm。
实施例4:可选的清洁剂-钝化剂处理
表7:清洁剂-钝化剂组合物
组分 | 功能 | %重量 |
DI水 | 溶剂 | 88.953% |
柠檬酸 | 络合剂 | 4.625% |
NaOH,50% | pH调节剂 | 5.842% |
PPG-2000 | 消泡剂 | 0.002% |
硅酸钠 | 腐蚀抑制剂 | 0.21% |
异丙醇 | 溶剂 | 0.018% |
焦磷酸钾 | 络合剂和腐蚀抑制剂 | 0.1% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.05% |
Tomadol 25-12 | 表面活性剂 | 0.2% |
总计 | 100% |
[0037]采用的测试方法类似于实施例1。一个区别为在这些测试中清洗-钝化步骤在室温下进行,例如约22℃。测试样品与实施例2中使用的相同(数量上和种类上)。
表8.实施例4中清洁剂-钝化剂的结果
时间 | 冲洗编号-空白 | 冲洗编号-试验 | 空白电导率 | 试验电导率 | 温度 |
0分钟 | 0 | 0 | 未确定 | N.D. | |
60分钟 | 0 | 0 | 11.63mS/cm | 21.5℃ | |
0分钟 | 1 | 1 | 196μS/cm | 21.9℃ | |
0分钟 | 2 | 2 | 12.18μS/cm | 21.8℃ | |
0分钟 | 3 | 3 | 2.32μS/cm | 21.9℃ | |
0分钟 | 4 | 4 | 1.97μS/cm | 21.7℃ | |
0分钟 | 5 | 5 | 3.27μS/cm | 1.62μS/cm | 21.6℃ |
20分钟 | 5 | 5 | 12.35μS/cm | 10.35μS/cm | 22.4℃ |
40分钟 | 5 | 5 | 18.36μS/cm | 13.63μS/cm | 21.9℃ |
60分钟 | 5 | 5 | 21.2μS/cm | 15.12μS/cm | 22.2℃ |
80分钟 | 5 | 5 | 23.4μS/cm | 16.20μS/cm | 22.0℃ |
100分钟 | 5 | 5 | 25.0μS/cm | 17.07μS/cm | 21.9℃ |
120分钟 | 5 | 5 | 26.5μS/cm | 17.95μS/cm | 21.6℃ |
20小时 | 5 | 5 | 52.4μS/cm | 32.1μS/cm | 21.6℃ |
0分钟 | 6 | 6 | 2.29μS/cm | 1.36μS/cm | 21.3℃ |
30分钟 | 6 | 6 | 3.98μS/cm | 2.88μS/cm | 21.7℃ |
60分钟 | 6 | 6 | 4.60μS/cm | 3.36μS/cm | 21.7℃ |
[0038]结果表明对于实施例4制剂,由于泡沫情况的原因,需要更多冲洗步骤。实施例4中在暴露于清洗-钝化处理后,5次DI水冲洗后的电导率为1.62μS/cm。
[0039]总之,实施例1至4的测试结果表明,由于腐蚀产生新的离子性物质以及从样品表面清除污染物可能并不完全的原因,单单用DI水多次冲洗样品并不足以保持低电导率。此外,在清洁剂-钝化剂处理中使用的表面活性剂也影响到清除清洗溶液所需的冲洗次数。清洗方法期间产生的泡沫可能是该问题的原因。最后,处理的钝化能力取决于处理组合物和应用温度。提高处理温度(例如至80℃)和使用适当配制的处理物可以得到合适的结果,即合适的清洗、用过的处理物容易冲洗清除、在样品表面形成高效和持久的保护钝化膜。
比较实施例5:仅用钝化剂处理
[0040]在该实施例中显示使用清洁剂-钝化剂处理对铝表面的增强腐蚀保护的优点。使表面积为8.04平方厘米同样的3003铝板试片按以下经受同样的处理,(1)在实施例1描述的溶液中,清洗-钝化温度80℃,20分钟;(2)在实施例1的溶液中,但温度为40℃;(3)仅用DI水;(4)不做处理-空白;和(5)在下面描述的钝化剂处理溶液中,80℃,20分钟。
表9.钝化剂处理
组分 | 功能 | %重量 |
DI水 | 溶剂 | 1.9743% |
乙二醇 | 溶剂 | 95.144% |
磷酸,75% | 腐蚀抑制剂/pH调节剂 | 0.6602% |
硼砂5mol | pH调节剂/腐蚀抑制剂 | 0.3975% |
NaOH,50% | pH调节剂 | 1.0948% |
SilquestY-5560硅烷 | 腐蚀抑制剂 | 0.0775% |
硅酸钠 | 腐蚀抑制剂 | 0.3847% |
PPG-2000 | 消泡剂 | 0.0007% |
硝酸钠 | 腐蚀抑制剂 | 0.2% |
异丙醇 | 溶剂 | 0.0060% |
荧光素钠染料 | 着色剂 | 0.002% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.0583% |
总计 | 100% |
[0041]处理之后,用DI水冲洗铝板,并浸没于用空气饱和的50%重量乙二醇+50%DI水+100ppm作为Cl的氯化物(来自NaCl)溶液中。30分钟之后,在从腐蚀电势区域(约-0.6V/AgAgCl至+1.0V/AgAgCl)进行包括线性极化和阳极极化的电化学测量。在图1中,曲线1为使用于80℃的实施例1中的清洁剂-钝化剂,曲线2为使用于40℃的实施例2中的清洁剂-钝化剂,曲线3为没有清洁剂-钝化剂处理的空白测试,曲线4为在80℃下去离子水处理,曲线5为如表9中那样在80℃下仅用钝化剂处理。阳极极化曲线结果(图1)显示,在80℃处理的实施例1溶液提供了最佳的总体腐蚀保护。阳极电流通常比空白测试(即没有处理)低多于一个数量级。换言之,腐蚀保护效率大于约90%。就具有稍微较高的钝化膜击穿电势和在比0.0V/AgAgCl更阳极的电势区域较低的阳极电流而言,在40℃处理的实施例1溶液提供了次最佳的腐蚀保护。在电势低于约0V/AgAgCl处的钝化膜击穿时,仅钝化剂处理就提供了最佳的腐蚀保护。去离子水处理相对空白提供非常轻微改善的腐蚀保护。
实施例6-清洁剂-钝化剂处理
表10-可选的清洁剂-钝化剂组合物
组分 | 功能 | %重量 |
DI水 | 溶剂 | 91.293% |
Bayhibit AM(或PBTC,50%) | 络合剂 | 4.625% |
NaOH,50% | pH调节剂 | 3.392% |
SilquestY5560硅烷 | 腐蚀抑制剂 | 0.08% |
硅酸钠 | 腐蚀抑制剂 | 0.21% |
焦磷酸钾 | 络合剂和腐蚀抑制剂 | 0.05% |
硝酸钠 | 腐蚀抑制剂 | 0.2% |
甲苯基三唑钠 | 腐蚀抑制剂 | 0.05% |
Pluronic L-61 | 表面活性剂 | 0.1% |
总计 | 100% |
注:在80℃下清洗期间在Al试片上发生大量氢释出反应,可能表明高的Al腐蚀速率。
样品的表面积为+/-198cm2。空白流体为300ml DI H2,测试流体为30ml清洁剂+270ml DI H2O。
表11-实施例6的清洁剂-钝化剂结果
时间 | 冲洗空白# | 冲洗试验# | 电导率空白 | 电导率试验 | 温度 |
0分钟 | 0 | -------- | 80.0℃ | ||
20分钟 | 0 | -------- | 80.0℃ | ||
0分钟 | 1 | 193.5μS/cm | 25.6℃ | ||
0分钟 | 2 | 9.91μS/cm | 23.7℃ | ||
0分钟 | 0 | 3 | 2.31μS/cm | 0.61μS/cm | 23.1℃ |
20分钟 | 0 | 3 | 11.05μS/cm | 2.71μS/cm | 22.5℃ |
40分钟 | 0 | 3 | 16.67μS/cm | 3 86μS/cm | 22.9℃ |
60分钟 | 0 | 3 | 21.2μS/cm | 5.53μS/cm | 22.7℃ |
80分钟 | 0 | 3 | 24.5μS/cm | 7.41μS/cm | 22.2℃ |
100分钟 | 0 | 3 | 26.5μS/cm | 8.93μS/cm | 22.3℃ |
120分钟 | 0 | 3 | 28.0μS/cm | 10.65μS/cm | 22.3℃ |
[0042]如表11所示,与水空白相比,即使在处理之后120分钟,清洁剂钝化剂也给出了大于2倍的电导率改善。
[0043]与简单的水洗相比,公开的清洁剂-钝化剂组合物导致暴露于模型系统的水的电导率降低。预计采用清洁剂-钝化剂处理降低燃料电池冷却剂系统中的循环冷却剂的电导率。如实施例所示,使用清洁剂和钝化剂导致循环污染物的减少以及表面腐蚀降低。因此,通过使用公开的清洁剂-钝化剂可以保持燃料电池冷却剂系统中循环冷却剂的电导率在可接受的范围之内。
[0044]此处公开的所有范围都是包括界限和可组合的。虽然参考优选的实施方案对本发明进行了描述,但本领域技术人员应该明了的是在不偏离本发明范围情况下可以进行各种变化,其中的要素可以用等价物取代。此外,根据本发明的教导,在不偏离其实质范围的情况下,可以进行多种修改以适应具体的情况或材料。因此,本发明并不意味着局限于所公开的预计为实施本发明的最佳方式的具体实施方案,本发明包括处于所附的权利要求范围之内的所有实施方案。
Claims (40)
1.一种用于处理燃料电池冷却剂系统的清洁剂-钝化剂组合物,所述组合物包含:
络合剂;
表面活性剂;
腐蚀抑制剂;和
溶剂;
其中清洁剂-钝化剂组合物不包含附加的不可生物降解的氨基羧酸盐。
2.权利要求1的清洁剂-钝化剂组合物,其中清洁剂-钝化剂组合物不包含附加的氨基羧酸盐。
3.权利要求1的清洁剂-钝化剂组合物,其中络合剂为羟基羧酸盐;膦酸盐;次磷酸盐;羧酸盐;二羧酸盐;基于丙烯酸酯的聚合物、共聚物或三元共聚物;基于马来酸的聚合物、共聚物或三元共聚物;聚天冬氨酸;基于天冬氨酸的共聚物;或包含一种或多种前述络合剂的组合。
4.权利要求3的清洁剂-钝化剂,其中络合剂为柠檬酸、酒石酸、葡糖酸、葡糖二酸、葡庚糖酸、乙醇酸、HEDP(1-1-羟基亚乙基-1,1-二膦酸)、PBTC(2-膦酰基丁烷-1,2,4-三羧酸)、AMP(氨基三(亚甲基膦酸))、HPA(羟基膦酰基乙酸)、HMDTMP(六亚甲基二胺四(亚甲基膦酸))、DTPA(二亚乙基三胺五(亚甲基膦酸))、膦酰基丁二酸或其单、双和低聚加合物、膦基丁二酸或其单、双和低聚加合物、草酸、苯甲酸、甲酸、乙酸、氨基磺酸、己二酸、丁二酸、过乙酸、聚丙烯酸酯、丙烯酸酯-丙烯酰胺共聚物、丙烯酸酯-AMPS(丙烯酰胺基亚甲基磺酸)共聚物、丙烯酸酯-马来酸酯共聚物、丙烯酸酯-羟基丙基丙烯酸酯共聚物、丙烯酸酯-磺酸酯共聚物、丙烯酸酯-丙烯酰胺-磺酸酯三元共聚物、胺取代磺烷基化丙烯酰胺丙烯酸酯三元共聚物、聚马来酸、聚马来酸酐、聚甲基丙烯酸、丙烯酸酯-甲基丙烯酸酯共聚物、苯乙烯磺酸酯-马来酸共聚物、次磷酸酯-丙烯酸酯共聚物、丙烯酸酯-AMPS-苯乙烯磺酸酯三元共聚物、丙烯酸酯-AMPS-次磷酸酯三元共聚物、聚天冬氨酸、基于天冬氨酸的共聚物,任何前述络合剂的异构体或盐,或包含一种或多种前述络合剂的组合。
5.权利要求4的清洁剂-钝化剂组合物,其中络合剂包含柠檬酸。
6.权利要求1的清洁剂-钝化剂组合物,其中腐蚀抑制剂为硅酸盐;带有包含1至20个碳原子的烷基基团的四烷基原硅酸酯;包含硅-碳键的基于有机硅烷的化合物;羧酸盐;C5-C16二羧酸盐;C5-C16单羧酸;新羧酸;烷基(C1-C14)环己烯酸或其盐;硝酸盐;亚硝酸盐;磷酸盐;吡咯;烃基三唑;噻唑;咪唑;正磷酸盐;焦磷酸盐;六偏磷酸盐;多磷酸盐;膦酸盐;次磷酸盐;钼酸盐;钒酸盐;钨酸盐;硼酸盐;硅酸盐;锌化合物;或包含一种或多种前述腐蚀抑制剂的组合。
7.权利要求6的清洁剂-钝化剂,其中腐蚀抑制剂为硅酸盐、包含硅-碳键的基于有机硅烷的化合物、四烷基原硅酸酯或其组合;吡咯;和焦磷酸盐。
8.权利要求1的清洁剂-钝化剂组合物,其中表面活性剂为环氧乙烷-环氧丙烷嵌段共聚物、烷氧基化醇、壬基苯基乙氧基化物、八苯基乙氧基化物、伯乙氧基化醇、仲乙氧基化醇、聚乙烯脂肪酸、聚环氧丙烷、聚乙二醇、二辛基磺基丁二酸钠、十二烷基苯磺酸钠、磺化二苯醚、乙氧基化醚胺;两性表面活性剂、脂肪酸的胺或咪唑啉衍生物、烷基萘磺酸钠、芳族或脂族磷酸酯、二甲苯磺酸钠、醇表面活性剂,或包含一种或多种前述表面活性剂的组合。
9.权利要求1的清洁剂-钝化剂组合物,所述组合物还包含消泡剂、pH调节剂、杀生物剂、着色剂、染料或包含一种或多种前述试剂的组合。
10.权利要求1的清洁剂-钝化剂组合物,其中溶剂为水、乙二醇、1,2-丙二醇、二乙二醇、三乙二醇、二丙二醇、1,3-丙二醇、丁二醇、甲醇、乙醇、丙醇、异丙醇、丁醇、糠醛、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述溶剂的组合。
11.权利要求1的清洁剂-钝化剂组合物,所述组合物为单组分清洁剂-钝化剂系统形式,pH为约pH4至约pH13。
12.权利要求1的清洁剂-钝化剂组合物,所述组合物为包括清洁组合物和钝化剂组合物的两组分组合物形式,其中清洁剂组合物的pH为约pH1至约pH13,钝化剂组合物的pH为约pH6至约pH13。
13.一种用于处理燃料电池冷却剂系统的清洁剂-钝化剂组合物,所述组合物包含:
络合剂;
表面活性剂;
硅酸盐、含有硅-碳键的基于有机硅烷的化合物、四烷基原硅酸酯或其组合;
吡咯;
焦磷酸盐;和
溶剂。
14.权利要求13的清洁剂-钝化剂组合物,其中络合剂为羟基羧酸盐;膦酸盐;次磷酸盐;羧酸盐;二羧酸盐;基于丙烯酸酯的聚合物、共聚物或三元共聚物;基于马来酸的聚合物、共聚物或三元共聚物;聚天冬氨酸;天冬氨酸共聚物;或包含一种或多种前述络合剂的组合。
15.权利要求14的清洁剂-钝化剂,其中络合剂为柠檬酸、酒石酸、葡糖酸、葡糖二酸、葡庚糖酸、乙醇酸、HEDP(1-1-羟基亚乙基-1,1-二膦酸)、PBTC(2-膦酰基丁烷-1,2,4-三羧酸)、AMP(氨基三(亚甲基膦酸))、HPA(羟基膦酰基乙酸)、HMDTMP(六亚甲基二胺四(亚甲基膦酸))、DTPA二亚乙基三胺五(亚甲基膦酸)、膦酰基丁二酸或其单、双和低聚加合物、膦基丁二酸或其单、双和低聚加合物、草酸、苯甲酸、甲酸、乙酸、氨基磺酸、己二酸、丁二酸、过乙酸、聚丙烯酸酯、丙烯酸酯-丙烯酰胺共聚物、丙烯酸酯-AMPS(丙烯酰胺基亚甲基磺酸)共聚物、丙烯酸酯-马来酸酯共聚物、丙烯酸酯-羟基丙基丙烯酸酯共聚物、丙烯酸酯-磺酸酯共聚物、丙烯酸酯-丙烯酰胺-磺酸酯三元共聚物、胺取代磺烷基化丙烯酰胺丙烯酸酯三元共聚物、聚马来酸、聚马来酸酐、聚甲基丙烯酸、丙烯酸酯-甲基丙烯酸酯共聚物、苯乙烯磺酸酯-马来酸共聚物、次磷酸酯-丙烯酸酯共聚物、丙烯酸酯-AMPS-苯乙烯磺酸酯三元共聚物、丙烯酸酯-AMPS-次磷酸酯三元共聚物、聚天冬氨酸、基于天冬氨酸的共聚物,任何前述络合剂的异构体或盐,或包含一种或多种前述络合剂的组合。
16.权利要求15的清洁剂-钝化剂组合物,其中络合剂包含柠檬酸。
17.权利要求13的清洁剂-钝化剂组合物,其中表面活性剂为环氧乙烷-环氧丙烷嵌段共聚物、烷氧基化醇、壬基苯基乙氧基化物、八苯基乙氧基化物、伯乙氧基化醇、仲乙氧基化醇、聚乙烯脂肪酸、聚环氧丙烷、聚乙二醇、二辛基磺基丁二酸钠、十二烷基苯磺酸钠、磺化二苯醚、乙氧基化醚胺;两性表面活性剂、脂肪酸的胺或咪唑啉衍生物、烷基萘磺酸钠、芳族或脂族磷酸酯、二甲苯磺酸钠、醇表面活性剂,或包含一种或多种前述表面活性剂的组合。
18.权利要求13的清洁剂-钝化剂组合物,所述组合物还包含消泡剂、pH调节剂、杀生物剂、着色剂、染料或包含一种或多种前述试剂的组合。
19.权利要求13的清洁剂-钝化剂组合物,其中溶剂为水、乙二醇、1,2-丙二醇、二乙二醇、三乙二醇、二丙二醇、1,3-丙二醇、丁二醇、甲醇、乙醇、丙醇、异丙醇、丁醇、糠醛、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述溶剂的组合。
20.权利要求13的清洁剂-钝化剂组合物,所述组合物为单组分清洁剂-钝化剂系统形式,pH为约pH4至约pH13。
21.权利要求13的清洁剂-钝化剂组合物,所述组合物为包括清洁组合物和钝化剂组合物的两组分组合物形式,其中清洁剂组合物的pH为约pH1至约pH13,钝化剂组合物的pH为约pH6至约pH13。
22.一种处理燃料电池冷却剂系统的方法,所述方法包括:
将燃料电池冷却剂系统与清洁剂-钝化剂组合物接触,将燃料电池冷却剂系统用冲洗溶剂进行冲洗。
23.权利要求22的方法,其中冲洗溶剂为水、甲醇、乙醇、丙醇、丁醇、糠醛、乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、丁二醇、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述溶剂的组合。
24.权利要求22的方法,其中清洁剂-钝化剂组合物包含:
络合剂,
表面活性剂,
腐蚀抑制剂,和
溶剂。
25.权利要求24的方法,其中络合剂不包含附加的不可生物降解的氨基羧酸盐。
26.权利要求24的方法,其中络合剂不包含附加的氨基羧酸盐。
27.权利要求24的方法,其中络合剂为羟基羧酸盐;膦酸盐;次磷酸盐;羧酸盐;二羧酸盐;基于丙烯酸酯的聚合物、共聚物或三元共聚物;聚天冬氨酸;天冬氨酸共聚物;或包含一种或多种前述络合剂的组合。
28.权利要求27的方法,其中络合剂为柠檬酸、酒石酸、葡糖酸、葡糖二酸、葡庚糖酸、乙醇酸、HEDP(1-1-羟基亚乙基-1,1-二膦酸)、PBTC(2-膦酰基丁烷-1,2,4-三羧酸)、AMP(氨基三(亚甲基膦酸))、HPA(羟基膦酰基乙酸)、HMDTMP(六亚甲基二胺四(亚甲基膦酸))、DTPA二亚乙基三胺五(亚甲基膦酸)、膦酰基丁二酸或其单、双和低聚加合物、膦基丁二酸或其单、双和低聚加合物、草酸、苯甲酸、甲酸、乙酸、氨基磺酸、己二酸、丁二酸、过乙酸;聚丙烯酸酯、丙烯酸酯-丙烯酰胺共聚物、丙烯酸酯-AMPS(丙烯酰胺基亚甲基磺酸)共聚物、丙烯酸酯-马来酸酯共聚物、丙烯酸酯-羟基丙基丙烯酸酯共聚物、丙烯酸酯-磺酸共聚物、丙烯酸酯-丙烯酰胺-磺酸三元共聚物、聚马来酸、聚马来酸酐、聚甲基丙烯酸、丙烯酸酯-甲基丙烯酸酯共聚物、苯乙烯磺酸酯-马来酸共聚物、次磷酸酯-丙烯酸酯共聚物、丙烯酸酯-AMPS-苯乙烯磺酸酯三元共聚物、丙烯酸酯-AMPS-次磷酸酯三元共聚物、聚天冬氨酸、基于天冬氨酸的共聚物,任何前述络合剂的异构体或盐,或包含一种或多种前述络合剂的组合。
29.权利要求28的方法,其中络合剂包含柠檬酸。
30.权利要求24的方法,其中腐蚀抑制剂为硅酸盐;带有包含1至20个碳原子的烷基基团的四烷基原硅酸酯;包含硅-碳键的基于有机硅烷的化合物;羧酸盐;C5-C16二羧酸盐;C5-C16单羧酸;新羧酸;烷基(C1-C14)环己烯酸或其盐;硝酸盐;亚硝酸盐;磷酸盐;吡咯;烃基三唑;噻唑;咪唑;正磷酸盐;焦磷酸盐;六偏磷酸盐;多磷酸盐;膦酸盐;次磷酸盐;钼酸盐;钒酸盐;钨酸盐;硼酸盐;硅酸盐;锌化合物;或包含一种或多种前述腐蚀抑制剂的组合。
31.权利要求30的方法,其中腐蚀抑制剂包含硅酸盐、包含硅-碳键的基于有机硅烷的化合物、四烷基原硅酸酯或其组合;吡咯;和焦磷酸盐。
32.权利要求24的方法,其中表面活性剂为环氧乙烷-丙烯嵌段共聚物、烷氧基化醇、壬基苯基乙氧基化物、八苯基乙氧基化物、伯乙氧基化醇、仲乙氧基化醇、聚乙烯脂肪酸、聚环氧丙烷、聚丙二醇、二辛基磺基丁二酸钠、十二烷基苯磺酸钠、磺化二苯醚、乙氧基化醚胺;两性表面活性剂、脂肪酸的胺或咪唑啉衍生物、烷基萘磺酸钠、芳族或脂族磷酸酯、二甲苯磺酸钠、醇表面活性剂,或包含一种或多种前述表面活性剂的组合。
33.权利要求24的方法,其中清洁剂-钝化剂组合物还包含消泡剂、pH调节剂、杀生物剂、着色剂、染料或包含一种或多种前述试剂的组合。
34.权利要求24的方法,其中溶剂为水、乙二醇、1,2-丙二醇、二乙二醇、三乙二醇、二丙二醇、1,3-丙二醇、丁二醇、甲醇、乙醇、丙醇、异丙醇、丁醇、糠醛、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述溶剂的组合。
35.权利要求24的方法,其中清洁剂-钝化剂组合物为单组分清洁剂-钝化剂系统形式,pH为约pH4至约pH13。
36.权利要求24的方法,其中清洁剂-钝化剂组合物为包括清洁组合物和钝化剂组合物的两组分组合物形式,其中清洁剂组合物的pH为约pH1至约pH13,钝化剂组合物的pH为约pH6至约pH13。
37.权利要求23的方法,其中与清洁剂、钝化剂或两者的接触在约10℃至约100℃的温度下进行。
38.权利要求23的方法,其中与清洁剂、钝化剂或两者的接触在约30℃至约100℃的温度下进行。
39.权利要求22的方法,其中接触使得在暴露于冷却剂约1小时之后冷却剂电导率足以保持低于约5 microseamens/cm,其中冷却剂包含约10%重量至约100%重量的水和约0%重量至约90%重量的醇。
40.权利要求39的方法,其中醇为甲醇、乙醇、丙醇、丁醇、糠醛、乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、丁二醇、丙三醇、丙三醇单乙基醚、丙三醇二甲基醚、1,2,6-己三醇、三羟甲基丙烷、甲氧基乙醇或包含一种或多种前述醇的组合。
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CN102653868A (zh) * | 2012-03-14 | 2012-09-05 | 王福平 | 新型不锈钢酸洗钝化液 |
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Also Published As
Publication number | Publication date |
---|---|
CN1981402B (zh) | 2013-01-23 |
ATE504952T1 (de) | 2011-04-15 |
US20050245411A1 (en) | 2005-11-03 |
JP2007536707A (ja) | 2007-12-13 |
US7442676B2 (en) | 2008-10-28 |
US6887597B1 (en) | 2005-05-03 |
DE602005027349D1 (de) | 2011-05-19 |
WO2005108644A3 (en) | 2006-03-09 |
EP1761966A2 (en) | 2007-03-14 |
WO2005108644A2 (en) | 2005-11-17 |
EP1761966B1 (en) | 2011-04-06 |
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