US3803047A - Organic phosphonic acid compound corrosion protection in aqueous systems - Google Patents
Organic phosphonic acid compound corrosion protection in aqueous systems Download PDFInfo
- Publication number
- US3803047A US3803047A US00300936A US30093672A US3803047A US 3803047 A US3803047 A US 3803047A US 00300936 A US00300936 A US 00300936A US 30093672 A US30093672 A US 30093672A US 3803047 A US3803047 A US 3803047A
- Authority
- US
- United States
- Prior art keywords
- zinc
- acid
- water
- diphosphonic acid
- phosphonic acid
- 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.)
- Expired - Lifetime
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 title claims abstract description 29
- -1 phosphonic acid compound Chemical class 0.000 title claims description 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 150000003851 azoles Chemical class 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 8
- 150000007513 acids Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 229940118149 zinc sulfate monohydrate Drugs 0.000 description 19
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 19
- 239000011701 zinc Substances 0.000 description 16
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 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 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 8
- 239000012964 benzotriazole Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 150000003854 isothiazoles Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002916 oxazoles Chemical class 0.000 description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 150000003217 pyrazoles Chemical class 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 150000003557 thiazoles Chemical class 0.000 description 6
- 150000003852 triazoles Chemical class 0.000 description 6
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 5
- 150000002545 isoxazoles Chemical class 0.000 description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- OWWOMIFQTFZNGK-UHFFFAOYSA-N 1-phosphonobutylphosphonic acid Chemical compound CCCC(P(O)(O)=O)P(O)(O)=O OWWOMIFQTFZNGK-UHFFFAOYSA-N 0.000 description 4
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 3
- PUVMVPFLXCHEOY-UHFFFAOYSA-N 3-phosphonopropylphosphonic acid Chemical compound OP(O)(=O)CCCP(O)(O)=O PUVMVPFLXCHEOY-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- LHTGSCQYYQRVJG-UHFFFAOYSA-J tetrasodium dioxido-oxo-(3-phosphonatopropyl)-lambda5-phosphane Chemical compound P([O-])([O-])(=O)CCCP([O-])([O-])=O.[Na+].[Na+].[Na+].[Na+] LHTGSCQYYQRVJG-UHFFFAOYSA-J 0.000 description 3
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 2
- AYQDAYSTSMCOCJ-UHFFFAOYSA-N 10-phosphonodecylphosphonic acid Chemical compound OP(O)(=O)CCCCCCCCCCP(O)(O)=O AYQDAYSTSMCOCJ-UHFFFAOYSA-N 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- YCEFKTFBNRAYRA-UHFFFAOYSA-N P(O)(O)=O.CO Chemical class P(O)(O)=O.CO YCEFKTFBNRAYRA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FMFWOUJBKKDDGH-UHFFFAOYSA-J dioxido-oxo-(phosphonatomethyl)-$l^{5}-phosphane;tin(4+) Chemical compound [Sn+4].[O-]P([O-])(=O)CP([O-])([O-])=O FMFWOUJBKKDDGH-UHFFFAOYSA-J 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- YJJMBWKVCPBJDJ-UHFFFAOYSA-N 1,2-benzothiazole-3-thione Chemical compound C1=CC=C2C(=S)NSC2=C1 YJJMBWKVCPBJDJ-UHFFFAOYSA-N 0.000 description 1
- VZDBJMCLRLLCTG-UHFFFAOYSA-N 1,2-benzoxazole-3-thione Chemical compound C1=CC=C2C(=S)NOC2=C1 VZDBJMCLRLLCTG-UHFFFAOYSA-N 0.000 description 1
- YDVARACJVYZWSP-UHFFFAOYSA-N 1,2-oxazole-3-thione Chemical compound SC=1C=CON=1 YDVARACJVYZWSP-UHFFFAOYSA-N 0.000 description 1
- NNXMKFQFURUZQB-UHFFFAOYSA-N 1,2-thiazole-3-thione Chemical compound SC=1C=CSN=1 NNXMKFQFURUZQB-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- IVFGIXMLURJXBZ-UHFFFAOYSA-N 1-phosphonopropylphosphonic acid Chemical compound CCC(P(O)(O)=O)P(O)(O)=O IVFGIXMLURJXBZ-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- HEEACTTWORLLPM-UHFFFAOYSA-N 2-(1h-imidazol-5-yl)ethanol Chemical compound OCCC1=CNC=N1 HEEACTTWORLLPM-UHFFFAOYSA-N 0.000 description 1
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-UHFFFAOYSA-N 0.000 description 1
- 150000004964 2-benzylimidazoles Chemical class 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VQTVFIMEENGCJA-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole Chemical compound CC=1C=NNC=1C VQTVFIMEENGCJA-UHFFFAOYSA-N 0.000 description 1
- DLHAWERXBUJHNY-UHFFFAOYSA-N 4-benzyl-1h-pyrazole Chemical compound C=1C=CC=CC=1CC=1C=NNC=1 DLHAWERXBUJHNY-UHFFFAOYSA-N 0.000 description 1
- LUEYUHCBBXWTQT-UHFFFAOYSA-N 4-phenyl-2h-triazole Chemical compound C1=NNN=C1C1=CC=CC=C1 LUEYUHCBBXWTQT-UHFFFAOYSA-N 0.000 description 1
- PJCTVLGNVGGVJR-UHFFFAOYSA-N 5-prop-2-enyl-1h-imidazole Chemical compound C=CCC1=CN=CN1 PJCTVLGNVGGVJR-UHFFFAOYSA-N 0.000 description 1
- ORZRMRUXSPNQQL-UHFFFAOYSA-N 6-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2C=NNC2=C1 ORZRMRUXSPNQQL-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FXBVGKCQLSQGBD-UHFFFAOYSA-N CCCCO.OP(=O)OP(O)=O Chemical compound CCCCO.OP(=O)OP(O)=O FXBVGKCQLSQGBD-UHFFFAOYSA-N 0.000 description 1
- HXYNGXRVDIIMTG-UHFFFAOYSA-N CCCO.OP(=O)OP(O)=O Chemical compound CCCO.OP(=O)OP(O)=O HXYNGXRVDIIMTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GWRZNGBJWWSWLD-UHFFFAOYSA-N P(O)(O)=O.C(C)CO Chemical compound P(O)(O)=O.C(C)CO GWRZNGBJWWSWLD-UHFFFAOYSA-N 0.000 description 1
- SPFXQZBXVCUHTR-UHFFFAOYSA-N P(O)(O)=O.OCC Chemical compound P(O)(O)=O.OCC SPFXQZBXVCUHTR-UHFFFAOYSA-N 0.000 description 1
- OMALBWKTCUHYBN-UHFFFAOYSA-N P(O)(O)=O.OCCCC Chemical compound P(O)(O)=O.OCCCC OMALBWKTCUHYBN-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WKJCTIHPMHMXIZ-UHFFFAOYSA-J dimagnesium dioxido-oxo-(phosphonatomethyl)-lambda5-phosphane Chemical compound C(P([O-])([O-])=O)P([O-])([O-])=O.[Mg+2].[Mg+2] WKJCTIHPMHMXIZ-UHFFFAOYSA-J 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910000165 zinc phosphate 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- 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
- C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/939—Corrosion inhibitor
Definitions
- This invention relates to a method and composition for preventing corrosion of metal surfaces in contact with aqueous systems.
- the corrosion inhibiting composition of this invention consists essentially of from 1 to 80 weight percent of an alkylene polyphosphonic acid having one of the following formulae A, B or C:
- m is an integer from 1 to 10
- R is hydrogen, or an alkyl group having from 1 to 4 carbons and R is hydroxyl, hydrogen, or an alkyl group having from 1 to 4 carbons
- R is an alkyl group having 1 to carbons, benzyl or phenyl
- R is an aliphatic radical having from 1 to 10 carbons, and the water-soluble salts and esters thereof; or mixtures thereof, and from 1 to 80 weight percent of an azole compound selected from a group consisting of triazoles, pyrazoles, imidazoles, isoxazoles, oxazoles, isothiazoles, thiazoles and mixtures thereof, and/or from 1 to 95 weight percent of a watersoluble zinc salt.
- Aqueous solutions of l to 70 weight percent of this composition are also encompassed within this invention.
- the method of this invention for preventing corrosion of metals in contact with an aqueous liquid comprises maintaining in the aqueous liquid from 1 to 10,000 ppm. of the alkylene polyphosphonic acid, salts or esters thereof, and from 1 to 10,000 ppm. of the azole compound and/or from 1 to 10,000 ppm. of a water-soluble zinc salt.
- Water-soluble inorganic chromates are widely used to treat industrial water systems to prevent corrosion of metal parts in contact therewith. When these chromates are employed alone, they are used in concentrations as low as 200 ppm. and as high as 10,000 ppm., depending upon the protection needed and the permissible cost. When these chromates are used in combinations with molecularly dehydrated inorganic phosphates such as disclosed in US Pat. No. 2,711,391,
- chromates are highly effective corrosion inhibitors, their use is subject to several difficulties. Chromates cause serious skin and eye irritations, and chromates cannot be used in aqueous systems such as cooling towers or air-wash units where the resulting spray will contact people. Chromate solutions, because they are toxic, often require chemical treatment before being discharged to waste systems. Furthermore, chromates degrade organic compounds mixed therewith, limiting the types or organic compounds which can be mixed with the chromates in dry mixtures and aqueous solutions.
- the composition contains an organic phosphonic acid compound in combination with an azole compound and/or a watersoluble zinc salt.
- compositions of this invention are useful for treating a variety of aqueous systems, that is, any aqueous system corrosive to metal surfaces in contact therewith.
- Suitable systems which can be treated according to this invention include water treatment systems, cooling towers, water circulating systems, and the like wherein fresh water, brines, sea water, sewage effluents, industrial waste waters, and the like are circulated in contact with metal surfaces.
- These compounds are useful in acid pickling baths, radiator coolers, hydraulic liquids, antifreezes, heat transfer mediums, and petroleum well treatments.
- the process of this invention is suitable for reducing the corrosion of iron, copper, aluminum, zinc and alloys containing these metals such as steel and other ferrous alloys, brass, and the like which are in contact with corrosive aqueous systems.
- compositions of this invention contain from 1 to percent of an organo-phosphonic acid compound.
- the preferred organo-phosphonic acid compound for use in the composition of this invention is an alkylene diphosphonic acid having the foregoing Formula A, such as those disclosed in US. Pat. Nos. 3,214,454 and 3,297,578, the entire disclosures of which are incorporated herein by reference.
- an alkylene diphosphonic acid having the foregoing Formula B or Formula C such as those disclosed in U.S. Pat. No.
- Suitable acids of this type include methylenediphosphonic acid; ethylidenediphosdihydroxyl, 1,4-diethyl, tetramethylenediphosphonic acid; 1,3-dihydroxy 1,3-dipropyl, trimethylenediphosphonic acid; 1,4-dibutyl, tetramethylenediphosphonic acid; dihydroxy, diethyl, ethylenediphosphonic acid; 4-hydroxy, 6-ethyl, hexamethylenediphosphonic acid; l-hydroxy, butylidenediphosphonic acid; butylidenediphosphonic acid; l-aminoethanel ,l-diphosphonic acid; l-aminopropanel, l-diphosphonic acid; 1- aminobenzyll ,l-diphosphonic acid; 1,6- diaminohexane-1,l,6,6-tetraphosphonic acid; I- aminoethane-l,
- the water-soluble salts of these acids such as the alkali metal, alkaline earth metal, zinc, cobalt, chromium, lead, tin, nickel, ammonium, or amine and lower alkanol amine salts can be used.
- esters of these acids with an aliphatic alcohol having from 1 to 4 carbons, or mixtures of the above acids, salts or esters can be used. Use of mixtures of any of the general types of organo-phosphonic acid compounds described above is also contemplated within the scope of this invention.
- R is independently selected from the group consisting of an alkyl group up to four carbon atoms and phosphonate groups, and R is selected from the group consisting of alkyl groups having up to 4 carbon atoms, when R, is a phosphonate group and where n is 0 to 6, when R is an alkyl group; and watersoluble salts thereof.
- methanol phosphonic acid compounds thus disclosed include, for example, l-hydroxy, ethylidene diphosphonic acid (i.e., ethanol, or methyl methanol, 1,1-diphosphonic acid); l-hydroxy. propylidene diphosphonic acid (i.e., ethyl methanol diphosphonic acid); l,o-dihydroxy-l,6-dimethyl, hexamethylene diphosphonic acid (i.e., tetramethylene bis (methyl methanol phosphonic acid)) and its sodium salt (Examples 44 and 1 l0): l,4-dihydroxy-1,4-diethyl.
- ethylidene diphosphonic acid i.e., ethanol, or methyl methanol, 1,1-diphosphonic acid
- propylidene diphosphonic acid i.e., ethyl methanol diphosphonic acid
- tetramethylene diphosphonic acid i.e., dimethylene bis- (ethylmethanol phosphonic acid)
- dimethylene bis- (ethylmethanol phosphonic acid) dimethylene bis- (ethylmethanol phosphonic acid)
- 1.3-dihydroxy-L3- dipropyl trimethylene diphosphonic acid i.e., methylene bis (propylmethanol phosphonic acid)) and its sodium salt
- dihydroxy, diethyl, ethylene diphosphonic acid i.e., bis(ethylemethanol phosphonic acid)
- sodium salt i.e., propyl methanol diphosphonic acid
- compositions of this invention also contain from 1 to and preferably from 25 to 45 percent of an azole compound and/or from 1 to and preferably from 25 ti 45 percent of a water-soluble zinc salt.
- both the azole compound and zinc salts are used in the composition of this invention is the stated concentrations.
- the use of the more common water-soluble zinc salts such as zinc nitrate (Zn(NO molecular weight 189) zinc chloride (ZnCl molecular weight 136.29) and zinc sulfate (ZnSO or ZnSO -H O, molecular weight 161.44 and 179.44, respectively) in the aforesaid concentrations will provide zinc ion (Zn) concentrations from as little as 0.345 weight percent (as 1 percent Zn(NO to as high as 45.5 weight percent (equivalent to 95 percent ZnCl
- the weight ratio of zinc (in the form of one of said water-soluble salts) to phosphonic acid compound may range from about 0.345280 to about 45.521 or, in other words, from about 1:232 to about 120.022.
- the weight ratio of zinc ion may range from about 8.64:80 (Zn equivalent in 25 weight percent of Zn(NO to about 21.511 (Zn equivalent in 45 weight percent of ZnCl or in other words, from about 1:9.27 to about [10.0465. As seen in the following specific Examples 5 and 7, a typical zinc to phosphonic acid compound weight ratio is 1:1.
- Azoles are nitrogen containing heterocyclic 5- membered ring compounds, and azoles which are suit able in the composition of this invention include triazoles, pyrazoles, imidazoles, isoxazoles, oxazoles, isothiazoles, thiazoles and mixtures thereof as disclosed in US. Pats. No. 2,618,608, No. 2,742,369, and No. 2,941,953.
- the triazoles which can be employed in the composition of this invention are any water-soluble 1,2,3- triazoles such as 1,2,3-triazole itself or a substituted 1,2,3-triazole where the substitution takes place in either the 4 or 5 position (or both) of the triazole ring as shown here by the structural formula:
- Suitable triazoles include benzotriazole (the preferred triazole); 4-phenyl-1.2,3-triazole; 1,2-napthotriazole; and 4-nitrobenzotriazole; and the like.
- pyrazoles which can be used in the composition of this invention include any water-soluble pyrazoles such as pyrazole itself or a substituted pyrazole where the substitution takes place in the 3, 4, or 5 position (or several of these positions) of the pyrazole ring as shown by the structural formula:
- Suitable pyrazoles include pyrazole: 3,5-dimethyl pyrazole: 6-nitroindazole: 4-benzyl pyrazole; 4,5-dimethyl pyrazole; and 3-allyl pyrazole; and the like.
- the imidazoles which can be used in the composition of this invention include any water-soluble imidazoles such as imidazole itself or a substituted imidazole position of this invention include imidazole; adenine; quanine; benzimidazole; S-methyl benzimidazole; 2-
- phenyl imidazole 2-benzyl imidazole; 4-allyl imidazole; 4-(betahydroxy ethyl)-imidazole; purine; 4-methyl imidazole; xanthine; hypoxanthene; 2-
- lsoxazoles which can be employed in the composition of this invention include any water-soluble isoxazole such as isoxazole itself or a substituted isoxazole where the substitution takes place in the 3, 4 or 5 position (or several of these positions) of the isoxazole ring as shown here by the structural formula:
- Suitable isoxazoles include isoxazole; 3- mercaptoisoxazole; 3-mercaptobenzisoxazole; benzisoxazole; and the like.
- Suitable oxazoles include oxazole; 2-mercaptoxazole; Z-mercaptobenzoxazole; and the like.
- the isothiazoles which can be employed in the process of this invention include any water-soluble isothiazoles such as isothiazole itself or a substituted isothiazole where the substitution takes place in either the 3, 4 or 5 position (or several of these positions) of the isothiazole ring as shown here by the structural formula:
- Suitable isothiazoles include isothiazole. 3- mercaptoisothiazole: 3-mercaptobenzisothiazole: benzisothiazole; and the like.
- suitable thiazoles include thiazole: 2- mercapthothiazole; Z-mercaptobenzothiazole; benzothiazole; and the like.
- the constituents substituted in the azole rings can be alkyl, aryl, aralkyl, alkylol, and alkenyl radicals so long as the substituted azole is water-soluble.
- the zinc salts which can be employed in the composition of this invention include water-soluble zinc salt such as zinc sulfate, zinc chloride, zinc nitrate, alkali metal-zinc phosphate glasses, crystalline alkali metalzinc polyphosphates, and the like.
- Aqueous systems can be treated with aqueous solutions containing from 1 to percent and preferably from 1 to 10 percent of the compositions of this invention. These solutions can be made by premixing the ingredients of this composition and then adding the mixture to water, or by adding the individual ingredients of the composition of this invention separately to water. These aqueous feed solutions are stable and can be stored prior to use.
- aqueous liquids from 1 to 10,000 ppm. and preferably from 1 to 100 of the organophosphonic acid compounds, and from 1 to l0,000 ppm. and preferably from 1 to 100 ppm. of the azole compounds and/or from 1 to 10,000 and preferably from 2 to 200 ppm. of the water-soluble zinc salts are maintained in aqueous liquid.
- both the azoles and zinc salts are maintained in the systems in the stated concentrations.
- the aqueous corrosion resistant solutions of this invention are solutions of at least 1 and preferablyfrom 5 to 200 ppm. of the compositions of this invention.
- the ingredients can be added to the aqueous solutions either in premixed solid or solution or individual solids or solutions to form this aqueous solution composition.
- compositions of this invention are non-toxic and prevent corrosion of metals in contact with aqueous liquids. These compositions can be substituted for chromate base corrosion inhibitors previously used where the toxicity of the chromate makes its use undesirable or where disposal of corrosion inhibiting solutions containing chromates raises serious water pollution problems requiring extensive pretreatment to remove the chromates prior to disposal of such solutions.
- the compositions of this invention in aqueous solutions prevent corrosion of metal parts such as heat exchangers, engine jackets, and pipes and particularly prevent metal loss, pitting, and tuberculation of iron base alloys, copper alloys, and aluminum alloys in contact with water.
- the circulating water was fed to a closed circulating test system at a rate of 5 gallons per day, the overflow from the test system being discharged to waste.
- circulating water having a temperature of 130 F. and pH of 6.5-7.0 was fed at a rate of 1 gallon per minute to a coupon chamber containing test coupons for the corrosion test.
- Water from the coupon chamber was then passed through an arsenical admirality brass tube surrounded by a jacket through which a heating fluid having an initial temperature of 240 F. was countercurrently passed.
- the circulating water was then cooled to 130 F. and recirculated through the system.
- the total circulating time for each test was 10 days.
- Examples 5, 6 and 7 corresponding to the compositions of this invention provide a corrosion protection far greater than would be expected in view of the effects of the individual components thereof.
- EXAMPLE 8 The corrosion rates in mils per year of aluminum in contact with liquid containing 10 ppm. Zn and 10 ppm. of benzotriazole according to the above test procedure was found to be 1.1.
- 1,2-naphthotriazole 15% zinc sulfate monohydrate 70% l-aminobenzyl-l ,1 'diphosphonic acid 15%; 4 nitrobenzotriazole 15%; zinc sulfate monohydrate 70% Sodium dihydroxy, diethyl,
- 1,2-naphthotriazole 50% l-aminobenzyl-l ,l-diphosphonic acid 50%; 4-nitrobenzotriazole 50% Sodium dihydroxy, diethyl,
- hexamethylenediphosphonate 30% zine sulfate monohydrate 70% 1 -amino-2-phenylethane-l ,l -diphosphonic acid 30%; zinc sulfate monohydrate 70% Sodium 1,3-dihydroxy, 1,3-dipropyl,
- a composition useful for inhibiting corrosion in aqueous systems consisting essentially of one part by weight zinc in the form of a watersoluble zinc salt; from 0.02 to about 300 parts by weight of a water-soluble organic phosphonate compound having the formula where R is independently selected from the group consisting of alkyl groups up to four carbon atoms, and
- R is selected from the group consisting of alkyl groups having up to four carbon atoms, when R, is a phosphonatc group;
- n is 0 to 6, when R is an alkyl group, and watersoluble salts and "esters thereof; and corrosion inhibiting amounts of a copper corrosion inhibitor selected from the group consisting of 1,2,3-triazoles, thiazoles, oxazoles, imidazoles, isoxazoles, isothiazoles and pyrazoles.
- composition of claim 1 in which the watersoluble zinc salt is zinc sulfate.
Abstract
Description
Claims (3)
- 2. The composition of claim 1 in which the water-soluble zinc salt is zinc sulfate.
- 3. The composition of claim 1 in which the phosphonate compound is ethanol 1,1-diphosphonic acid or water-soluble salt thereof.
- 4. A method of inhibiting corrosion in aqueous systems comprising maintaining therein an amount of the composition of claim 1 to provide up to about 100 ppm. copper corrosion inhibitor.
Priority Applications (1)
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US00300936A US3803047A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
Applications Claiming Priority (3)
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US58115166A | 1966-09-22 | 1966-09-22 | |
US64560067A | 1967-06-13 | 1967-06-13 | |
US00300936A US3803047A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
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US3803047A true US3803047A (en) | 1974-04-09 |
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US00300936A Expired - Lifetime US3803047A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
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Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3899293A (en) * | 1973-08-28 | 1975-08-12 | Nl Industries Inc | Method for inhibiting the corrosion of iron and alloys thereof in an aqueous environment with sulfite compositions |
US3935125A (en) * | 1974-06-25 | 1976-01-27 | Chemed Corporation | Method and composition for inhibiting corrosion in aqueous systems |
US3969237A (en) * | 1973-03-22 | 1976-07-13 | Mobil Oil Corporation | Lubricant compositions containing benzotriazole derivatives as copper passivators |
US3971734A (en) * | 1973-08-28 | 1976-07-27 | Nl Industries, Inc. | Sulfite compositions, aqueous sulfite solutions and method of decreasing their rate of oxidation |
US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
US4061589A (en) * | 1977-01-17 | 1977-12-06 | Chemed Corporation | Corrosion inhibitor for cooling water systems |
US4076501A (en) * | 1971-06-26 | 1978-02-28 | Ciba-Geigy Corporation | Corrosion inhibition of water systems with phosphonic acids |
US4101441A (en) * | 1975-12-29 | 1978-07-18 | Chemed Corporation | Composition and method of inhibiting corrosion |
US4240925A (en) * | 1978-08-02 | 1980-12-23 | Petrolite Corporation | Inhibition of pitting corrosion |
US4246030A (en) * | 1978-12-08 | 1981-01-20 | The Mogul Corporation | Corrosion inhibiting compositions and the process for using same |
DE2942903A1 (en) * | 1979-10-24 | 1981-05-07 | Chemische Werke Hüls AG, 4370 Marl | CAVITATION-RESISTANT, FROST-SAFE COOLING OR HEAT TRANSFER LIQUIDS |
US4411865A (en) * | 1979-04-05 | 1983-10-25 | Betz Laboratories, Inc. | Method of corrosion inhibition in aqueous mediums |
EP0109200A1 (en) * | 1982-10-28 | 1984-05-23 | Betz Europe, Inc. | High calcium tolerant deposit control method |
US4554090A (en) * | 1984-03-09 | 1985-11-19 | Jones L W | Combination corrosion/scale inhibitor |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US4663053A (en) * | 1982-05-03 | 1987-05-05 | Betz Laboratories, Inc. | Method for inhibiting corrosion and deposition in aqueous systems |
US4717542A (en) * | 1987-01-23 | 1988-01-05 | W. R. Grace & Co. | Inhibiting corrosion of iron base metals |
US4810405A (en) * | 1987-10-21 | 1989-03-07 | Dearborn Chemical Company, Limited | Rust removal and composition thereof |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US5002697A (en) * | 1988-03-15 | 1991-03-26 | Nalco Chemical Company | Molybdate-containing corrosion inhibitors |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
GB2331999A (en) * | 1997-10-28 | 1999-06-09 | Ibm | Copper preservative treatment using azoles |
US6299983B1 (en) | 1997-06-27 | 2001-10-09 | E. I. Du Pont De Nemours And Company | Derivatized metallic surfaces, composites of functionalized polymers with such metallic surfaces and processes for formation thereof |
US11760666B2 (en) | 2018-03-08 | 2023-09-19 | Bl Technologies, Inc. | Methods and compositions to reduce azoles and AOX corrosion inhibitors |
-
1972
- 1972-10-26 US US00300936A patent/US3803047A/en not_active Expired - Lifetime
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4076501A (en) * | 1971-06-26 | 1978-02-28 | Ciba-Geigy Corporation | Corrosion inhibition of water systems with phosphonic acids |
US3969237A (en) * | 1973-03-22 | 1976-07-13 | Mobil Oil Corporation | Lubricant compositions containing benzotriazole derivatives as copper passivators |
US3899293A (en) * | 1973-08-28 | 1975-08-12 | Nl Industries Inc | Method for inhibiting the corrosion of iron and alloys thereof in an aqueous environment with sulfite compositions |
US3971734A (en) * | 1973-08-28 | 1976-07-27 | Nl Industries, Inc. | Sulfite compositions, aqueous sulfite solutions and method of decreasing their rate of oxidation |
US3935125A (en) * | 1974-06-25 | 1976-01-27 | Chemed Corporation | Method and composition for inhibiting corrosion in aqueous systems |
US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
US4101441A (en) * | 1975-12-29 | 1978-07-18 | Chemed Corporation | Composition and method of inhibiting corrosion |
US4061589A (en) * | 1977-01-17 | 1977-12-06 | Chemed Corporation | Corrosion inhibitor for cooling water systems |
US4240925A (en) * | 1978-08-02 | 1980-12-23 | Petrolite Corporation | Inhibition of pitting corrosion |
US4246030A (en) * | 1978-12-08 | 1981-01-20 | The Mogul Corporation | Corrosion inhibiting compositions and the process for using same |
US4411865A (en) * | 1979-04-05 | 1983-10-25 | Betz Laboratories, Inc. | Method of corrosion inhibition in aqueous mediums |
DE2942903A1 (en) * | 1979-10-24 | 1981-05-07 | Chemische Werke Hüls AG, 4370 Marl | CAVITATION-RESISTANT, FROST-SAFE COOLING OR HEAT TRANSFER LIQUIDS |
US4663053A (en) * | 1982-05-03 | 1987-05-05 | Betz Laboratories, Inc. | Method for inhibiting corrosion and deposition in aqueous systems |
EP0109200A1 (en) * | 1982-10-28 | 1984-05-23 | Betz Europe, Inc. | High calcium tolerant deposit control method |
US4479878A (en) * | 1982-10-28 | 1984-10-30 | Betz Laboratories, Inc. | High calcium tolerant deposit control method |
US4554090A (en) * | 1984-03-09 | 1985-11-19 | Jones L W | Combination corrosion/scale inhibitor |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US4717542A (en) * | 1987-01-23 | 1988-01-05 | W. R. Grace & Co. | Inhibiting corrosion of iron base metals |
US4810405A (en) * | 1987-10-21 | 1989-03-07 | Dearborn Chemical Company, Limited | Rust removal and composition thereof |
EP0313335A1 (en) * | 1987-10-21 | 1989-04-26 | Grace Dearborn Inc. | Rust removal and composition therefor |
US5002697A (en) * | 1988-03-15 | 1991-03-26 | Nalco Chemical Company | Molybdate-containing corrosion inhibitors |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5312953A (en) * | 1988-11-09 | 1994-05-17 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US6299983B1 (en) | 1997-06-27 | 2001-10-09 | E. I. Du Pont De Nemours And Company | Derivatized metallic surfaces, composites of functionalized polymers with such metallic surfaces and processes for formation thereof |
GB2331999A (en) * | 1997-10-28 | 1999-06-09 | Ibm | Copper preservative treatment using azoles |
GB2331999B (en) * | 1997-10-28 | 2003-01-22 | Ibm | Copper preservative treatment |
US6635123B2 (en) | 1997-10-28 | 2003-10-21 | International Business Machines Corporation | Copper preservative treatment |
US20040020566A1 (en) * | 1997-10-28 | 2004-02-05 | International Business Machines Corporation | Cooper preservative treatment |
US6815088B2 (en) | 1997-10-28 | 2004-11-09 | International Business Machines Corporation | Copper preservative treatment |
US11760666B2 (en) | 2018-03-08 | 2023-09-19 | Bl Technologies, Inc. | Methods and compositions to reduce azoles and AOX corrosion inhibitors |
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