JPS6257715B2 - - Google Patents
Info
- Publication number
- JPS6257715B2 JPS6257715B2 JP7532781A JP7532781A JPS6257715B2 JP S6257715 B2 JPS6257715 B2 JP S6257715B2 JP 7532781 A JP7532781 A JP 7532781A JP 7532781 A JP7532781 A JP 7532781A JP S6257715 B2 JPS6257715 B2 JP S6257715B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- salt
- anticorrosive agent
- alkaline
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000005260 corrosion Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 16
- -1 nitrous acid alkaline salts Chemical class 0.000 claims description 14
- 159000000011 group IA salts Chemical class 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 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 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical group OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000011133 lead Substances 0.000 claims 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- 229920001444 polymaleic acid Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- YPEMKASELPCGPB-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(=C)C(O)=O YPEMKASELPCGPB-UHFFFAOYSA-N 0.000 description 1
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QWTHCBHISCTOJD-UHFFFAOYSA-N methyl prop-2-enoate 2-methylprop-2-enoic acid prop-2-enoic acid Chemical compound CC(C(=O)O)=C.C(C=C)(=O)O.C(C=C)(=O)OC QWTHCBHISCTOJD-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229940013123 stannous chloride Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
この発明は、鉄、軟鋼、鋼、鋳鉄の如き鉄系金
属の防食剤に関し、詳しくは熱交換器、冷却水、
ラジエーター、ボイラー等の高温水系において優
れた効果が発揮される鉄系金属の防食剤に関す
る。
近年、水の利用事情が悪化した結果、例えば冷
却水系統ではブロー水量を抑え、水を循環再利用
することにより水の節約を図つている。またボイ
ラー等においてもノンブロー方式が次第に採用さ
れるようになつてきている。しかし、このような
水の循環再利用下においては、水中の塩類の濃度
が高まりスケールも発生し易く、かような高濃縮
水が接触する系の種々の金属は腐食が進み易く、
これらの対策すなわち水処理対策は非常に困難な
問題となつている。
これらの点に鑑み、ことに循環系高濃縮水用と
してグルコン酸又はその塩とモリブデン酸塩に特
定のアクリル酸系重合体を配合させたことよりな
る防食剤(特公昭53―43376号公報参照)が提案
されている。
この発明は、モリブデン酸塩を一成分とする防
食剤、ことに上記三成分からなる防食剤を更に研
究することによりなされたものであり、上記三成
分からなる薬剤に重金属イオンを併用させた場
合、併用しない場合に比較し、高温水系中で著し
く優れた防食効果が発揮されるという事実を見い
出したことによりなされたものである。
かくしてこの発明によれば、
(イ) モリブデン酸ならびにそのアルカリ性塩、タ
ングステン酸ならびにそのアルカリ性塩および
亜硝酸のアルカリ性塩より選ばれた1種又は2
種以上、
(ロ) 脂肪族オキシカルボン酸またはそのアルカリ
性塩、
(ハ) 重金属イオンを水中で容易に放出しうる化合
物および
(ニ) 分子量500〜100000で水溶性のオレフイン系
化合物の重合体または共重合体、を有効成分と
して特定比で含有する高温水系用防食剤が提供
される。
この発明に使用するモリブデン酸、タングステ
ン酸および亜硝酸のアルカリ性塩としては、リチ
ウム、ナトリウムならびにカリウム塩の如きアル
カリ金属塩およびアンモニウム塩が挙げられ、経
済性等の点でモリブデン酸ナトリウム、モリブデ
ン酸アンモニウム、タングステン酸ナトリウム、
亜硝酸ナトリウムおよび亜硝酸アンモニウムが好
適に使用できる。また、これら2種以上の組合せ
を用いても何らさしつかえはない。
この発明に使用する肪脂族オキシカルボン酸と
しては、グリコール酸、クエン酸、リンゴ酸、酒
石酸、乳酸、グルコン酸等およびこれらの混合物
が好適に使用できる。また、脂肪族オキシカルボ
ン酸のアルカリ性塩としては、リチウム、ナトリ
ウムならびにカリウム塩の如きアルカリ金属塩お
よびアンモニウム塩等が挙げられる。これらのう
ち、グルコン酸、リンゴ酸およびクエン酸ならび
にそれらのナトリウム塩またはアンモニウム塩の
使用が好ましい。
この発明に使用する重金属イオンを水中で容易
に放出しうる化合物としては、亜鉛、マンガン、
スズ、コバルト、ニツケル、チタン、ジルコニウ
ム、銅、鉛等の硫酸塩、塩酸塩、硝酸塩、スルフ
アミン酸塩等およびこれらの混合物が挙げられ
る。これらのうち亜鉛、マンガン、スズおよびニ
ツケルの塩が好ましく、ことにボイラー水に添加
して用いる場合はマンガンおよびスズの塩が好ま
しい。
この発明に使用するオレフイン系化合物の重合
体または共重合体としては、アクリル酸およびそ
の低級アルキルエステルならびに低級ヒドロキシ
アルキルエステル、メタクリル酸およびその低級
アルキルエステルならびに低級ヒドロキシアルキ
ルエステル、アクリルアミド、メタクリルアミ
ド、アクリルアミド―N―アルカンスルホン酸、
マレイン酸、フマル酸、イタコン酸、ビニルアル
コール、アリルアルコール、メタリルアルコー
ル、アクロレイン、メタクロレイン、アリルスル
ホン酸、メタリルスルホン酸およびアクリロニト
リルの群から選ばれた1種または2種以上の化合
物の重合体または共重合体が挙げられ、これらは
上記各化合物を公知の重合条件に付すことにより
得られる。これらのうちアクリル酸、メタクリル
酸、マレイン酸、アクリルアミド、アクリルアミ
ド―N―プロパンスルホン酸、アクリル酸メチ
ル、アクリル酸エチル、メタクリル酸メチルおよ
びメタクリル酸エチルの群から選ばれた化合物の
1種または2種以上の重合体または共重合体が好
ましい。具体的には、ポリアクリル酸、ポリメタ
クリル酸、ポリマレイン酸、アクリル酸―メタク
リル酸コポリマー、アクリル酸―マレイン酸コポ
リマー、メタクリル酸―マレイン酸コポリマー、
アクリル酸―アクリルアミドコポリマー、アクリ
ル酸―アクリルアミド―N―プロパンスルホン酸
コポリマー、アクリル酸―メタクリル酸―アクリ
ル酸メチルターポリマー等が挙げられる。
上記の如きオレフイン系化合物の重合体または
共重合体は、水溶性である必要がある。また、実
質的に水溶性であつても分子量が100000以上であ
ると凝集作用が生じてくるので好ましくなく、通
常、分子量500〜100000のものが好ましい。こと
に、合成上の容易性等の点から、アクリル酸もし
くはメタクリル酸系重合体は分子量1000〜20000
のものが適しており、ポリマレイン酸は分子量
500〜2000のものが適している。なお、ここで分
子量とはオストワルド粘度計により算定した粘度
平均分子量をいう。一方上記の如き分子量を有す
るものでも水に溶解し難い場合には重合分子中の
遊離酸やそのエステル部分を対応する易溶解性塩
(アルカリ金属塩やアンモニウム塩のごときアル
カリ性塩)に変換することによりその溶解性を高
めることが所望の効果を得るために望ましい。
この発明の上記四成分は、通常、水に溶解した
液剤又は直接混合した粉剤の形態で製剤化して用
いるのが適している。水溶液として製剤化する場
合、そのPHは中性前後に保つことが望ましい。酸
性状態では、モリブデン酸やタングステル酸が遊
離して縮合したり、亜硝酸が分解したり、脂肪族
オキシカルボン酸が徐々に酸化したりするので好
ましくない。従つて、例えば水酸化ナトリウム等
のアルカリをPH調整用に配合しておくことが望ま
しい。
また、(イ),(ロ),(ハ)および(ニ)の各化合物の相乗
効
果が発揮されるのに好適な配合比は(イ)の化合物の
重量を1とした場合、(ロ):(ハ):(ニ)が重量比で0.2
〜30:0.1〜5:0.1〜5であり、好ましくは0.5〜
10:0.1〜1.5:0.2〜1.6である。また、液剤の場
合、四成分の合計濃度は各化合物の溶解度やPH等
に左右され、特に限定されるものではないが、通
常5〜60重量%程度が製剤安定性の点で適当であ
る。なお、液剤中に、安定剤等の添加剤が若干配
合されていても何んらさしつかえない。
以上の如き四成分を有効成分として含有する製
剤を使用するに当つて、防食対象系への添加量
は、防食対象系の水質、防食面積等の条件により
異なるため特に限定されないが、通常、有効成分
の合計量として1〜2000ppm、好ましくは15〜
300ppm程度の添加によつてその目的を達成する
ことができる。
従つて、この発明は、前記化合物(イ),(ロ),(ハ)お
よび(ニ)を防食対象系に添加することからなる金属
の防食方法をも提供するものである。この場合、
各有効成分はそれぞれ単一製剤として別々に添加
されてもよい。
この発明の防食剤は、熱交換器、冷却水、ラジ
エーター、ボイラー等の高温水系の防食に有用で
あり、ことに循環系高濃縮水等の塩類濃度が高く
非常に腐食性の強い条件やスケール発生性の強い
条件においても優れた鉄系金属の防食効果、さら
にはスケール防止効果を発揮し、ピツチングコロ
ージヨン等の防止にも有効である。
次に、この発明を参考例、製剤例及び実施例に
て更に詳しく説明するが、これによつてこの発明
は限定されるものではない。
参考例
次のような方式の防食テストを行つた。薬剤は
上記(イ)〜(ニ)の各成分の種々の組合せについて行つ
た。
軟鋼テストピース(市販品名SPCC)30mm×50
mm×1mmの形状のものをステンレス製の撹拌棒に
懸吊し、所定濃度の薬剤の入つた試験液に浸漬す
る。試験液は平底ビーカに入つていてその液量は
1である。平底ビーカは環状のマントルヒータ
ーに包囲され、サーモスタツトで水温を調節して
いて一定温度に保持している。撹拌棒は回転モー
タと接続され1分間100回転(100rpm)にテスト
ピースを回転する。以上の装置を用いて水温を50
℃に保ちつゝ撹拌下5日のテストを行つた。使用
した試験水の水質は大阪市水5倍濃縮水である。
その水質を表1に示す。
The present invention relates to anticorrosive agents for ferrous metals such as iron, mild steel, steel, and cast iron, and specifically relates to heat exchangers, cooling water,
This invention relates to a corrosion inhibitor for iron-based metals that exhibits excellent effects in high-temperature water systems such as radiators and boilers. In recent years, as a result of worsening water usage conditions, efforts have been made to conserve water by, for example, reducing the amount of blow water in cooling water systems and recycling and reusing water. In addition, non-blow systems are increasingly being adopted in boilers and the like. However, under such water circulation and reuse, the concentration of salts in the water increases and scale tends to occur, and various metals that come into contact with such highly concentrated water are prone to corrosion.
These measures, namely water treatment measures, have become extremely difficult problems. In view of these points, an anticorrosive agent made by blending gluconic acid or its salt and a molybdate with a specific acrylic acid polymer is especially suitable for highly concentrated water in the circulation system (see Japanese Patent Publication No. 43376/1983). ) has been proposed. This invention was achieved through further research into anticorrosive agents containing molybdate as one component, especially anticorrosive agents containing the three components mentioned above. This was achieved based on the discovery that a significantly superior anticorrosive effect is exhibited in a high-temperature water system compared to when they are not used together. Thus, according to the present invention, (a) one or two selected from molybdic acid and its alkaline salts, tungstic acid and its alkaline salts, and nitrous acid alkaline salts;
(b) aliphatic oxycarboxylic acids or their alkaline salts; (c) compounds that can easily release heavy metal ions in water; and (d) polymers or co-operatives of water-soluble olefinic compounds with a molecular weight of 500 to 100,000. A corrosion inhibitor for high-temperature water systems containing a polymer as an active ingredient in a specific ratio is provided. The alkaline salts of molybdic acid, tungstic acid, and nitrous acid used in this invention include alkali metal salts such as lithium, sodium, and potassium salts, and ammonium salts. , sodium tungstate,
Sodium nitrite and ammonium nitrite can be preferably used. Furthermore, there is no problem in using a combination of two or more of these. As the aliphatic oxycarboxylic acid used in this invention, glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, gluconic acid, etc., and mixtures thereof can be suitably used. Further, examples of alkaline salts of aliphatic oxycarboxylic acids include alkali metal salts such as lithium, sodium, and potassium salts, and ammonium salts. Among these, preference is given to using gluconic acid, malic acid and citric acid and their sodium or ammonium salts. Compounds that can easily release heavy metal ions in water used in this invention include zinc, manganese,
Examples include sulfates, hydrochlorides, nitrates, sulfamates, etc. of tin, cobalt, nickel, titanium, zirconium, copper, lead, etc., and mixtures thereof. Among these, salts of zinc, manganese, tin and nickel are preferred, and salts of manganese and tin are particularly preferred when added to boiler water. Polymers or copolymers of olefin compounds used in this invention include acrylic acid and its lower alkyl esters and lower hydroxyalkyl esters, methacrylic acid and its lower alkyl esters and lower hydroxyalkyl esters, acrylamide, methacrylamide, and acrylamide. -N-alkanesulfonic acid,
One or more compounds selected from the group of maleic acid, fumaric acid, itaconic acid, vinyl alcohol, allyl alcohol, methallyl alcohol, acrolein, methacrolein, allyl sulfonic acid, methallyl sulfonic acid, and acrylonitrile. Examples include polymers and copolymers, which can be obtained by subjecting each of the above compounds to known polymerization conditions. One or two of these compounds selected from the group of acrylic acid, methacrylic acid, maleic acid, acrylamide, acrylamide-N-propanesulfonic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The above polymers or copolymers are preferred. Specifically, polyacrylic acid, polymethacrylic acid, polymaleic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic acid copolymer, methacrylic acid-maleic acid copolymer,
Examples include acrylic acid-acrylamide copolymer, acrylic acid-acrylamide-N-propanesulfonic acid copolymer, and acrylic acid-methacrylic acid-methyl acrylate terpolymer. The polymer or copolymer of the olefinic compound as described above must be water-soluble. Further, even if it is substantially water-soluble, if the molecular weight is 100,000 or more, aggregation will occur, which is undesirable, and a molecular weight of 500 to 100,000 is usually preferable. In particular, from the viewpoint of ease of synthesis, acrylic acid or methacrylic acid polymers have a molecular weight of 1,000 to 20,000.
Polymaleic acid has a molecular weight of
Something between 500 and 2000 is suitable. In addition, the molecular weight here refers to the viscosity average molecular weight calculated by an Ostwald viscometer. On the other hand, if it is difficult to dissolve in water even if it has the above molecular weight, the free acid or its ester moiety in the polymer molecule may be converted into a corresponding easily soluble salt (alkaline salt such as an alkali metal salt or ammonium salt). It is desirable to increase its solubility by increasing its solubility in order to obtain the desired effect. The above-mentioned four components of the present invention are usually suitably formulated and used in the form of a solution dissolved in water or a powder prepared by directly mixing them. When formulating as an aqueous solution, it is desirable to maintain its pH around neutrality. Acidic conditions are not preferable because molybdic acid and tungsteric acid are liberated and condensed, nitrous acid is decomposed, and aliphatic oxycarboxylic acids are gradually oxidized. Therefore, it is desirable to add an alkali such as sodium hydroxide for pH adjustment. In addition, when the weight of the compound (A) is 1, the compounding ratio suitable for exhibiting the synergistic effect of each compound (A), (B), (C), and (D) is (B). :(C) :(D) is 0.2 in weight ratio
~30:0.1~5:0.1~5, preferably 0.5~
10:0.1~1.5:0.2~1.6. Further, in the case of a liquid preparation, the total concentration of the four components depends on the solubility and pH of each compound, and is not particularly limited, but usually about 5 to 60% by weight is appropriate from the viewpoint of formulation stability. Incidentally, there is no problem even if some additives such as stabilizers are blended into the liquid preparation. When using a preparation containing the above four ingredients as active ingredients, the amount added to the system to be protected against corrosion is not particularly limited as it varies depending on conditions such as water quality and area to be protected against corrosion, but it is usually effective. 1 to 2000 ppm as the total amount of ingredients, preferably 15 to 2000 ppm
The purpose can be achieved by adding about 300 ppm. Therefore, the present invention also provides a method for preventing corrosion of metals, which comprises adding the compounds (a), (b), (c) and (d) to a system to be protected against corrosion. in this case,
Each active ingredient may be added separately as a single formulation. The anticorrosive agent of the present invention is useful for preventing corrosion in high-temperature water systems such as heat exchangers, cooling water, radiators, boilers, etc., and is particularly useful in highly corrosive conditions such as highly concentrated water in circulation systems with high salt concentrations and highly corrosive conditions. It exhibits excellent anti-corrosion effects for iron-based metals even under conditions where corrosion is highly likely to occur, and also has anti-scaling effects, and is also effective in preventing pitting corrosion. Next, this invention will be explained in more detail with reference examples, formulation examples, and examples, but the invention is not limited thereby. Reference example A corrosion protection test was conducted using the following method. Various combinations of the ingredients (a) to (d) above were used as drugs. Mild steel test piece (commercial product name SPCC) 30mm x 50
A specimen measuring 1 mm x 1 mm is suspended from a stainless steel stirring rod and immersed in a test solution containing a drug at a predetermined concentration. The test solution is placed in a flat bottom beaker and its volume is 1. The flat-bottomed beaker is surrounded by an annular heating mantle, and a thermostat controls the water temperature to maintain a constant temperature. The stirring rod is connected to a rotating motor and rotates the test piece at 100 revolutions per minute (100 rpm). Use the above device to lower the water temperature to 50
The test was carried out for 5 days while maintaining the temperature at ℃ and stirring. The quality of the test water used was 5 times concentrated Osaka city water.
The water quality is shown in Table 1.
【表】
テスト終了後、テストピースを取出し乾燥し、
その重量を測定する。この重量をM1(mg)とす
る。次にJISKO100の方法に準じてテストピース
を処理し、乾燥後その重量を測定してM2(mg)
とする。次に、これをもとにm.d.d.(mg/day・
dm2)を次式に従つて算出する。
m.d.d.
=テストピースの試験前の重量(mg)−M2/テスト
ピース面積(dm2)×テスト日数
=腐食減量/0.3142×5
次にテスト終了後の溶液を東洋ロ紙No.6にて
500ml分ロ別し、得られた沈澱を110℃の恒温にて
1日乾燥してその乾燥重量を測定する。一方、上
述のM1,M2の値よりM1―M2を算出し、テストピ
ースの付着物の重量とする。以上の手順をへて、
スケール析出量を次式に定義する。
スケール析出量=沈澱の乾燥重量×2+(M1―
M2)(mg/)
即ち、1当りの試験液より生じたスケールの
発生量を意味する。
以上得られた結果を比較例と共に表2に示す。[Table] After the test, remove the test piece and dry it.
Measure its weight. Let this weight be M 1 (mg). Next, process the test piece according to the JISKO100 method, measure its weight after drying, and calculate M2 (mg).
shall be. Next, based on this, mdd (mg/day・
dm 2 ) is calculated according to the following formula. mdd = weight of test piece before test (mg) - M 2 / test piece area (dm 2 ) x number of test days = corrosion loss / 0.3142 x 5 Next, after the test, the solution was placed on Toyoro paper No. 6. hand
Separate into 500 ml portions, dry the resulting precipitate at a constant temperature of 110°C for one day, and measure its dry weight. On the other hand, M 1 −M 2 is calculated from the above-mentioned values of M 1 and M 2 and is used as the weight of the deposit on the test piece. After going through the above steps,
The amount of scale precipitation is defined by the following formula. Amount of scale precipitation = Dry weight of precipitate x 2 + (M 1 -
M 2 ) (mg/) That is, it means the amount of scale generated from one test solution. The results obtained above are shown in Table 2 together with comparative examples.
【表】【table】
【表】【table】
【表】
大阪市水5倍濃縮水を用いた試験結果より、薬
剤無添加時においては比較例1で示される如くス
ケール析出量404mg/、m.d.d.215と高いスケー
ル析出、腐食傾向にあることがわかる。又本発明
の4成分のうち3成分を45〜50ppm添加した場
合(比較例2〜5参照)、比較例2においては防
食効果は良好であるがスケール析出量41.0mg/
とスケール析出傾向にあり好ましくなく、又比較
例5(従来公知の3成分系、特公昭53―43376号
発明に相当)においてはスケール析出は抑制され
るもののm.d.d.20と満足な防食効果が得られない
ことがわかる。このように3成分系においてはス
ケール、腐食の両面にわたり良好な効果を有する
ものは見い出せない。
上記3成分系に比較して本願発明の4成分系に
おいては参考例1〜7及び9〜15において示され
る如く(イ)成分としてモリブデン酸ナトリウム、モ
リブデン酸アンモニウム、タングステン酸ナトリ
ウム及び亜硝酸ナトリウムを(ロ)成分としてグルコ
ン酸ナトリウム、クエン酸、リンゴ酸及びリンゴ
酸ナトリウムの一種又は2種以上を(ハ)成分として
塩化亜鉛、硫酸亜鉛、塩化第1スズ、硫酸マンガ
ン及び塩化ニツケルの1種又は2種以上を(ニ)成分
としてポリマレイン酸、ポリアクリル酸ナトリウ
ム、アクリル酸―メタクリル酸コポリマー、ポリ
メタクリル酸カリウム、アクリル酸―アクリルア
ミド―N―プロパンスルホン酸コポリマー、メタ
クリル酸―アクリルアミドコポリマー、アクリル
酸―アクリル酸メチルコポリマーを(イ)成分の化合
物の重量を1として(ロ)成分:(ハ)成分:(ニ)成分の割
合を重量比で0.5〜4:0.1〜1.2:0.2〜1.3となる
ように31〜84ppm(40〜50ppmが主体)添加す
ることによりスケール析出量は1.1〜13.3mg/
、m.d.d. 0.5〜6.0と低温水系においてもスケ
ール、腐食の両面にわたり良好な効果を有するこ
とがわかる。又防食効果においては、下記の説明
の如く3成分系に比較して顕著な相乗効果が発揮
されていることがわかる。例えば比較例3.4と参
考例2とを比較すると、3成分系の添加量は
45ppmであり、4成分系の添加量は42ppmであ
る。防食効果については、4成分系のm.d.d.は3
成分系のそれに比較して約1/6〜1/7と激減してお
り顕著な相乗効果が発揮されていることがわか
る。又スケール析出防止効果についても3成分系
の約1/5〜1/7となつていることもわかる。次に比
較例5と参考例9とを比較すると3成分系の添加
量は50ppmであり、4成分系の添加量は42ppm
と減少しているにもかかわらず4成分系のm.d.d.
は3成分系のそれに比較して約1/9となつており
顕著な相乗効果が発揮されていることがわかる。
又スケール析出防止効果についても3成分系の1/
2以下となつていることがわかる。次に比較例2
と比較例2にポリアクリル酸ナトリウムを添加し
た参考例9とを比較すると、3成分系の添加量は
50ppmであり、4成分系の添加量は42ppmであ
る。ポリアクリル酸ナトリウムはスケール析出防
止剤として公知であるが、単独において腐食抑制
効果は実質的に無い。参考例9の4成分系におい
ては単にスケール防止効果が良好となるばかりで
はなくモリブデン酸ナトリウム、グルコン酸ナト
リウム、塩化亜鉛の添加量が比較例2の3成分系
の3/5に減少しているにもかかわらずm.d.dは3
成分系の1/5となつており顕著な相乗効果が発揮
されていることがわかる。又参考例8で示される
如く薬剤添加量を比較例2,5で示される3成分
系の約2/5である21ppmにまで低減しても良好な
スケール析出、腐食防止効果が発揮されているこ
とがわかる。
又比較例6及び7は、公知の4成分系の防食剤
である特開昭53―149836号の発明の試験結果であ
る。グルコン酸ナトリウム、塩化亜鉛及びポリマ
レイン酸にトリアゾール化合物を添加した4成分
系である比較例6及び7と参考例2とを比較する
と比較例6及び7の添加量は55ppmであり参考
例2の添加量は42ppmと低添加量であるにもか
かわらず参考例2のm.d.d.は比較例6.7のそれの
1/3〜1/6となつており本願発明の4成分系の防食
剤は他の公知の4成分系の防食剤と比較しても低
温水系においても顕著な防食効果を発揮すること
がわかる。
製剤例
この発明の4成分を含有する製剤をいくつか試
み表3に示す如き処方を得た。これらの各製剤に
ついて参考例と同様のテストを行い表3の如き結
果を得た。[Table] From the test results using Osaka city water 5 times concentrated water, it can be seen that when no chemicals were added, there was a high scale precipitation amount of 404 mg/mdd/mdd215 as shown in Comparative Example 1, and a tendency towards corrosion. Furthermore, when three of the four components of the present invention are added at 45 to 50 ppm (see Comparative Examples 2 to 5), the anticorrosive effect is good in Comparative Example 2, but the amount of scale precipitation is 41.0 mg/
However, in Comparative Example 5 (conventionally known three-component system, corresponding to the invention of Japanese Patent Publication No. 53-43376), although scale precipitation is suppressed, a satisfactory corrosion prevention effect with mdd20 cannot be obtained. I understand that. As described above, no three-component system has been found that has good effects on both scaling and corrosion. Compared to the above three-component system, the four-component system of the present invention contains sodium molybdate, ammonium molybdate, sodium tungstate, and sodium nitrite as component (a), as shown in Reference Examples 1 to 7 and 9 to 15. (b) One or more of sodium gluconate, citric acid, malic acid, and sodium malate as the ingredient; and one or more of zinc chloride, zinc sulfate, stannous chloride, manganese sulfate, and nickel chloride as the ingredient (c). Polymaleic acid, sodium polyacrylate, acrylic acid-methacrylic acid copolymer, polypotassium methacrylate, acrylic acid-acrylamide-N-propanesulfonic acid copolymer, methacrylic acid-acrylamide copolymer, acrylic acid- The weight ratio of the methyl acrylate copolymer (a) is 1, and the weight ratio of the (b) component: (c) component: (d) component is 0.5 to 4: 0.1 to 1.2: 0.2 to 1.3. By adding 31 to 84 ppm (mainly 40 to 50 ppm), the amount of scale precipitation can be reduced to 1.1 to 13.3 mg/
It can be seen that it has good effects on both scale and corrosion even in low-temperature water systems with mdd 0.5 to 6.0. In terms of anticorrosion effect, it can be seen that a remarkable synergistic effect is exhibited compared to the three-component system as explained below. For example, when comparing Comparative Example 3.4 and Reference Example 2, the amount of the three-component system added is
The amount added in the four-component system is 42 ppm. Regarding the anti-corrosion effect, the mdd of the four-component system is 3.
It can be seen that the amount is drastically reduced to about 1/6 to 1/7 compared to that of the component system, and a remarkable synergistic effect is being exerted. It can also be seen that the scale precipitation prevention effect is about 1/5 to 1/7 that of the three-component system. Next, comparing Comparative Example 5 and Reference Example 9, the amount added in the three-component system is 50 ppm, and the amount added in the four-component system is 42 ppm.
Despite the decrease, the mdd of the four-component system
is approximately 1/9 of that of the three-component system, indicating that a remarkable synergistic effect is being exerted.
In addition, the effect of preventing scale precipitation is 1/1 of that of the three-component system.
It can be seen that it is less than 2. Next, comparative example 2
Comparing with Reference Example 9 in which sodium polyacrylate was added to Comparative Example 2, the amount of the three-component system added was
50 ppm, and the amount added in the four-component system is 42 ppm. Sodium polyacrylate is known as a scale precipitation inhibitor, but alone it has virtually no corrosion inhibiting effect. The four-component system of Reference Example 9 not only has a good scale prevention effect, but also the added amounts of sodium molybdate, sodium gluconate, and zinc chloride are reduced to 3/5 of the three-component system of Comparative Example 2. Despite this, mdd is 3
It is 1/5 of the component system, indicating that a remarkable synergistic effect is being exerted. Furthermore, as shown in Reference Example 8, even when the amount of the chemical added was reduced to 21 ppm, which is about 2/5 of the three-component system shown in Comparative Examples 2 and 5, good scale precipitation and corrosion prevention effects were exhibited. I understand that. Comparative Examples 6 and 7 are the test results of the invention of JP-A-53-149836, which is a known four-component anticorrosive agent. Comparing Comparative Examples 6 and 7, which are four-component systems in which a triazole compound is added to sodium gluconate, zinc chloride, and polymaleic acid, and Reference Example 2, the amount added in Comparative Examples 6 and 7 is 55 ppm, and the amount added in Reference Example 2 is 55 ppm. Although the amount added is as low as 42 ppm, the mdd of Reference Example 2 is lower than that of Comparative Example 6.7.
It is 1/3 to 1/6, which shows that the four-component corrosion inhibitor of the present invention exhibits a remarkable anticorrosion effect even in low-temperature water systems compared to other known four-component corrosion inhibitors. . Formulation Examples Several formulations containing the four ingredients of this invention were tried and the formulations shown in Table 3 were obtained. The same tests as in the reference example were conducted for each of these preparations, and the results shown in Table 3 were obtained.
【表】【table】
【表】
実施例
中、低圧用ボイラーを対象として次のようなテ
ストを行つた。参考例で用いたSPCCのテストピ
ースを懸吊し100rpmで回転しうる装置を付設し
たオートクレーブを用いる。使用する試験水の量
は800mlである。このオートクレーブを用いて200
℃,16Kg/cm2の圧力下でのテストピースの腐食を
テストする。腐食条件を強くするため試験水は大
阪市水軟水の20倍濃縮液をPH9に調節した水を用
い、所定量の薬剤を添加し、撹拌棒に懸吊したテ
ストピースを液中に浸漬する。100rpmの撹拌の
下200℃,16Kg/cm2の加圧下2日間のテストを行
いテストピースの腐食減量を測定した。また生じ
たピツチングの数を調べその数を記録した。得ら
れた結果を表5に、又、その用いた試験水の水質
を表4にそれぞれ示す。[Table] Example The following tests were conducted on medium and low pressure boilers. An autoclave equipped with a device capable of suspending the SPCC test piece used in the reference example and rotating it at 100 rpm is used. The amount of test water used is 800ml. 200 using this autoclave
℃, test the corrosion of the test piece under the pressure of 16Kg/ cm2 . In order to strengthen the corrosive conditions, the test water used was a 20-fold concentrated solution of Osaka city water softened water adjusted to pH 9, a predetermined amount of chemicals was added, and a test piece suspended from a stirring rod was immersed in the solution. A test was carried out for 2 days at 200° C. and under a pressure of 16 kg/cm 2 under stirring at 100 rpm, and the corrosion loss of the test piece was measured. The number of pittings that occurred was also checked and recorded. The obtained results are shown in Table 5, and the quality of the test water used is shown in Table 4.
【表】【table】
【表】
上記結果が示す如く、ボイラー水を対象とした
試験において、(イ)成分としてモリブデン酸ナトリ
ウム及びタングステン酸ナトリウムを(ロ)成分とし
てグルコン酸ナトリウム、グルコン酸及びクエン
酸ナトリウムを(ハ)成分として硫酸マンガン及び塩
化第1スズを(ニ)成分としてアクリル酸―メタクリ
ル酸コポリマー、アクリル酸―アクリル酸メチル
コポリマー、アクリル酸―マレイン酸コポリマー
及びポリアクリル酸ナトリウムを(イ)成分の化合物
の重量を1として(ロ)成分:(ハ)成分:(ニ)成分の割合
を重量比で2〜10:1:0.3〜0.8となるように43
〜64ppm添加することにより本願発明の4成分
系防食剤は、ピツチングを抑え、優れた防食効果
を発揮することがわかる。
そして、テストピースのボイラー水接触面を、
顕微鏡で観察すると、全面に緻密な被膜が見ら
れ、X線回折分析でこの被膜は、Fe3O4を主体と
するものであることが認められた。また、この被
膜はJIS K―0100の方法に準じテストピースの酸
洗浄後においても除去されにくい性質を持ち従来
処理では見られない強固なものであつた。従つて
上記の優れたピツチング防止効果は、この被膜形
成によるものと考えられる。一方従来の防食剤で
は、腐食速度を著しく低下しうるものであつても
必ずしもピツチング発生防止につながらず、ピツ
チング防止用として別に亜硫酸ナトリウムやヒド
ラジン等の脱酸素剤の添加が必要であつた。この
発明の防食剤ではかかる脱酸素剤の併用添加は不
要であることがわかる。[Table] As shown in the above results, in a test targeting boiler water, sodium molybdate and sodium tungstate were used as the (a) component, and sodium gluconate, gluconic acid, and sodium citrate were used as the (b) component. Manganese sulfate and stannous chloride as components (2), acrylic acid-methacrylic acid copolymer, acrylic acid-methyl acrylate copolymer, acrylic acid-maleic acid copolymer, and sodium polyacrylate (2) component weight of compound Assuming that 1, the ratio of component (b): component (c): component (d) should be 2 to 10:1:0.3 to 0.8 by weight43
It can be seen that by adding ~64 ppm, the four-component anticorrosive agent of the present invention suppresses pitting and exhibits an excellent anticorrosion effect. Then, the boiler water contact surface of the test piece was
When observed under a microscope, a dense film was seen over the entire surface, and X-ray diffraction analysis confirmed that this film was mainly composed of Fe 3 O 4 . Furthermore, this film was difficult to remove even after the test piece was washed with acid according to the method of JIS K-0100, and was strong and not seen in conventional treatments. Therefore, it is thought that the excellent pitting prevention effect described above is due to the formation of this film. On the other hand, with conventional anticorrosive agents, even if they can significantly reduce the corrosion rate, they do not necessarily prevent the occurrence of pitting, and it is necessary to separately add an oxygen scavenger such as sodium sulfite or hydrazine to prevent pitting. It can be seen that the anticorrosive agent of the present invention does not require the combined addition of such an oxygen scavenger.
Claims (1)
塩、タングステン酸ならびにそのアルカリ性塩
および亜硝酸のアルカリ性塩より選ばれた1種
または2種以上、 (ロ) 脂肪族オキシカルボン酸またはそのアルカリ
性塩、 (ハ) 重金属イオンを水中で容易に放出しうる化合
物および (ニ) 分子量500〜100000で水溶性の、オレフイン
系化合物の重合体または共重合体、を有効成分
として含有し、(イ),(ロ),(ハ)および(ニ)の各有効成
分の配合比が重量比で(イ):(ロ):(ハ):(ニ)が1:
0.2〜30:0.1〜5:0.1〜5であることを特徴と
する高温水系用防食剤。 2 モリブデン酸のアルカリ性塩、タングステン
酸のアルカリ性塩および亜硝酸のアルカリ性塩
が、それぞれアルカリ金属塩またはアンモニウム
塩である特許請求の範囲第1項記載の防食剤。 3 脂肪族オキシカルボン酸またはそのアルカリ
性塩が、グリコール酸、クエン酸、リンゴ酸、酒
石酸、乳酸もしくはグルコン酸またはそれらのア
ルカリ金属塩もしくはアンモニウム塩である特許
請求の範囲第1項または第2項記載の防食剤。 4 重金属イオンを水中で容易に放出しうる化合
物が、亜鉛、マンガン、スズ、コバルト、ニツケ
ル、チタン、銅または鉛の硫酸塩、塩酸塩、硝酸
塩またはスルフアミン酸塩である特許請求の範囲
第1〜3項いずれかに記載の防食剤。 5 オレフイン系化合物の重合体または共重合体
が、アクリル酸およびその低級アルキルエステル
ならびに低級ヒドロキシアルキルエステル、メタ
クリル酸およびその低級アルキルエステルならび
に低級ヒドロキシアルキルエステル、アクリルア
ミド、メタクリルアミド、アクリルアミド―N―
アルカンスルホン酸、マレイン酸、フマル酸、イ
タコン酸、ビニルアルコール、アリルアルコー
ル、メタリルアルコール、アクロレイン、メタク
ロレイン、アリルスルホン酸、メタリルスルホン
酸およびアクリロニトリルの群から選ばれた1種
又は2種以上の化合物の重合体または共重合体で
ある特許請求の範囲第1〜4項いずれかに記載の
防食剤。 6 オレフイン系化合物の重合体または共重合体
が、アクリル酸、メタクリル酸、マレイン酸、ア
クリルアミド、アクリルアミド―N―プロパンス
ルホン酸、アクリル酸メチル、アクリル酸エチ
ル、メタクリル酸メチルおよびメタクリル酸エチ
ルの群から選ばれた1種または2種以上の重合体
または共重合体である特許請求の範囲第1〜4項
いずれかに記載の防食剤。 7 (イ),(ロ),(ハ)および(ニ)の各有効成分の配合比
が
重量比で(イ):(ロ):(ハ):(ニ)が1:0.5〜10:0.1〜
1.5:0.2〜1.6である特許請求の範囲第1〜6項の
いずれかに記載の防食剤。[Scope of Claims] 1 (a) one or more selected from molybdic acid and its alkaline salts, tungstic acid and its alkaline salts, and nitrous acid alkaline salts; (b) aliphatic oxycarboxylic acids or their It contains as active ingredients an alkaline salt, (3) a compound that can easily release heavy metal ions in water, and (2) a water-soluble polymer or copolymer of an olefin compound with a molecular weight of 500 to 100,000; ), (b), (c), and (d), the weight ratio of each active ingredient is (a): (b): (c): (d) is 1:
0.2-30:0.1-5:0.1-5 anticorrosive agent for high temperature water systems. 2. The anticorrosive agent according to claim 1, wherein the alkaline salt of molybdic acid, the alkaline salt of tungstic acid, and the alkaline salt of nitrous acid are each an alkali metal salt or an ammonium salt. 3. Claim 1 or 2, wherein the aliphatic oxycarboxylic acid or its alkaline salt is glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, or gluconic acid, or an alkali metal salt or ammonium salt thereof. anti-corrosion agent. 4. Claims 1 to 4, wherein the compound capable of easily releasing heavy metal ions in water is a sulfate, hydrochloride, nitrate, or sulfamate of zinc, manganese, tin, cobalt, nickel, titanium, copper, or lead. The anticorrosive agent according to any one of Item 3. 5 Polymers or copolymers of olefin compounds are acrylic acid and its lower alkyl esters and lower hydroxyalkyl esters, methacrylic acid and its lower alkyl esters and lower hydroxyalkyl esters, acrylamide, methacrylamide, acrylamide-N-
One or more selected from the group of alkanesulfonic acid, maleic acid, fumaric acid, itaconic acid, vinyl alcohol, allyl alcohol, methallyl alcohol, acrolein, methacrolein, allylsulfonic acid, methallylsulfonic acid, and acrylonitrile. The anticorrosive agent according to any one of claims 1 to 4, which is a polymer or copolymer of the compound. 6 The polymer or copolymer of olefinic compounds is selected from the group of acrylic acid, methacrylic acid, maleic acid, acrylamide, acrylamide-N-propanesulfonic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The anticorrosive agent according to any one of claims 1 to 4, which is one or more selected polymers or copolymers. 7. The weight ratio of each active ingredient (a), (b), (c) and (d) is (a):(b):(c):(d) from 1:0.5 to 10:0.1. ~
1.5: The anticorrosive agent according to any one of claims 1 to 6, which has a ratio of 0.2 to 1.6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7532781A JPS57192270A (en) | 1981-05-18 | 1981-05-18 | Corrosion inhibitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7532781A JPS57192270A (en) | 1981-05-18 | 1981-05-18 | Corrosion inhibitor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57192270A JPS57192270A (en) | 1982-11-26 |
JPS6257715B2 true JPS6257715B2 (en) | 1987-12-02 |
Family
ID=13573050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7532781A Granted JPS57192270A (en) | 1981-05-18 | 1981-05-18 | Corrosion inhibitor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57192270A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010266124A (en) * | 2009-05-14 | 2010-11-25 | Kurita Water Ind Ltd | Water treatment agent adding method in simple boiler |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993886A (en) * | 1982-11-17 | 1984-05-30 | Katayama Chem Works Co Ltd | Anticorrosive for metal |
CA2020858C (en) * | 1989-07-14 | 2000-08-08 | Sakae Katayama | Water treatment agent and water treatment method for boiler |
JP4682273B2 (en) * | 2000-12-12 | 2011-05-11 | 株式会社片山化学工業研究所 | Water treatment method for circulating cooling water system |
JPWO2005091412A1 (en) * | 2004-03-22 | 2007-08-30 | シーシーアイ株式会社 | Coolant composition for fuel cell |
CN106048616A (en) * | 2010-11-11 | 2016-10-26 | 里弗领袖可再生能源公司 | Corrosion inhibiting composition |
WO2014085262A1 (en) | 2012-11-28 | 2014-06-05 | Rivertop Renewables | Corrosion inhibiting, freezing point lowering compositions |
US9670124B2 (en) | 2013-03-13 | 2017-06-06 | Rivertop Renewables, Inc. | Nitric acid oxidation process |
EP2970079A4 (en) | 2013-03-13 | 2016-11-30 | Rivertop Renewables Inc | Improved nitric acid oxidation processes |
JP2019203178A (en) * | 2018-05-25 | 2019-11-28 | 株式会社アーレスティ | Metal fatigue resistance adding agent and metal fatigue resistance adding method |
-
1981
- 1981-05-18 JP JP7532781A patent/JPS57192270A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010266124A (en) * | 2009-05-14 | 2010-11-25 | Kurita Water Ind Ltd | Water treatment agent adding method in simple boiler |
Also Published As
Publication number | Publication date |
---|---|
JPS57192270A (en) | 1982-11-26 |
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