EP0225051B1 - The treatment of aqueous systems - Google Patents
The treatment of aqueous systems Download PDFInfo
- Publication number
- EP0225051B1 EP0225051B1 EP86308419A EP86308419A EP0225051B1 EP 0225051 B1 EP0225051 B1 EP 0225051B1 EP 86308419 A EP86308419 A EP 86308419A EP 86308419 A EP86308419 A EP 86308419A EP 0225051 B1 EP0225051 B1 EP 0225051B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- zinc
- hydrogen
- methyl
- vinyl
- 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
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- 239000013522 chelant Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 allyl carboxylic acid Chemical class 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005260 corrosion Methods 0.000 claims description 19
- 230000007797 corrosion Effects 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-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
- 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 5
- 239000004471 Glycine Substances 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
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 5
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical group OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 claims description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- SFJPGSCMZIUEDJ-UHFFFAOYSA-N 2-[2-[[carboxy-(2-hydroxy-4-methylphenyl)methyl]amino]ethylamino]-2-(2-hydroxy-4-methylphenyl)acetic acid Chemical compound OC1=CC(C)=CC=C1C(C(O)=O)NCCNC(C(O)=O)C1=CC=C(C)C=C1O SFJPGSCMZIUEDJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- 235000009529 zinc sulphate Nutrition 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 2
- 229910006069 SO3H Inorganic materials 0.000 claims 2
- 239000001530 fumaric acid Substances 0.000 claims 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 2
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 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 1
- XLJGIXLDEYIALO-UHFFFAOYSA-N 2-(carboxymethylamino)-4-hydroxybutanoic acid Chemical compound OCCC(C(O)=O)NCC(O)=O XLJGIXLDEYIALO-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- JTPLPDIKCDKODU-UHFFFAOYSA-N acetic acid;2-(2-aminoethylamino)ethanol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO JTPLPDIKCDKODU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 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
Definitions
- the present invention relates to the treatment of aqueous systems and, more particularly, to reducing or eliminating corrosion in aqueous systems.
- inorganic salts such as nitrites and chromates, inorganic mono and polyphosphates, certain water soluble polymers including naturally occurring materials such as lignins and starches as well as synthetic materials such as polyacrylates, as well as organic phosphonates.
- zinc salts for this purpose. Indeed, it is known to use zinc salts in combination with organic type corrosion inhibitors, principally organic phosphonates and polyacrylates.
- AT-B-332 699 discloses preventing corrosion using a phosphonate and, optionally, a zinc salt.
- a method of treating an aqueous system which comprises adding thereto a zinc salt, a chelant having the formula set out below and either a product containing at least one phosphorus-containing acid group and at least one carboxylic acid group or an acrylic, vinyl or allyl carboxylic acid polymer.
- any water soluble zinc salt can be used in the present invention.
- Typical salts which can be used include zinc sulphate, zinc chloride, zinc nitrate and zinc acetate, zinc sulphate monohydrate and zinc chloride being particularly preferred.
- the third component used in the present invention will, in general, be a phosphonate.
- the materials used contain at least two acid groups, one of which is a phosphonate group and the other is a carboxylic acid group, at least the two said acid groups being attached to carbon atoms.
- Preferred phosphonates include hydroxy phosphonoacetic acid and 2-phosphono butane-1,2,4-tricarboxylic acid, the latter being particularly preferred.
- these preferred phosphonates possess the general formula wherein R is hydrogen, alkyl, alkenyl or alkynyl having up to 4 carbon atoms; phenyl; cycloalkyl having 3 to 6 carbon atoms; benzyl; phenethyl or wherein R' is hydrogen, alkyl having 1 to 4 carbon atoms or carboxyl, R" is hydrogen or methyl and R''' is carboxyl or phosphonate.
- a polymeric material and, in particular, carboxylic acid polymers which contain a chain phosphorus atom which forms part of an acid group.
- the molecular weight of such polymers is relatively low, generally below 5,000, the preferred molecular weight being from 250 to 750, especially about 500.
- a particularly suitable polymer is that sold as "Belclene 500", a registered Trade Mark of Ciba-Geigy.
- a synergistic effect although most pronounced when the phosphorus containing materials are used, can also be obtained when a polycarboxylic acid is used, typically one having a molecular weight from 1,000 to 5,000.
- Such polymers may be derived from acrylic, vinyl or allyl carboxylic monomers, typically acrylic, methacrylic, maleic, fumaric, itaconic, crotonic or cinnamic acid alone or with a suitable comonomer.
- Such comonomers include acrylamide, (meth)acrylate esters or hydroxy esters e.g.
- hydroxypropyl esters vinyl pyrrolidone, vinyl acetate, acrylonitrile, vinyl methyl ether, 2-acrylamido-2-methyl-propane sulphonic acid, vinyl or allyl sulphonic acid and styrene sulphonic acid as well as cationic monomers such as diallyl dimethyl ammonium chloride, dimethylamino ethylacrylate or methacrylate, optionally quaternised with, for example, dimethyl sulphate or methyl chloride.
- cationic monomers such as diallyl dimethyl ammonium chloride, dimethylamino ethylacrylate or methacrylate, optionally quaternised with, for example, dimethyl sulphate or methyl chloride.
- the chelants which can be used in the method of the present invention possess the formula where R1 is hydrogen, hydroxyethyl or carboxymethyl, preferably carboxymethyl, R2 is hydrogen, hydroxyphenyl, preferably ortho-hydroxyphenyl, which is optionally methyl or sulphonic acid substituted, or carboxyl, R4 is hydrogen or carboxyl, where R1, R2 and R4 are as defined above and X is -(CH2)2- or - (CH2)3 - with the proviso that at least one of R2 and R3 contains a hydroxyphenyl group.
- the phenyl groups may be substituted, if desired, preferably by one or more halogen atoms.
- the chelant is to be used in aqueous systems which possess a high pH and a relatively high temperature it is preferred that at least one of R1, R2 and R3 contains a hydroxyl group.
- the most preferred chelants possess a nitrogen ligand, a carboxylic acid group and a hydroxyl group.
- Preferred chelants for use in the present invention include N,N'-di(-2-hydroxybenzyl-)trimethylenediamine-N, N'-diacetic acid, N,N'ethylene-bis-[2-(2-hydroxy-4-methyl-phenyl)-glycine], ethylenediamine N, N'-bis-[2-hydroxyphenylacetic acid] and N, N-di(2-hydroxy-5-sulphonic acid benzyl)glycine which is especially preferred not only on account of its effectiveness but also on account of its excellent solubility properties which facilitate the formulation of compositions.
- the present invention also provides a composition suitable for addition to an aqueous system which comprises a water soluble zinc salt, a product containing at least one phosphorus containing acid group and at least one carboxylic acid group or an acrylic, vinyl or allyl carboxylic acid polymer, and a chelant. In such a situation, it may be desirable to add further quantities of chelant as required.
- the composition will be an aqueous formulation containing, generally, 1% to 2% by weight of zinc salt (as zinc), 4% to 10% by weight of the phosphorus containing material or polymer and 1% to 25% by weight, especially about 5% by weight, of the chelant.
- zinc salt as zinc
- 4% to 10% by weight of the phosphorus containing material or polymer 4% to 10% by weight of the phosphorus containing material or polymer
- 1% to 25% by weight especially about 5% by weight, of the chelant.
- a further surprising feature of the present invention is that the presence of the combination of chelant and phosphorus containing compound and/or acrylic vinyl or allyl carboxylic acid polymer enables one to reduce the amount of zinc salt. It is usual in the art to employ amounts of the order of 2 to 5ppm zinc. However, with ever increasing restrictions on concentrations of zinc in discharges there is a constant demand to reduce the amounts of zinc used. It has been found that by using the additional ingredients it is possible to reduce the amount of zinc to, say, about 1ppm for comparable effectiveness. In such circumstances it is preferred to employ about 4ppm of the phosphorus compound and about 2.5 to 5ppm of chelant. If, on the other hand, one uses 2.5ppm of zinc then it is preferred to use about 10ppm of phosphorus compound and about 5ppm of chelant.
- the combination of the present invention together with other ingredients including phosphates, biocides, yellow metal corrosion inhibitors such as benzotriazole and tolyltriazole as well as other polymers which act as dispersants such as polyacrylic acid, polymaleic acid and copolymers of maleic acid with styrene sulphonic acid.
- dispersants especially a copolymer of methacrylic acid and acrylamide is particularly advantageous, especially one in which the mole ratio is about 1:3, and further enhances the corrosion protection given by the three component system.
- the molecular weight of the homopolymers will be 1,000 to 10,000 while that of the copolymers will be 1,000 to 50,000.
- Examples 15 - 34 were carried out at 54°C.
- Example 42 in relation to Example 43 shows the effect of using Chelant 2 in enabling one to reduce the concentration of zinc/phosphate.
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Abstract
Description
- The present invention relates to the treatment of aqueous systems and, more particularly, to reducing or eliminating corrosion in aqueous systems.
- Many different types of material have been employed to prevent or inhibit corrosion in aqueous systems. These include inorganic salts such as nitrites and chromates, inorganic mono and polyphosphates, certain water soluble polymers including naturally occurring materials such as lignins and starches as well as synthetic materials such as polyacrylates, as well as organic phosphonates. In addition, it is well known to use zinc salts for this purpose. Indeed, it is known to use zinc salts in combination with organic type corrosion inhibitors, principally organic phosphonates and polyacrylates.
- The use of zinc salts enables one to passivate corrosion of the metal in contact with the system. It is generally believed that localised high concentrations of hydroxide ions arise at sites of corrosion on the metal surface because, due to the galvanic cell effect, oxygen present in the water is reduced to hydroxide ions at the cathodic sites. These hydroxide ions then react with zinc ions of the zinc salt to give zinc hydroxide which in turn yields a protective film on the metal surface.
- While this passivation system works reasonably satisfactorily in some aqueous media it is known that the use of zinc salts, with or without the organic type corrosion inhibitor, is ineffective when the pH of the system is high, for example at pH from 8.2 to 9.0. Such a pH can be present when the water is hard, or is otherwise alkaline ie of low hardness and high alkalinity as can be the case with base exchanged water. Under such circumstances, the zinc hydroxide precipitates prematurely in the system water and therefore does not form a protective film over the metal. Thus in such systems the zinc actually becomes a foulant of the system. Similar problems arise when the temperature of the aqueous system is raised, for example to at least 40°C as can occur when the aqueous system is used as cooling water which comes into contact with hot metal surfaces. AT-B-332 699 discloses preventing corrosion using a phosphonate and, optionally, a zinc salt.
- It has now surprisingly been found, according to the present invention, that more effective corrosion inhibition can be obtained when a zinc salt is used together with a class of phosphonate or similar material and, in addition, a specific class of chelant. It has been found that this combination is capable of being effective under a combination of severe pH and temperature conditions. It is considerably more effective than existing zinc/organic products on pre-corroded mild steel surfaces since the combination is capable of stifling existing corrosion as well as enabling much faster passivation of the rusty surface to be brought about. Thus the combination, as well as inhibiting corrosion, also acts as an on line cleaning agent by removing old rust.
- According to the present invention there is provided a method of treating an aqueous system which comprises adding thereto a zinc salt, a chelant having the formula set out below and either a product containing at least one phosphorus-containing acid group and at least one carboxylic acid group or an acrylic, vinyl or allyl carboxylic acid polymer.
- Generally, any water soluble zinc salt can be used in the present invention. Typical salts which can be used include zinc sulphate, zinc chloride, zinc nitrate and zinc acetate, zinc sulphate monohydrate and zinc chloride being particularly preferred.
- The third component used in the present invention will, in general, be a phosphonate. Preferably, the materials used contain at least two acid groups, one of which is a phosphonate group and the other is a carboxylic acid group, at least the two said acid groups being attached to carbon atoms.
- Preferred phosphonates include hydroxy phosphonoacetic acid and 2-phosphono butane-1,2,4-tricarboxylic acid, the latter being particularly preferred. Thus these preferred phosphonates possess the general formula
wherein R is hydrogen, alkyl, alkenyl or alkynyl having up to 4 carbon atoms; phenyl; cycloalkyl having 3 to 6 carbon atoms; benzyl; phenethyl or
wherein R' is hydrogen, alkyl having 1 to 4 carbon atoms or carboxyl, R" is hydrogen or methyl and R''' is carboxyl or phosphonate. - It is also possible to employ as the third component in the method a polymeric material and, in particular, carboxylic acid polymers which contain a chain phosphorus atom which forms part of an acid group. Thus these polymeric materials are preferably phosphino polycarboxylic acids, typically those having the formula
where N + M = 4 to 20
The molecular weight of such polymers is relatively low, generally below 5,000, the preferred molecular weight being from 250 to 750, especially about 500. A particularly suitable polymer is that sold as "Belclene 500", a registered Trade Mark of Ciba-Geigy. - It has also been found that a synergistic effect, although most pronounced when the phosphorus containing materials are used, can also be obtained when a polycarboxylic acid is used, typically one having a molecular weight from 1,000 to 5,000. Such polymers may be derived from acrylic, vinyl or allyl carboxylic monomers, typically acrylic, methacrylic, maleic, fumaric, itaconic, crotonic or cinnamic acid alone or with a suitable comonomer. Such comonomers include acrylamide, (meth)acrylate esters or hydroxy esters e.g. hydroxypropyl esters, vinyl pyrrolidone, vinyl acetate, acrylonitrile, vinyl methyl ether, 2-acrylamido-2-methyl-propane sulphonic acid, vinyl or allyl sulphonic acid and styrene sulphonic acid as well as cationic monomers such as diallyl dimethyl ammonium chloride, dimethylamino ethylacrylate or methacrylate, optionally quaternised with, for example, dimethyl sulphate or methyl chloride.
The chelants which can be used in the method of the present invention possess the formula
where R¹ is hydrogen, hydroxyethyl or carboxymethyl, preferably carboxymethyl, R² is hydrogen, hydroxyphenyl, preferably ortho-hydroxyphenyl, which is optionally methyl or sulphonic acid substituted, or carboxyl, R⁴ is hydrogen or carboxyl,
where R¹, R² and R⁴ are as defined above and
X is -(CH₂)₂- or - (CH₂)₃ - with the proviso that at least one of R² and R³ contains a hydroxyphenyl group. The phenyl groups may be substituted, if desired, preferably by one or more halogen atoms. - If the chelant is to be used in aqueous systems which possess a high pH and a relatively high temperature it is preferred that at least one of R¹, R² and R³ contains a hydroxyl group. Thus the most preferred chelants possess a nitrogen ligand, a carboxylic acid group and a hydroxyl group.
- Preferred chelants for use in the present invention include N,N'-di(-2-hydroxybenzyl-)trimethylenediamine-N, N'-diacetic acid, N,N'ethylene-bis-[2-(2-hydroxy-4-methyl-phenyl)-glycine], ethylenediamine N, N'-bis-[2-hydroxyphenylacetic acid] and N, N-di(2-hydroxy-5-sulphonic acid benzyl)glycine which is especially preferred not only on account of its effectiveness but also on account of its excellent solubility properties which facilitate the formulation of compositions.
- In general, from 1 to 10 parts by weight of chelant and from 4 to 6 parts by weight of the phosphorus containing compound are employed to 1 part of the zinc salt. While in certain circumstances it may be desirable to add the individual components separately, in other situations it will be convenient to add the components together in the form of a composition. Accordingly, the present invention also provides a composition suitable for addition to an aqueous system which comprises a water soluble zinc salt, a product containing at least one phosphorus containing acid group and at least one carboxylic acid group or an acrylic, vinyl or allyl carboxylic acid polymer, and a chelant. In such a situation, it may be desirable to add further quantities of chelant as required. Typically, the composition will be an aqueous formulation containing, generally, 1% to 2% by weight of zinc salt (as zinc), 4% to 10% by weight of the phosphorus containing material or polymer and 1% to 25% by weight, especially about 5% by weight, of the chelant.
- A further surprising feature of the present invention is that the presence of the combination of chelant and phosphorus containing compound and/or acrylic vinyl or allyl carboxylic acid polymer enables one to reduce the amount of zinc salt. It is usual in the art to employ amounts of the order of 2 to 5ppm zinc. However, with ever increasing restrictions on concentrations of zinc in discharges there is a constant demand to reduce the amounts of zinc used. It has been found that by using the additional ingredients it is possible to reduce the amount of zinc to, say, about 1ppm for comparable effectiveness. In such circumstances it is preferred to employ about 4ppm of the phosphorus compound and about 2.5 to 5ppm of chelant. If, on the other hand, one uses 2.5ppm of zinc then it is preferred to use about 10ppm of phosphorus compound and about 5ppm of chelant.
- It is also possible to use the combination of the present invention together with other ingredients including phosphates, biocides, yellow metal corrosion inhibitors such as benzotriazole and tolyltriazole as well as other polymers which act as dispersants such as polyacrylic acid, polymaleic acid and copolymers of maleic acid with styrene sulphonic acid. In particular, it has been found that the use of certain dispersants, especially a copolymer of methacrylic acid and acrylamide is particularly advantageous, especially one in which the mole ratio is about 1:3, and further enhances the corrosion protection given by the three component system. In general the molecular weight of the homopolymers will be 1,000 to 10,000 while that of the copolymers will be 1,000 to 50,000.
- The use of a phosphate is particularly noteworthy since zinc phosphate is effective in low water hardness systems because the zinc phosphate itself gives protection. By using the chelant and phosphorus containing compound as well it is possible, as previously discussed, to use significantly lower quantities of zinc.
- The following Examples further illustrate the present invention.
- In these Examples tests were carried out on a laboratory scale recirculating rig consisting of a plastic vessel holding 8 litres of water and connected by tubing to a circulating pump the water passing from the pump through a glass rack holding the metal test coupons ('line') and returning to the plastic vessel. Any evaporation was made up by the addition of de-ionised water. Metal test coupons were also suspended in the plastic vessel ('Pond'). The corrosion rate was calculated from the weight of metal lost during test. The water temperature was maintained by means of a heater/thermostat arrangement. The conditions of the test were as follows:
- System Water
- : 150ppm Ca hardness/150ppm 'M' Alkalinity
- Water pH
- : 8.8
- Water Temperature
- : 54°C or 40°C (as stated)
- Flow Rate: Line
- : 2 ft/sec
- Pond
- : 0.2 ft/sec
- Duration of Test
- : 3 days
- Initial Passivation
- : 1 day at 3 times normal maintenance dose.
-
-
- i) The blend of zinc/chelant/phosphonate is superior to zinc/phosphonate or zinc/chelant.
- ii) the best chelants are Chelants 1, 2,3 and 9.
- iii) Phosphonate 1 gives significantly better results than comparative Phosphonate 2.
-
- Chelant 1 = N, N'-di(-2 hydroxybenzyl trimethylenediamine-N,N'-diacetic acid
- Chelant 2 = N,N' Ethylene-bis- [2(2-hydroxy-4 methyl-phenyl) - glycine]
- Chelant 3 = Ethylenediamine N, N'bis-[2 hydroxyl phenyl acetic acid]
- Chelant 4 = Ethylenediamine tetraacetic acid.
- Chelant 5 = N,N-di (2 hydroxy ethyl) glycine.
- Chelant 6 = N-Hydroxyethyl,N,N' Ethylenediamine triacetic acid.
- Chelant 7 = 2-hydroxyethyl iminodiacetic acid.
- Chelant 8 = Diethylene triamine penta acetic acid.
- Chelant 9 = N,N-di(2 hydroxy -5-sulphonic acid benzyl) glycine
- Phosphonate 1 = 2-Phosphonobutane 1,2,4 tricarboxylic acid.
- Phosphonate 2 = Hydroxy ethylidene di-phosphonic acid.
- Phosphonate 3 = Hydroxy phosphonoacetic acid.
- Phosphino 1 = Phosphino polyacrylic acid, M.Wt. approx 500 (sold commercially as "Belclene 500" Ciba Geigy).
- Polymer 1 =
- Copolymer of methacrylic acid/acrylamide, mole ratio 1:3, M.Wt. 35,000.
- Polymer 2 =
- Polyacrylic acid, M.Wt.1000.
- Polymer 3 =
- Polyacrylic acid, M.Wt.4500.
-
- i) The excellent corrosion inhibiting properties of the zinc/chelant/phosphonate combinations are maintained at the higher test temperature; this should be compared with Chelant 8 which does not contain a hydroxy group (Example 32). The excellent corrosion inhibition is also maintained when the phosphonate is replaced by the phosphino-polycarboxylic acid in the 3 component combination.
- ii) The presence of Polymer 1, (Example 20), enhances the corrosion protection conferred by the 4 component blend over that given by the corresponding 3 component blend, (Example 19), without polymer.
- iii) The improvement brought about by the presence of the chelant with the zinc/polyacrylic acid combination.
- These Examples illustrate the effect of longer term tests. These were carried out on a laboratory scale simulated open, evaporative, recirculating cooling water system incorporating mild steel heat exchanger together with feed and bleed facilities which enable the system to run at a given concentration factor throughout the 14 day test. The test conditions were as follows:
- System Water
- : 160ppm Calcium hardness 50ppm Magnesium hardness 200ppm 'M' Alkalinity
- Water Temperature (Pond)
- : 50°C
- pH
- : 8.8
- Flow Rate through heat exchanger
- : 0.3 ft/sec
- Flow Rate through coupon chamber
- : 1.5 ft/sec
- Heat flux on exchanger
- : 75 kj/m⁻²/sec⁻¹
- Duration of test
- : 14 days
- Initial passivation
- : 3 x normal maintenance dose, allowed to decay from start of test.
- It was noticed that when Chelant 2 was in use (Examples 35 to 38), the corrosion which initiated on the heat exchanger was rapidly stifled whereas in Example 40 corrosion spread throughout the test. Chelant 4 was largely ineffective; in fact, the results indicate aggression. This shows that this chelant is unsuitable where there is a heat exchanger giving a high surface temperature.
- Example 42 in relation to Example 43 shows the effect of using Chelant 2 in enabling one to reduce the concentration of zinc/phosphate.
Claims (27)
- A method of treating an aqueous system which comprises adding thereto a water-soluble zinc salt, a chelant which possesses the formula
- A method according to claim 1 in which the zinc salt is zinc sulphate, zinc chloride, zinc nitrate or zinc acetate.
- A method according to claim 1 or 2 in which the phosphonate has the general formula
- A method according to claim 3 in which the phosphonate is hydroxy-phosphonoacetic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid.
- A method according to claim 1 or 2 in which the polymer is a copolymer of acrylic, methacrylic, maleic, fumaric, itaconic, crotonic or cinnamic acid with acrylamide, an acrylate or methacrylate ester or hydroxy ester, vinyl pyrrolidone, vinyl acetate, acrylonitrile, vinyl methyl ether, 2-acrylamido-2-methyl-propane sulphonic acid, vinyl, allyl or styrene sulphonic acid, or diallyldimethyl ammonium chloride or dimethylamino ethyl acrylate or methacrylate, optionally quaternised with dimethyl sulphate or methyl chloride.
- A method according to claim 1 or 2 in which the polymer is a polymer of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or crotonic acid, having a molecular weight from 1000 to 5000.
- A method according to any one of claims 1 to 7 in which the chelant is N,N'-di(2-hydroxybenzyl)-trimethylenediamine-N,N'-diacetic acid, N,N'ethyenebis-[2(2-hydroxy-4-methyl-phenyl)-glycine}, ethylenediamine N,N'-bis-[2-hydroxyphenylacetic acid] or N,N-di (2-hydroxy-5-sulphonic acid benzyl) glycine.
- A method according to any one of the preceding claims in which the zinc salt is added in an amount to provide up to 5 ppm zinc.
- A method according to claim 10 in which the zinc salt is added to provide up to 2 ppm zinc.
- A method according to any one of the preceding claims in which 1 to 10 parts by weight of chelant are added per part by weight of the zinc salt.
- A method according to any one of the preceding claims in which 4 to 6 parts by weight of the phosphorus and carboxylic acid group containing compound are added per part by weight of the zinc salt.
- A method according to any one of the preceding claims in which the system water attains a temperature of at least 40° C.
- A method according to any one of the preceding claims in which the system water attains a pH of at least 8.2.
- A composition suitable for addition to an aqueous system which comprises a water-soluble zinc salt, a product containing at least one phosphorus-containing acid group and at least one carboxylic acid group or an acrylic, vinyl or allyl carboxylic acid polymer, and a chelant which possesses the formula
- A composition according to claim 16 in which the zinc salt is zinc sulphate, zinc chloride, zinc nitrate or zinc acetate.
- A composition according to claim 16 or 17 which is agueous and contains 1 to 2% by weight of zinc salt (as zinc), 4 to 10% by weight of the phosphorus and carboxylic acid group containing material or polymer and 1 to 25% by weight of the chelant.
- A composition according to any one of claims 16 to 18 which also comprises a phosphate, biocide, yellow metal corrosion inhibitor or dispersant.
- A composition according to claim 19 in which the dispersant is a copolymer of methacrylic acid and acrylamide.
- A composition according to any one of claims 16 to 20 in which the phosphonate has the general formula
- A composition according to claim 21 in which the phosphonate is hydroxy-phosphonoacetic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid.
- A composition according to any one of claims 16 and 18 to 20 in which the polymer is a copolymer of acrylic, methacrylic, maleic, fumaric, itaconic, crotonic or cinnamic acid with acrylamide, an acrylate or methacrylate ester or hydroxy ester, vinyl pyrrolidine, vinyl acetate, acrylonitrile, vinyl methyl ether, 2-acrylamido--2-methyl-propane sulphonic acid, vinyl, allyl or styrene sulphonic acid, or diallyldimethyl ammonium chloride or dimethylamino ethyl acrylate or methacrylate, optionally quaternised with dimethyl sulphate or methyl chloride.
- A composition according to any one of claims 16 and 18 to 20 in which the polymer is a polymer of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or crotonic acid, having a molecular weight from 1000 to 5000.
- A composition according to any one of claims 16 to 26 in which the chelant is N,N'-di(2-hydroxybenzyl)-trimethyl-enediamine-N,N'-diacetic acid, N,N'ethylenebis-[2(2-hydroxy-4-methyl-phenyl)-glycine], ethylenediamine N,N'-bis-[2-hydroxyphenylacetic acid] or N,N-di(2-hydroxy-5-sulphonic acid benzyl) glycine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86308419T ATE72678T1 (en) | 1985-10-29 | 1986-10-29 | TREATMENT OF AQUEOUS SYSTEMS. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8526590 | 1985-10-29 | ||
GB08526590A GB2184109A (en) | 1985-10-29 | 1985-10-29 | The treatment of aqueous systems |
GB08623464A GB2183624A (en) | 1985-10-29 | 1986-09-30 | Anti-corrosion treatment of aqueous systems |
GB8623464 | 1986-09-30 |
Publications (2)
Publication Number | Publication Date |
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EP0225051A1 EP0225051A1 (en) | 1987-06-10 |
EP0225051B1 true EP0225051B1 (en) | 1992-02-19 |
Family
ID=26289944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86308419A Expired EP0225051B1 (en) | 1985-10-29 | 1986-10-29 | The treatment of aqueous systems |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0225051B1 (en) |
AT (1) | ATE72678T1 (en) |
AU (1) | AU6456486A (en) |
CA (1) | CA1332138C (en) |
DE (1) | DE3683928D1 (en) |
ES (1) | ES2038595T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8765656B2 (en) | 2006-08-02 | 2014-07-01 | Ch2O Incorporated | Disinfecting/mineral treating composition and methods comprising a chlorite or chlorate salt |
CN110158094A (en) * | 2019-07-11 | 2019-08-23 | 北京中天兰清环境科技有限公司 | A kind of formula and preparation method of the without phosphorus carbon steel corrosion inhibitor of composite efficient |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4717542A (en) * | 1987-01-23 | 1988-01-05 | W. R. Grace & Co. | Inhibiting corrosion of iron base metals |
NZ226331A (en) * | 1987-10-05 | 1991-08-27 | Calgon Corp | Method of inhibiting corrosion of metallic surfaces in aqueous systems using acrylic polymers and zinc ions; compositions therefor |
EP0364030A1 (en) * | 1988-10-11 | 1990-04-18 | Calgon Corporation | Synergistic compositions and method for inhibiting carbon steel corrosion in aqueous systems |
US5171477A (en) * | 1991-05-31 | 1992-12-15 | W. R. Grace & Co.-Conn. | Corrosion inhibition in chelant solutions |
ES2059273B1 (en) * | 1993-02-09 | 1995-10-01 | Miret Lab | DISPERSING AND INHIBITING COMPOSITIONS OF INCRUSTATION AND / OR CORROSION IN INDUSTRIAL WATER CIRCUITS. |
US5518629A (en) * | 1993-07-29 | 1996-05-21 | Betz Laboratories, Inc. | Methods for controlling scale formation in acqueous systems |
WO2000039359A1 (en) * | 1998-12-29 | 2000-07-06 | Calgon Corporation | Corrosion inhibitor compositions and methods to control metal corrosion in brine systems |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3669901A (en) * | 1970-10-22 | 1972-06-13 | William Bruce Murray | Corrosion inhibitor composition containing zinc, sulfamate, and phosphate ions |
US3794603A (en) * | 1972-01-17 | 1974-02-26 | Sherwin Williams Co | Zn++-benzotriazole-h2so4 corrosioninhibitor |
AU452099B2 (en) * | 1972-08-02 | 1974-08-29 | Applied Chemicals Pty. Limited | Aqueous corrosion inhibiting compositions |
DE2333353C2 (en) * | 1973-06-30 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | Process for preventing corrosion in water-bearing systems and anti-corrosion agents for carrying out the process |
US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
US4042451A (en) * | 1975-08-05 | 1977-08-16 | M&T Chemicals Inc. | Selected stripping of nickel-iron alloys from ferrous substrates |
DK231879A (en) * | 1978-06-05 | 1979-12-06 | Calgon Corp | PROCEDURE FOR CORROSION INHIBITION AND PRODUCT FOR USE IN THE PERFORMANCE OF THE PROCEDURE |
GB2118159B (en) * | 1982-04-20 | 1985-09-04 | Dearborn Chemicals Ltd | The treatment of aqueous systems |
-
1986
- 1986-10-27 CA CA000521449A patent/CA1332138C/en not_active Expired - Lifetime
- 1986-10-29 AU AU64564/86A patent/AU6456486A/en not_active Abandoned
- 1986-10-29 DE DE8686308419T patent/DE3683928D1/en not_active Expired - Lifetime
- 1986-10-29 AT AT86308419T patent/ATE72678T1/en active
- 1986-10-29 ES ES198686308419T patent/ES2038595T3/en not_active Expired - Lifetime
- 1986-10-29 EP EP86308419A patent/EP0225051B1/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8765656B2 (en) | 2006-08-02 | 2014-07-01 | Ch2O Incorporated | Disinfecting/mineral treating composition and methods comprising a chlorite or chlorate salt |
CN110158094A (en) * | 2019-07-11 | 2019-08-23 | 北京中天兰清环境科技有限公司 | A kind of formula and preparation method of the without phosphorus carbon steel corrosion inhibitor of composite efficient |
Also Published As
Publication number | Publication date |
---|---|
DE3683928D1 (en) | 1992-03-26 |
ES2038595T3 (en) | 1993-08-01 |
EP0225051A1 (en) | 1987-06-10 |
CA1332138C (en) | 1994-09-27 |
ATE72678T1 (en) | 1992-03-15 |
AU6456486A (en) | 1987-04-30 |
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