EP0225051A1 - Behandlung von wässrigen Systemen - Google Patents
Behandlung von wässrigen Systemen Download PDFInfo
- Publication number
- EP0225051A1 EP0225051A1 EP86308419A EP86308419A EP0225051A1 EP 0225051 A1 EP0225051 A1 EP 0225051A1 EP 86308419 A EP86308419 A EP 86308419A EP 86308419 A EP86308419 A EP 86308419A EP 0225051 A1 EP0225051 A1 EP 0225051A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- acid
- chelant
- carboxylic acid
- weight
- 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.)
- Granted
Links
- 239000013522 chelant Substances 0.000 claims abstract description 36
- 150000003751 zinc Chemical class 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- -1 allyl carboxylic acid Chemical class 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 238000005260 corrosion Methods 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 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
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical group OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 229920003145 methacrylic acid copolymer Polymers 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
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 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 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 2
- 229940050176 methyl chloride Drugs 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-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
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 235000009529 zinc sulphate Nutrition 0.000 claims description 2
- FOUZISDNESEYLX-UHFFFAOYSA-N 2-(2-hydroxyethylazaniumyl)acetate Chemical compound OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 claims 1
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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
- XLJGIXLDEYIALO-UHFFFAOYSA-N 2-(carboxymethylamino)-4-hydroxybutanoic acid Chemical compound OCCC(C(O)=O)NCC(O)=O XLJGIXLDEYIALO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 239000003446 ligand Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 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
- 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
- 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
- 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
- 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
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 239000011976 maleic acid 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
- 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
- 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
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 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.
- a method of treating an aqueous system which comprises adding thereto a zinc salt, a chelant 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.
- 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" by 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.
- chelants which can be used in the method of the present invention are generally compounds with a nitrogen ligand which are effective chelants for iron. Usually, these chelants will also possess a carboxylic acid group.
- a preferred group of chelants possesses the formula R3 - - - CR2 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 -.
- 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 faciliate the formulation of compositions, as well as N,N-di(2-hydroxyethyl) glycine, N-hydroxyethyl N,N' ,N'-ethylenediamine triacetic acid and 2-hydroxyethyl iminodiacetic acid.
- Ethylenediamine tetraacetic acid and diethylene triamine pentaacetic acid can also be mentioned although they are less preferred since they do not contain
- 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 phophorus 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 phophorus 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.
- test 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.
- Examples 15 - 34 were carried out at 54°C.
- 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.
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86308419T ATE72678T1 (de) | 1985-10-29 | 1986-10-29 | Behandlung von waessrigen systemen. |
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 |
|---|---|
| EP0225051A1 true EP0225051A1 (de) | 1987-06-10 |
| EP0225051B1 EP0225051B1 (de) | 1992-02-19 |
Family
ID=26289944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86308419A Expired EP0225051B1 (de) | 1985-10-29 | 1986-10-29 | Behandlung von wässrigen Systemen |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0225051B1 (de) |
| AT (1) | ATE72678T1 (de) |
| AU (1) | AU6456486A (de) |
| CA (1) | CA1332138C (de) |
| DE (1) | DE3683928D1 (de) |
| ES (1) | ES2038595T3 (de) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0277412A1 (de) * | 1987-01-23 | 1988-08-10 | W.R. Grace & Co.-Conn. | Korrosionsinhibierung von Eisenmetallen |
| EP0311192A1 (de) * | 1987-10-05 | 1989-04-12 | Calgon Corporation | Verfahren zur Beeinflussung der Korrosion bei hohem pH-Wert |
| EP0364030A1 (de) * | 1988-10-11 | 1990-04-18 | Calgon Corporation | Synergistische Gemische und Verfahren zur Verhinderung der Korrosion an Kohlenstoffhaltigem Stahl in wässrigen Systemen |
| US5171477A (en) * | 1991-05-31 | 1992-12-15 | W. R. Grace & Co.-Conn. | Corrosion inhibition in chelant solutions |
| ES2059273A1 (es) * | 1993-02-09 | 1994-11-01 | Miret Lab | Composiciones dispersantes e inhibidoras de la incrustacion y/o de la corrosion en circuitos de aguas industriales. |
| EP0714859A3 (de) * | 1994-11-29 | 1997-05-07 | Betz Europ Inc | Verfahren zur Kesselsteinbekämpfung in wässrigen Systemen |
| WO2000039359A1 (en) * | 1998-12-29 | 2000-07-06 | Calgon Corporation | Corrosion inhibitor compositions and methods to control metal corrosion in brine systems |
| US8513176B2 (en) | 2006-08-02 | 2013-08-20 | Ch2O Incorporated | Disinfecting and mineral deposit eliminating composition and methods |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158094A (zh) * | 2019-07-11 | 2019-08-23 | 北京中天兰清环境科技有限公司 | 一种复合型高效无磷碳钢缓蚀剂的配方及制备方法 |
Citations (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 |
| DE2338352A1 (de) * | 1972-08-02 | 1974-02-28 | Applied Chem Pty Ltd | Korrosionsschutzmittel zur inhibierung der wasserkorrosion |
| AT332699B (de) * | 1973-06-30 | 1976-10-11 | Bayer Ag | Mittel zur verhinderung von korrosion und steinansatz in wasserfuhrenden systemen |
| DE2635295A1 (de) * | 1975-08-05 | 1977-02-24 | M & T Chemicals Inc | Verfahren und zusammensetzung zur entfernung von nickel-, nickel/eisen- und nickel/eisen/kobalt-ueberzuegen von metallsubstraten |
| US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
| EP0006065A2 (de) * | 1978-06-05 | 1979-12-12 | Calgon Corporation | Zusammensetzung und Verfahren zum Korrosionsschutz |
| DE3314008A1 (de) * | 1982-04-20 | 1983-10-20 | Dearborn Chemicals Ltd., Widnes, Cheshire | Verfahren zur korrosionsbekaempfung in waessrigen systemen, dafuer geeignete zusammensetzung und deren verwendung |
-
1986
- 1986-10-27 CA CA000521449A patent/CA1332138C/en not_active Expired - Lifetime
- 1986-10-29 AT AT86308419T patent/ATE72678T1/de active
- 1986-10-29 ES ES198686308419T patent/ES2038595T3/es not_active Expired - Lifetime
- 1986-10-29 AU AU64564/86A patent/AU6456486A/en not_active Abandoned
- 1986-10-29 DE DE8686308419T patent/DE3683928D1/de not_active Expired - Lifetime
- 1986-10-29 EP EP86308419A patent/EP0225051B1/de not_active Expired
Patent Citations (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 |
| DE2338352A1 (de) * | 1972-08-02 | 1974-02-28 | Applied Chem Pty Ltd | Korrosionsschutzmittel zur inhibierung der wasserkorrosion |
| AT332699B (de) * | 1973-06-30 | 1976-10-11 | Bayer Ag | Mittel zur verhinderung von korrosion und steinansatz in wasserfuhrenden systemen |
| US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
| DE2635295A1 (de) * | 1975-08-05 | 1977-02-24 | M & T Chemicals Inc | Verfahren und zusammensetzung zur entfernung von nickel-, nickel/eisen- und nickel/eisen/kobalt-ueberzuegen von metallsubstraten |
| EP0006065A2 (de) * | 1978-06-05 | 1979-12-12 | Calgon Corporation | Zusammensetzung und Verfahren zum Korrosionsschutz |
| DE3314008A1 (de) * | 1982-04-20 | 1983-10-20 | Dearborn Chemicals Ltd., Widnes, Cheshire | Verfahren zur korrosionsbekaempfung in waessrigen systemen, dafuer geeignete zusammensetzung und deren verwendung |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0277412A1 (de) * | 1987-01-23 | 1988-08-10 | W.R. Grace & Co.-Conn. | Korrosionsinhibierung von Eisenmetallen |
| EP0311192A1 (de) * | 1987-10-05 | 1989-04-12 | Calgon Corporation | Verfahren zur Beeinflussung der Korrosion bei hohem pH-Wert |
| AU619764B2 (en) * | 1987-10-05 | 1992-02-06 | Calgon Corporation | Method of controlling corrosion at high ph |
| EP0364030A1 (de) * | 1988-10-11 | 1990-04-18 | Calgon Corporation | Synergistische Gemische und Verfahren zur Verhinderung der Korrosion an Kohlenstoffhaltigem Stahl in wässrigen Systemen |
| US5171477A (en) * | 1991-05-31 | 1992-12-15 | W. R. Grace & Co.-Conn. | Corrosion inhibition in chelant solutions |
| ES2059273A1 (es) * | 1993-02-09 | 1994-11-01 | Miret Lab | Composiciones dispersantes e inhibidoras de la incrustacion y/o de la corrosion en circuitos de aguas industriales. |
| EP0714859A3 (de) * | 1994-11-29 | 1997-05-07 | Betz Europ Inc | Verfahren zur Kesselsteinbekämpfung in wässrigen Systemen |
| WO2000039359A1 (en) * | 1998-12-29 | 2000-07-06 | Calgon Corporation | Corrosion inhibitor compositions and methods to control metal corrosion in brine systems |
| US8513176B2 (en) | 2006-08-02 | 2013-08-20 | Ch2O Incorporated | Disinfecting and mineral deposit eliminating composition and methods |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3683928D1 (de) | 1992-03-26 |
| ATE72678T1 (de) | 1992-03-15 |
| CA1332138C (en) | 1994-09-27 |
| ES2038595T3 (es) | 1993-08-01 |
| AU6456486A (en) | 1987-04-30 |
| EP0225051B1 (de) | 1992-02-19 |
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