US3133028A - Corrosion inhibition - Google Patents
Corrosion inhibition Download PDFInfo
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- US3133028A US3133028A US9422A US942260A US3133028A US 3133028 A US3133028 A US 3133028A US 9422 A US9422 A US 9422A US 942260 A US942260 A US 942260A US 3133028 A US3133028 A US 3133028A
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- Prior art keywords
- water
- soluble
- corrosion
- zinc
- compounds
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- 238000005260 corrosion Methods 0.000 title claims description 33
- 230000007797 corrosion Effects 0.000 title claims description 33
- 230000005764 inhibitory process Effects 0.000 title description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000004615 ingredient Substances 0.000 claims description 16
- -1 FERROUS METALS Chemical class 0.000 claims description 14
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 22
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 12
- 150000003752 zinc compounds Chemical class 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 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 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 230000000153 supplemental effect Effects 0.000 description 4
- 150000003567 thiocyanates Chemical class 0.000 description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000623377 Terminalia elliptica Species 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- CAKJEGSGMRHDLS-UHFFFAOYSA-N [K].[Cr].[Cr] Chemical compound [K].[Cr].[Cr] CAKJEGSGMRHDLS-UHFFFAOYSA-N 0.000 description 1
- MVJKIOIYFVWOPI-UHFFFAOYSA-N [Zn].NC(N)=S Chemical compound [Zn].NC(N)=S MVJKIOIYFVWOPI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- GNGPZOYIJXYNRV-UHFFFAOYSA-N diazanium 2-sulfanylbutanedioate Chemical compound C(C(S)CC(=O)[O-])(=O)[O-].[NH4+].[NH4+] GNGPZOYIJXYNRV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical class [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical class [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- PNYWWCYVJKNSJY-UHFFFAOYSA-N thiocyanic acid thiourea Chemical compound SC#N.NC(N)=S PNYWWCYVJKNSJY-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
- Ciaims. ⁇ (Cl. 252 -389) This invention relates to the inhibition of corrosion of metals which come into'contact with water as, for-example,
- water-soluble thiourea compounds of the type represented -by' the formula where R, R R and R are each selected from the group consistingof hydrogen, alkali metal, and alkyl radicals containing from 1 to 4.carbon atoms such as methyl, ethyl, propyl, .isopropyl, butyl'and isobutyl. It also has been found'that water-solublethiocarboxylic acids and salts 1 thereof can be utilized as, for example, thioglycolicacid, thiodiglycolicacid'and thiomalic acid and the ammonium and sodium salts thereof.
- water-soluble thiocyanates are thiocyanic acid and the inorganic salts of thiocyanic acid, particularlythealkali-metal thiocyanates, namely, sodium, potassium, ammoniumand lithium thiocyanates.
- Other watersoluble thiocyanate compounds which, in aqueous soluf .20 A greatdealof work has been done in-the 'fieldof' corphates; Water-soluble hexavalent chromium compounds such as sodinm and potassium chromates.anddichromates;
- the present invention is based upon discoveries which result in new and useful corrosion inhibition compositions andfsignificant improvements in regard to inhibition of corrosion of ferrous andother metals through the utilization of suchcompositions.
- hexavalent chromium compounds are, -as' indicated above," well known in the art.” They include, particularly the alkali'metal chromat'es and dichromates such as sodium'chromate, potassium dichromate, ammonium dichromate, and chromium trioxide in their anhydrous and hydrate forms.
- alkali'metal chromat'es and dichromates such as sodium'chromate, potassium dichromate, ammonium dichromate, and chromium trioxide in their anhydrous and hydrate forms.
- concentration in the water of the ingredients utilized'pursuant to the presentinvention are quite variable.
- concentration may range from about 1 to "10,000 ppm, better stillfrom 2to 100 p.p.m., and
- the chemical compounds which are used in conjunction i with the water-soluble hexavalent chromium compounds pursuant to the present invention are water-soluble thio- 5 asNa CrO In the case of the thiocyanates, the thiourea'c'oinpounds and the thiocarboxylic acid compounds,
- the concentratio mayrange" from about 0:01 top.p.m., better still'from 0.0l1toi-25 ppm, and particularly desirably from 0.02 to 10 ppm.
- thewconcentration may'raiige from names to 25 p.p.m., better still from 0.5 to 15 p'.p.m.,-and particularly desirably from'l to 8 ppm. calculated as zinc.
- Example 10 Sodium dichromate 100 Chromic acid (as Cr O 65 Zinc sulfate 25 Ammonium thiocyanate 0.2
- Example 11 Sodium dichromate '1 100 Chromic acid (as Cr O 20 Zinc sulfate 6 Thiourea 0.3
- Example 1 The following table shows the unusual results and Ammonium dichromate 100 synergistic coaction of the ingredients in compositions Ammonium thiocyanate 0- made in accordance with the present invention.
- Example 2 40 It will be seen, from the foregoing table, that hexavalent Potassium dichromate 10o chromium alone in the amount of ppm. as hexavalent Onium thiocyanat; 02 chromium ion caused extensive pitting and showed a cor- Zinc Sulfate ""f'" rosion rate of 10 mils per year. Hexavalent chromium in admixture with trivalent chromium showed moderate Example 3 pitting and a corrosion rate in the range of 12 to 7 mils Potassium dichmmate 100 per year.
- Hexavalent chromium and zinc ions with and Thiourea 2 without certain supplemental agents showed from extensive to some pitting and a corrosion rate of from 10 to Example 4 .4 mils per year.
- the Potassium dichrom 100 addition of as little as 0.02 to 0.05 ppm. of thiocyanate Thiourea 0.2 n is case sodium thiocyanate) or thiourea to 8 ppm.
- a corrosion inhibiting composition useful upon 100 fi g g z gg gzgg 0.2 v addition to water to lnhibit corrosion of ferrous metals m y n in contact with said water said composition consisting Example 7 essentially of the following ingredients in substantially Ammonium dichromate 100 the following parts by weight in relation to each other: Ammomum thloglycolate A member selected from the group con- Example 8 sisting of water-soluble chromates Ammonium dichmmate 100 and dichromates 1 to 10,000 Ammonium thiomalate 0.3 (calculated as I i Na CIO Exam? 9 9 Water-soluble thiocyanate compound 0.01 to 100. Sodium dichromatc 100 Chromic acid (as Cr O 15.6 2.
- a composition in accordance with claim 2 including from 1 to '8 parts of a water-soluble zinc compound 4.
- a corrosion inhibiting composition useful upon addition to water to inhibit corrosion of ferrous metals in contact with said water said composition consisting essentially of the following ingredients in substantially the following parts by Weight in relation to each other:
- V A member selected from the group consisting of water-soluble chrornates and ;dichromates 1 m 10,000
- R, R R and R are each selected from the group consisting of hydrogen, alkali metal, and alkyl" radicals containing from. 1 to 4 carbon atoms r 0.01 to 200.-
- composition in accordance with claim 4 including from 0.5 to 25 parts calculated as zinc.
- a corrosion inhibiting composition useful upon addition to water to inhibit corrosion of ferrous metals in a contact with saidwater said composition consisting essentially of the following ingredients in substantially the following parts by weight in relation to each other: i
- V A member selected from the group consistingof water-s oluble chromates and dichromates 2 to 100 a (calculated as NfizCIO). I Thiourea -4. 0.01 to 25.
- composition useful upon addition to water to inhibit corrosion of ferrous metals incontact with said Water, said composition consisting essentially of the following ingredients in substantially the following parts by weight in relation to each other:
- Hexavalent chromium calculated as Na CrO 1 to 10,000 Water-soluble zinc compound calculated as in zinc ion 0.5 to 20 Ammonium thiocyanate a 0.01 to 200 10.
- the method of retarding the corrosion of a ferrous metal upon contact with water which comprises effecting such contact in the presence of a Water-soluble corrosion inhibitor dissolved in said water, said inhibitor consisting essentially of a 'water-soluble hexavalent chromium compound, a water-soluble zinc compound, and a watersoluble thiocyanate, said ingredients being present in the water in the following amounts in terms of p.p.m.:
- a Water-soluble corrosion inhibitor dissolved in said water, said inhibitor consisting essentially of a water-soluble hexavalent chromium compound, "a water-soluble zinc compound, and thiourea, said ingredients being present in the Water in the following'anrounts in terms of p.p.m.: I
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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)
Description
been mentioned above.
1 j CQRROSION'INHEBITION Kenkere 1. 'Channabasappa, Chicago, 111., assignor to Wright Chemical Corporation, Chicagmlll.
:NoDrawing. Filed Feb. -18, 1950, Ser. No. 9,422
' 11 Ciaims. \(Cl. 252 -389) This invention relates to the inhibition of corrosion of metals which come into'contact with water as, for-example,
in water circulation systems, particularly industrial water systems such as utilize heat exchangers, cooling towers and like installations. While it is; especially concerned with ,the protection against corrosion of ferrous .metals such-as iron and steel, it is alsouseful for inhibiting corrosion of other metals in contact with water, particularly flowing a water, as, for example, copper, copper alloys such as brass ,andbronze, aluminumandaluminumbase.alloys,..couples a of such metals with ferrous metals, and other metals and alloys commonly-used in industrial water systems or Water circulation systems.
rosion inhibition of metals used in water systems where circulating watercomes into contact with such metal sur-v faces. Among the materials utilized. as additives to the water to effect corrosion inhibition of the aforesaid types of metals are water-soluble phosphates of variousitypes including monosodium-phosphate and sodium polyphos- United, States Patent 3,133,028 Patented May 12, 19:64
,. v ce 'cyanates, and/or water-soluble thiourea compounds of the type represented -by' the formula where R, R R and R are each selected from the group consistingof hydrogen, alkali metal, and alkyl radicals containing from 1 to 4.carbon atoms such as methyl, ethyl, propyl, .isopropyl, butyl'and isobutyl. It also has been found'that water-solublethiocarboxylic acids and salts 1 thereof can be utilized as, for example, thioglycolicacid, thiodiglycolicacid'and thiomalic acid and the ammonium and sodium salts thereof.
Among the water-soluble thiocyanates are thiocyanic acid and the inorganic salts of thiocyanic acid, particularlythealkali-metal thiocyanates, namely, sodium, potassium, ammoniumand lithium thiocyanates. Other watersoluble thiocyanate compounds which, in aqueous soluf .20 A greatdealof work has been done in-the 'fieldof' corphates; Water-soluble hexavalent chromium compounds such as sodinm and potassium chromates.anddichromates;
1 and various combinations of ingredients as, for instance,
mixtures of water-soluble trivalent and hexavalent chrov fe'rricyanides, and water-soluble chromates. Typical of 'such'a'pproaches are disclosedin US. Patents Nos. 2,793,- 93 2; 2,887,085 and 2,901,437. While improvement in corrosion inhibition is obtained by'following such and other practices of the priorart, nevertheless not infr e uently problems of scaling and pitting arise and, in addi- ..tion, the matter of cost of the' corrosion inhibiting compositions is a factor of material consideration.
The present invention is based upon discoveries which result in new and useful corrosion inhibition compositions andfsignificant improvements in regard to inhibition of corrosion of ferrous andother metals through the utilization of suchcompositions.
Ithas been discovered that the employment, in con- I junction with water-soluble hexavalent chromium compounds, of certain chemical compounds, hereafter ,de-
scribed, brings aboutmarked improvement in the corrosion inhibition properties of said hexavalent chromium compounds when dissolved in water and said water is in contact with or is circulated'in contact with ferrous metals and other metals in water systems such as have themselves particularly in regard to 'very substantially reduced scaling, which is'one of the serious objections, for
1 example, of theuse of polyphosphates and various other materials heretofore suggested 'as corrosion inhibiting materials, and in regard to substantial absence of pitting Another important advantage resides in the fact that the compounds; mixtures of certain fln'ols, water-soluble zinc compounds, and water-soluble polyphosphates; and mixtures of water-solublepolyphosphates, water-soluble urea compounds.
Ithas also been found to be particularly desirable to employ, in' conjunction with the water-soluble hexavalent chromium compound, one or more water-soluble zinc compounds, particularly zinc compounds such as zinc sulfate,zinc chloride, sodium 'zincate, and zinc oxide and 'zinc carbonate in acid solutions in which they are soluble.
Other water-solublezinc compounds which, in aqueous solution,ion-ize to produce zincions can be utilized. Where the zinc compounds are used, it will be understood that such-will -be selected, in relation to the hexavalent chromium compound or compounds and thiocyanate or thiourea compound, as to be compatible therewith.
With water-soluble hexavalent chromium compounds -are, -as' indicated above," well known in the art." They include, particularly the alkali'metal chromat'es and dichromates such as sodium'chromate, potassium dichromate, ammonium dichromate, and chromium trioxide in their anhydrous and hydrate forms. U l
The ranges "of concentration in the water of the ingredients utilized'pursuant to the presentinvention are quite variable. Thus; in the'case' of the hexavalent chromium compound; the concentration may range from about 1 to "10,000 ppm, better stillfrom 2to 100 p.p.m., and
particularly desirably from 5' to'30 p.p .m., all calculated These improvements manifest v invention makes possible the utilization of reduced concentrations of hexavalent chromium compounds, thereby resulting in savings in cost.
7 The chemical compounds which are used in conjunction i with the water-soluble hexavalent chromium compounds pursuant to the present invention are water-soluble thio- 5 asNa CrO In the case of the thiocyanates, the thiourea'c'oinpounds and the thiocarboxylic acid compounds,
the concentratio mayrange" from about 0:01 top.p.m., better still'from 0.0l1toi-25 ppm, and particularly desirably from 0.02 to 10 ppm. Inthe case of the zinc 'compounds,"'where the same are used, thewconcentration may'raiige from names to 25 p.p.m., better still from 0.5 to 15 p'.p.m.,-and particularly desirably from'l to 8 ppm. calculated as zinc.
It .will. be understood that, if desired,- supplemental ingredients can be added to the compositions of the present invention or to water containing the compositions of the invention, so long as the amounts-or character of such supplemental ingredients are not such as unduly ad'- versely affectthe desired properties of said compositions or water containing the" same. 'ThuS,'f0I"XamP1e,jtri* Mixvalent chromium compounds, phosphates and polyphosphates, and thiols can be added in relatively minor amounts. It is preferred, however, not to utilize said or other supplemental ingredients.
The following examples are illustrative of corrosion inhibiting compositions falling within the scope of the invention. It will be appreciated that other compositions can readily be prepared in the light of the guiding principles and teachings provided herein. All parts listed are by weight.
Example 10 Sodium dichromate 100 Chromic acid (as Cr O 65 Zinc sulfate 25 Ammonium thiocyanate 0.2
Example 11 Sodium dichromate '1 100 Chromic acid (as Cr O 20 Zinc sulfate 6 Thiourea 0.3
Example 1 The following table shows the unusual results and Ammonium dichromate 100 synergistic coaction of the ingredients in compositions Ammonium thiocyanate 0- made in accordance with the present invention.
RECIRCU LATIN G COOLING TOWER Duration of test, days 28 pH range 6.08.0 Chloride as NaCl '1O100O Total hardness 10-1000 Heat exchanger temperature F 70-400 Sulfate as Na2SO4 p.p.m. 10-1500 VI+ III+ II+ Water Corro- Test N0. Orion, Or ion, Zn ion, soluble Type of organic Type of Attack sion p.p.1n. p.p.m. ppm. phosphate, compound, p.p.m. rate,
p.p.m. MPY
20 Extensive pitting. 10 8 do 20 8 Moderate pitting 12 s d 7 3 do 7 8 Extensive pitting. 10 8 Some pitting 5 8 Sullonate, 1.- d 4 8 Citrate, 0.05 do 6 8 Ethylene diamine Moderate pitting 7 gegracetic acid, 8 2 Thi0 cyanate,0.02- Negligible 1 8 1 Thiourea, 0.02 do 1 8 Thiocyanate, 0.05... do 1 8 (Ortho) Some pittin 4 *Mils per year.
Example 2 40 It will be seen, from the foregoing table, that hexavalent Potassium dichromate 10o chromium alone in the amount of ppm. as hexavalent Onium thiocyanat; 02 chromium ion caused extensive pitting and showed a cor- Zinc Sulfate ""f'" rosion rate of 10 mils per year. Hexavalent chromium in admixture with trivalent chromium showed moderate Example 3 pitting and a corrosion rate in the range of 12 to 7 mils Potassium dichmmate 100 per year. Hexavalent chromium and zinc ions with and Thiourea 2 without certain supplemental agents showed from extensive to some pitting and a corrosion rate of from 10 to Example 4 .4 mils per year. In sharp contrast to the above, the Potassium dichrom 100 addition of as little as 0.02 to 0.05 ppm. of thiocyanate Thiourea 0.2 n is case sodium thiocyanate) or thiourea to 8 ppm. Zinc sulfate 40 f eXavalcnt chromium ion, with and without from 2 to E am [e 5 1 ppm. of zinc ion, showed no pitting and a corrosion x 17 rate of less than 1 mil per year. The coaction between Sodium dichromate 100 the hexavalent chromium and the thiocyanate or thiourea, Ammonium thiocyanat 5 in the presence as well as without the presence of the Thiourea zinc ion, demonstrates a highly surprising and effective S9d1um polyphosphate 10 'syllfilgistic-like action, Zinc ulfa 5 What is claimed as new and desired to be protected by Example 6 Letters'Patent of the United States is: 1. A corrosion inhibiting composition useful upon 100 fi g g z gg gzgg 0.2 v addition to water to lnhibit corrosion of ferrous metals m y n in contact with said water, said composition consisting Example 7 essentially of the following ingredients in substantially Ammonium dichromate 100 the following parts by weight in relation to each other: Ammomum thloglycolate A member selected from the group con- Example 8 sisting of water-soluble chromates Ammonium dichmmate 100 and dichromates 1 to 10,000 Ammonium thiomalate 0.3 (calculated as I i Na CIO Exam? 9 9 Water-soluble thiocyanate compound 0.01 to 100. Sodium dichromatc 100 Chromic acid (as Cr O 15.6 2. A corrosion m lbl ll'lg composition useful upon addl- Zinc oxide Q 6.5 tion to water to inhibit corrosion of ferrous metals in Ammonium thiocyanate 0.2 contact with said water, said composition consisting escalculated as zinc.
sentially of the following ingredients in substantially the following parts by weight in relation to each other:
A memberselected from the group consisting of Waterasoluhle chromates and 'dichro'mates 2 to 100 1 (calculated as Na CrO Water-soluble thiocyanate compountL- 0.01 to 25.
3. A composition in accordance with claim 2, including from 1 to '8 parts of a water-soluble zinc compound 4. A corrosion inhibiting composition useful upon addition to water to inhibit corrosion of ferrous metals in contact with said water, said composition consisting essentially of the following ingredients in substantially the following parts by Weight in relation to each other:
V A member selected from the group consisting of water-soluble chrornates and ;dichromates 1 m 10,000
' a (calculated as v V Na CrO A thiourea compound corresponding R\ E /R2 N o-N 12 R;
where R, R R and R are each selected from the group consisting of hydrogen, alkali metal, and alkyl" radicals containing from. 1 to 4 carbon atoms r 0.01 to 200.-
6. A composition in accordance with claim 4, including from 0.5 to 25 parts calculated as zinc.
- 6. A corrosion inhibiting composition useful upon addition to water to inhibit corrosion of ferrous metals in a contact with saidwater, said composition consisting essentially of the following ingredients in substantially the following parts by weight in relation to each other: i
V A member selected from the group consistingof water-s oluble chromates and dichromates 2 to 100 a (calculated as NfizCIO). I Thiourea -4. 0.01 to 25.
- '7.j'A corrosion inhibiting composition useful upon addition to water to inhibit corrosion of ferrous metals incontact with said Water, said composition consisting essentially of the following ingredients in substantially the following parts by weight in relation to each other:
A member selected from the group consisting of water-soluble chromates and dichromates 5 to 30 (calculated as g V Na CrO V Chomic aCid 5 to 30 Thiourea 0.02 to 10 8. A process of protecting ferrous metals against corrosion by water circulated in contact therewith, the step which consists essentially, in adding to the water the following ingredients in the stated concentration in ppm. basedon the water:
' calculated 7 Hex-avalent chromium as Na2CIO4 o Water-soluble thiocyanate compound---" 0.01 to 9. A process of protecting ferrous metals against corrosion by water circulated in contact therewith, the step which consists essentially in adding to the water the following ingredients in the stated concentrations inppm. based on the water: i
Hexavalent chromium calculated as Na CrO 1 to 10,000 Water-soluble zinc compound calculated as in zinc ion 0.5 to 20 Ammonium thiocyanate a 0.01 to 200 10. The method of retarding the corrosion of a ferrous metal upon contact with water which comprises effecting such contact in the presence of a Water-soluble corrosion inhibitor dissolved in said water, said inhibitor consisting essentially of a 'water-soluble hexavalent chromium compound, a water-soluble zinc compound, and a watersoluble thiocyanate, said ingredients being present in the water in the following amounts in terms of p.p.m.:
Hexayalent chromium compound (calculated as Na CrOQ- -l 5 to 30 Zinc compound (calculated as zinc ion) 1 to 8 Thiocyanate 0.02 to 10 11. The method of retarding the corrosion of a ferrous metal upon contact with water which comprises,
effecting such contact in the presence of a Water-soluble corrosion inhibitor dissolved in said water, said inhibitor consisting essentially of a water-soluble hexavalent chromium compound, "a water-soluble zinc compound, and thiourea, said ingredients being present in the Water in the following'anrounts in terms of p.p.m.: I
Hex-avalent chromium compound (calculated as Na CrO 5to 30 Zinc compound (calculated as zinc ion) lto 8' Thiourea r 0.02 to 10 References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A CORROSION INHIBITING COMPOSITION USEFUL UPON ADDITION TO WATER TO INHIBIT CORROSION OF FERROUS METALS IN CONTACT WITH SAID WATER, SAID COMPOSITION CONSISTING ESSENTIALLY OF THE FOLLOWING INGREDIENTS IN SUBSTANTIALLY THE FOLLOWING PARTS BY WEIGHT IN RELATION TO EACH OTHER:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9422A US3133028A (en) | 1960-02-18 | 1960-02-18 | Corrosion inhibition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9422A US3133028A (en) | 1960-02-18 | 1960-02-18 | Corrosion inhibition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3133028A true US3133028A (en) | 1964-05-12 |
Family
ID=21737547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US9422A Expired - Lifetime US3133028A (en) | 1960-02-18 | 1960-02-18 | Corrosion inhibition |
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| US (1) | US3133028A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288684A (en) * | 1963-11-19 | 1966-11-29 | Pennsalt Chemicals Corp | Liquid mixtures of thioureas |
| US3513031A (en) * | 1967-07-27 | 1970-05-19 | Solomon Zaromb | Gas-depolarized cell with aluminum anode |
| US4541946A (en) * | 1981-03-12 | 1985-09-17 | Standard Oil Company | Corrosion inhibitor for amine gas sweetening systems |
| WO1986004634A1 (en) * | 1985-02-04 | 1986-08-14 | The Dow Chemical Company | Corrosion inhibitor for high density brines |
| US4728446A (en) * | 1984-07-31 | 1988-03-01 | The Dow Chemical Company | Corrosion inhibitor for brines |
| US4756874A (en) * | 1986-12-22 | 1988-07-12 | General Electric Company | Minimization of radioactive material deposition in water-cooled nuclear reactors |
| AU576585B2 (en) * | 1984-07-31 | 1988-09-01 | Dow Chemical Company, The | Corrosion inhibitor containing zinc and thiocyanate and brine |
| US5843373A (en) * | 1997-08-22 | 1998-12-01 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
| US5843299A (en) * | 1997-08-22 | 1998-12-01 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
| WO1999010444A1 (en) * | 1997-08-22 | 1999-03-04 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
| US6036888A (en) * | 1997-08-22 | 2000-03-14 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
| US6187227B1 (en) | 1998-06-02 | 2001-02-13 | Betzdearborn | Thiacrown ether compound corrosion inhibitors for alkanolamine units |
| EP3936790A1 (en) * | 2020-07-08 | 2022-01-12 | Vaillant GmbH | Catalytic alkane degradation |
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|---|---|---|---|---|
| US3288684A (en) * | 1963-11-19 | 1966-11-29 | Pennsalt Chemicals Corp | Liquid mixtures of thioureas |
| US3513031A (en) * | 1967-07-27 | 1970-05-19 | Solomon Zaromb | Gas-depolarized cell with aluminum anode |
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| US4728446A (en) * | 1984-07-31 | 1988-03-01 | The Dow Chemical Company | Corrosion inhibitor for brines |
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| US5985179A (en) * | 1997-08-22 | 1999-11-16 | Betzdearborn, Inc. | Corrosion inhibitor for alkanolamine units |
| US6036888A (en) * | 1997-08-22 | 2000-03-14 | Betzdearborn Inc. | Corrosion inhibitor for alkanolamine units |
| US6187227B1 (en) | 1998-06-02 | 2001-02-13 | Betzdearborn | Thiacrown ether compound corrosion inhibitors for alkanolamine units |
| EP3936790A1 (en) * | 2020-07-08 | 2022-01-12 | Vaillant GmbH | Catalytic alkane degradation |
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