US3147244A - Composition for treating materials - Google Patents
Composition for treating materials Download PDFInfo
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- US3147244A US3147244A US100829A US10082961A US3147244A US 3147244 A US3147244 A US 3147244A US 100829 A US100829 A US 100829A US 10082961 A US10082961 A US 10082961A US 3147244 A US3147244 A US 3147244A
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- Prior art keywords
- solution
- metal
- acid
- total solution
- inhibitor
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 18
- 239000000463 material Substances 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000009972 noncorrosive effect Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 15
- -1 iron and steel Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/164—Organic compounds containing a carbon-carbon triple bond
Definitions
- aqueous acid solutions are utilized for removing scale or film from metallic surfaces, as in de-scaling, boiler line tie-liming, and cleaning refinery equipment and oil wells.
- aliphatic hydrocarbon radicals coming within the meaning of R are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl, nonadecyl, eiocosyl, heneicosyl, and docosyl. It is preferred that this aliphatic hydrocarbon radical have from about 12 to 18 carbon atoms.
- aliphatic hydrocarbon radicals coming within the meaning of R are methyl, ethyl, and propyl.
- radicals coming within the meaning of the letter X are iodide, bromide, chloride, and fluoride. It is preferred that chloride be utilized.
- the aliphatic hydrocarbon radical R may be derived from certain naturally occurring fats and oils, such as soy bean oil, coconut oil, tallow and the like. Tallow ordinarily comprises a mixture of the following aliphatic radicals: dodecyl, tetradecyl, tetradecenyl, hexadecyl, hexadecenyl, octadecyl, octadecenyl, octadecadienyl, and eicosyl.
- Coconut oil or cocoa ordinarily comprises a mixture of hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, and octadecadienyl radicals.
- Soy bean oil or soya ordinarily comprises a mixture of hexadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl and eicosyl radicals.
- acids may be used with these quaternary ammonium compounds such as sulfuric, hydrochloric, phosphoric, sulfamic, and citric acids. It has been found that sulfuric and hydrochloric acids are particularly useful. Acid concentrations may vary greatly, although dilute aqueous acid solutions are usually used. Concentration of the acid solution will ordinarily range from about 2 to about 20% by weight.
- concentration of these quaternary ammonium compounds in the metal cleaning composition also has wide variation. However, it is preferred that the concentration be from about 0.01 to 2.0 weight percent, based on total solution. Optimum concentration of the inhibiting compound has been found to range from about 0.1 to about 0.3 weight percent, based on total solution.
- dibutylthiourea may be added to the acid and quaternary ammonium compound.
- good results are obtained with the quaternary ammonium compound and dibutylthiourea in an aqueous acid solution.
- Example I Clean, weighed mild steel coupons were exposed to two solutions, one with the inhibitor and one without the inhibitor, for six hours. After the test period was completed, the coupons were removed from the acid solution, dried, cleaned and then reweighed. The corrosion rate of the coupons was calculated in pounds per square foot per day.
- a 15% hydrochloric acid solution was utilized for both solutions.
- 0.25 weight percent, based on total solution, of dimethyl dodecyl propargyl ammonium chloride was added at 200 F.
- the corrosion rate was 7.9 pounds per square foot per day, whereas the inhibited solution showed a corrosion rate of only .0305 pound per square foot per day. 1
- Example 11 1 Test procedures were the same as in Example I, except that 0.3% FeCl was added to both acid solutions. The corrosion rate without the inhibitor was 8.25 pounds per square foot per day whereas with the inhibitor, the corrosion rate was 0.056 pound per square foot per day.
- Example III Test procedures were the same as previously described, except that a 15% H SO acid solution was used.
- the corrosion inhibitor added was dimethyl, dodecyl propargyl ammonium chloride, the concentration being 0.3 weight percent, based on total solution.
- the corrosion rate without the inhibitor was 2.52 pounds per square foot per day, whereas the corrosion rate with the inhibitor was .099 pound per square foot per day.
- Example IV The procedure followed here was the same as in Example III, except the inhibitor contained 3 parts of the quaternary ammonium compound and one part dibutylthiourea.
- the corrosion rate without the inhibitor was 2.52 pounds per square foot per day whereas with the inhibitor, including the quaternary and dibutylthiourea, the corrosion rate was .0169 pound per square foot per day.
- Example V Test procedures were the same as before, except the acid solution was 15% hydrochloric acid.
- One of the acid solutions contained 0.25 weight percent, based on total solution, of dimethyl octadecyl propargyl ammonium chloride. With the inhibitor, the corrosion rate was .428 pound per square foot per day and without the inhibitor, the corrosion rate was 7.9 pounds per square foot per day.
- Example VI Test procedures were the same as in Example V, except that 0.3% FeCl was added to each of the acid solutions. With the inhibitor, the corrosion rate was .590 pound per square foot per day, whereas without the inhibitor, the corrosion rate was 8.25 pounds per square foot per day.
- a substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and about 0.01 to 2.0% by weight based on total solution, of a compound having the general formula:
- R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms
- R is an aliphatic hydrocarbon radical having from 1 to 3 carbon atoms
- X is a halide
- a substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and about 0.01 to 2.0% by weight based on total solution, of a compound having the formula:
- R is an aliphatic hydrocarbon radical having from about 12 to 18 carbon atoms.
- a substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and from about 0.01 to 2.0% by weight, based on total solution, of dimethyl dodecyl propargyl ammonium chloride.
- aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids and about 0.01 to 2.0% by weight based on total solution, of a compound having the general formula:
- R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms
- R is an aliphatic hydrocarbon radical having from about 1 to 3 carbon atoms
- X is a halide
- aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids and about 0.01 to 2.0% by weight based on total solution, of dimethyl dodecyl propargyl ammonium chloride.
- a substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight, based on total solution, of sulfuric acid, and about 0.01 to 2.0% by weight, based on total solution, of a compound having the general formula:
- R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms
- R is an aliphatic hydrocarbon radical having from about 1 to 3 carbon atoms
- X is a halide
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
2 5 2 1 4 8 CROSS REFERENCE EXAMlNER United States Patent 0 3,147,244 COMPOSITION FOR TREATING MATERIALS Byron E. Marsh, Brookfield, Eric Jungermann, La Grange, and Charles E. Tippett, Chicago, 111., assignors t0 Armour and Company, Chicago, 111., a corporation of Delaware No Drawing. Filed Apr. 5, 1961, Ser. No. 100,829 7 Claims. (Cl. 252-136) This invention relates to compositions for treating metals and to processes for treating metallic surfaces with such compositions.
It is well-known that aqueous acid solutions are utilized for removing scale or film from metallic surfaces, as in de-scaling, boiler line tie-liming, and cleaning refinery equipment and oil wells.
For example, in the working of metals, particularly iron and steel, a scale or oxide forms on the exterior of the metal. So, it becomes necessary to clean the scale or oxide from the surface. In order to accomplish this, it has been the practice to treat the metal with an acid solution, such as hydrochloric, phosphoric, sulfuric, sulfamic and citric acids, although others are also commonly used. This method of cleaning metal surfaces, commonly called pickling, has been practiced not only on ferrous metals, but also on non-ferrous metals, such as aluminum, zinc, brass, etc.
Although the acid solution performs an adequate job of cleaning metal surfaces, it has been a problem that the cleaned metal surface becomes subject to corrosive attack from the acid.
It is therefore an object of this invention to provide a metal cleaning composition which is substantially noncorrosive to metals.
It is a further object of this invention to provide a process for cleaning metals, which process is effective but substantially non-corrosive to the metal being cleaned.
It is a further object of this invention to provide a metal cleaning composition which will act effectively in separating coatings and films from the metal surface While at the same time avoiding corrosive action on the metal.
It is a further object of this invention to provide a metal cleaning composition which is easily adaptable to industrial metal cleaning operations.
Further objects and purposes of this invention will become obvious as the specification proceeds.
We have now discovered new, substantially non-corrosive metal cleaning compositions which include essentially a quaternary ammonium compound having the general wherein R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms, R is an aliphatic hydrocarbon radical having from 1 to 3 carbon atoms, and X is a halide. These compounds are most effective in acid solutions.
Examples of aliphatic hydrocarbon radicals coming within the meaning of R are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl, nonadecyl, eiocosyl, heneicosyl, and docosyl. It is preferred that this aliphatic hydrocarbon radical have from about 12 to 18 carbon atoms.
Examples of aliphatic hydrocarbon radicals coming within the meaning of R are methyl, ethyl, and propyl.
3,147,244 Patented Sept. 1, 1964 ice It is preferred that this aliphatic hydrocarbon radical have one carbon atom.
Examples of radicals coming within the meaning of the letter X are iodide, bromide, chloride, and fluoride. It is preferred that chloride be utilized.
Mixtures of the above described compound may readily be used in the present invention. The aliphatic hydrocarbon radical R may be derived from certain naturally occurring fats and oils, such as soy bean oil, coconut oil, tallow and the like. Tallow ordinarily comprises a mixture of the following aliphatic radicals: dodecyl, tetradecyl, tetradecenyl, hexadecyl, hexadecenyl, octadecyl, octadecenyl, octadecadienyl, and eicosyl. Coconut oil or cocoa ordinarily comprises a mixture of hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, and octadecadienyl radicals. Soy bean oil or soya ordinarily comprises a mixture of hexadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl and eicosyl radicals.
Many acids may be used with these quaternary ammonium compounds such as sulfuric, hydrochloric, phosphoric, sulfamic, and citric acids. It has been found that sulfuric and hydrochloric acids are particularly useful. Acid concentrations may vary greatly, although dilute aqueous acid solutions are usually used. Concentration of the acid solution will ordinarily range from about 2 to about 20% by weight.
The concentration of these quaternary ammonium compounds in the metal cleaning composition also has wide variation. However, it is preferred that the concentration be from about 0.01 to 2.0 weight percent, based on total solution. Optimum concentration of the inhibiting compound has been found to range from about 0.1 to about 0.3 weight percent, based on total solution.
In our non-corrosive process for treating, metals we contact the metal surface to be cleaned with the quaternary ammonium compounds above described. An aqueous solution of any of these compounds may be passed against the metal by washing, spraying or brushing, thus to clean the metal while at the same time avoiding corrosion and the formation of objectionable films, we find that the process is most effective when the treating solution is an aqueous acid solution of the special quaternary ammonium compound.
We have further found that dibutylthiourea may be added to the acid and quaternary ammonium compound. For example, good results are obtained with the quaternary ammonium compound and dibutylthiourea in an aqueous acid solution.
The following examples more fully illustrate the in vention, but it is not intended that the invention be limited to the exact procedures or concentrations utilized. Rather, it is intended that all equivalents obvious to those skilled in the art be included within the scope of the invention.
Example I Clean, weighed mild steel coupons were exposed to two solutions, one with the inhibitor and one without the inhibitor, for six hours. After the test period was completed, the coupons were removed from the acid solution, dried, cleaned and then reweighed. The corrosion rate of the coupons was calculated in pounds per square foot per day.
A 15% hydrochloric acid solution was utilized for both solutions. In the inhibited solution, 0.25 weight percent, based on total solution, of dimethyl dodecyl propargyl ammonium chloride was added at 200 F. In the uninhibited solution, the corrosion rate was 7.9 pounds per square foot per day, whereas the inhibited solution showed a corrosion rate of only .0305 pound per square foot per day. 1
Example 11 1 Test procedures were the same as in Example I, except that 0.3% FeCl was added to both acid solutions. The corrosion rate without the inhibitor was 8.25 pounds per square foot per day whereas with the inhibitor, the corrosion rate was 0.056 pound per square foot per day.
Example III Test procedures were the same as previously described, except that a 15% H SO acid solution was used. The corrosion inhibitor added was dimethyl, dodecyl propargyl ammonium chloride, the concentration being 0.3 weight percent, based on total solution. The corrosion rate without the inhibitor was 2.52 pounds per square foot per day, whereas the corrosion rate with the inhibitor was .099 pound per square foot per day.
Example IV The procedure followed here was the same as in Example III, except the inhibitor contained 3 parts of the quaternary ammonium compound and one part dibutylthiourea. The corrosion rate without the inhibitor was 2.52 pounds per square foot per day whereas with the inhibitor, including the quaternary and dibutylthiourea, the corrosion rate was .0169 pound per square foot per day.
Example V Test procedures were the same as before, except the acid solution was 15% hydrochloric acid. One of the acid solutions contained 0.25 weight percent, based on total solution, of dimethyl octadecyl propargyl ammonium chloride. With the inhibitor, the corrosion rate was .428 pound per square foot per day and without the inhibitor, the corrosion rate was 7.9 pounds per square foot per day.
Example VI Test procedures were the same as in Example V, except that 0.3% FeCl was added to each of the acid solutions. With the inhibitor, the corrosion rate was .590 pound per square foot per day, whereas without the inhibitor, the corrosion rate was 8.25 pounds per square foot per day.
Now that the invention has been described, we claim:
1. A substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and about 0.01 to 2.0% by weight based on total solution, of a compound having the general formula:
wherein R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms, R is an aliphatic hydrocarbon radical having from 1 to 3 carbon atoms, and X is a halide.
2. A substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and about 0.01 to 2.0% by weight based on total solution, of a compound having the formula:
wherein R is an aliphatic hydrocarbon radical having from about 12 to 18 carbon atoms.
3. A substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids, and from about 0.01 to 2.0% by weight, based on total solution, of dimethyl dodecyl propargyl ammonium chloride.
4. In a process for cleaning metal surfaces, the step of contacting the metal surface with an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids and about 0.01 to 2.0% by weight based on total solution, of a compound having the general formula:
wherein R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms, R is an aliphatic hydrocarbon radical having from about 1 to 3 carbon atoms, and X is a halide.
5. In a process for cleaning metal surfaces, the step of contacting the metal surface with an aqueous solution of about 2 to 20% by weight based on total solution, of an acid selected from the group consisting of sulfuric, phosphoric, hydrochloric, sulfamic and citric acids and about 0.01 to 2.0% by weight based on total solution, of dimethyl dodecyl propargyl ammonium chloride.
6. A substantially non-corrosive metal cleaning composition comprising an aqueous solution of about 2 to 20% by weight, based on total solution, of sulfuric acid, and about 0.01 to 2.0% by weight, based on total solution, of a compound having the general formula:
formula:
| RN-0Hz-GE0H X- wherein R is an aliphatic hydrocarbon radical having from about 8 to 22 carbon atoms, R is an aliphatic hydrocarbon radical having from about 1 to 3 carbon atoms, and X is a halide.
References Cited in the file of this patent UNITED STATES PATENTS 2,994,644 Wachter Aug. 1, 1961 3,047,510 Cizek July 31, 1962 FOREIGN PATENTS 858,719 Great Britain Ian. 11, 1961 OTHER REFERENCES Bolle et al.: Chemical Abstracts, Preparation of Quaternary Ammonium Derivatives (1955), page 10, 921b. Faster et al.: Acetylenic Corrosion Inhibitors, Ind. and Eng. Chem., volume 51, No. 7, July 1959, pages 825-828.
Claims (1)
1. A SUBSTANTIALLY NON-CORROSIVE METAL CLEANING COMPOSITION COMPRISING AN AQUEOUS SOLUTION OF ABOUT 2 TO 20% BY WEIGHT BASED ON TOTAL SOLUTION, OF AN ACID SELECTED FROM THE GROUP CONSISTING OF SULFURIC, PHOSPHORIC, HYDROCHLORIC, SULFAMIC AND CITRIC ACIDS, AND ABOUT 0.01 TO 2.0% BY WEIGHT BASED ON TOTAL SOLUTION, OF A COMPOUND HAVING THE GENERAL FORMULA:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US100829A US3147244A (en) | 1961-04-05 | 1961-04-05 | Composition for treating materials |
| GB13041/62A GB951729A (en) | 1961-04-05 | 1962-04-04 | Improved composition and process for treating metals |
| FR7377A FR1319135A (en) | 1961-04-05 | 1962-04-05 | Composition for metal processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US100829A US3147244A (en) | 1961-04-05 | 1961-04-05 | Composition for treating materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3147244A true US3147244A (en) | 1964-09-01 |
Family
ID=22281747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US100829A Expired - Lifetime US3147244A (en) | 1961-04-05 | 1961-04-05 | Composition for treating materials |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3147244A (en) |
| FR (1) | FR1319135A (en) |
| GB (1) | GB951729A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3260673A (en) * | 1964-01-27 | 1966-07-12 | Monsanto Co | Corrosion inhibited phosphoric acid composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388206A (en) * | 1981-12-01 | 1983-06-14 | Gaf Corporation | Corrosion inhibitors |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858719A (en) * | 1957-04-12 | 1961-01-11 | Schering Ag | New quaternary ammonium compounds and a process for their manufacture |
| US2994644A (en) * | 1958-03-03 | 1961-08-01 | Phillips Petroleum Co | Purification and drying of liquids |
| US3047510A (en) * | 1957-06-05 | 1962-07-31 | Armour & Co | Corrosion inhibiting compositions and process |
-
1961
- 1961-04-05 US US100829A patent/US3147244A/en not_active Expired - Lifetime
-
1962
- 1962-04-04 GB GB13041/62A patent/GB951729A/en not_active Expired
- 1962-04-05 FR FR7377A patent/FR1319135A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858719A (en) * | 1957-04-12 | 1961-01-11 | Schering Ag | New quaternary ammonium compounds and a process for their manufacture |
| US3047510A (en) * | 1957-06-05 | 1962-07-31 | Armour & Co | Corrosion inhibiting compositions and process |
| US2994644A (en) * | 1958-03-03 | 1961-08-01 | Phillips Petroleum Co | Purification and drying of liquids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3260673A (en) * | 1964-01-27 | 1966-07-12 | Monsanto Co | Corrosion inhibited phosphoric acid composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB951729A (en) | 1964-03-11 |
| FR1319135A (en) | 1963-02-22 |
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