US3434973A - Pyrylium salts as pickling inhibitors - Google Patents
Pyrylium salts as pickling inhibitors Download PDFInfo
- Publication number
- US3434973A US3434973A US561758A US3434973DA US3434973A US 3434973 A US3434973 A US 3434973A US 561758 A US561758 A US 561758A US 3434973D A US3434973D A US 3434973DA US 3434973 A US3434973 A US 3434973A
- Authority
- US
- United States
- Prior art keywords
- pickling
- pyrylium salts
- triphenylpyrylium
- tetrachloroferrate
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005554 pickling Methods 0.000 title claims description 19
- 239000003112 inhibitor Substances 0.000 title claims description 10
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 title description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- AGOUUEWPLMNUJL-UHFFFAOYSA-N 2,4,6-triphenylpyrylium Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 AGOUUEWPLMNUJL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LLXFXZZMORASIB-UHFFFAOYSA-N 2,3,4-triphenylpyrylium Chemical compound C1=CC=CC=C1C1=CC=[O+]C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 LLXFXZZMORASIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium alkylarylsulfonates Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
Definitions
- This invention relates to pyrylium salts as picking inhibitors for iron and steel.
- the invention also pertains to pickling compositions containing the aforesaid pyrylium salts.
- triarylpyrylium salts wherein the structure admits of a planar configuration. Accordingly the triarylpyrylium salt should be free of large or bulky groups which might prevent the molecule from assuming a planar arrangement. It is our opinion that such substituents hinder adsorption of the inhibitor to the freshly exposed metal surface.
- Triphenylpyrylium tetrachloroferrate is an example of a preferred arylpyrylium salt. It can be obtained by the reaction of benzaldehyde with acetophenone using an acidic condensing agent. For details of the preparation reference is made to the aforecited US. patent.
- the 2,4,6-triphenylpyrylium tetrachloroferrate is unusual in that it provides practical inhibition at rem-arkably low concentrations. In fact it affords excellent protection when formulated in a pickling bath at concentrations as low as 0.02% by weight or less.
- the practical range for the additive is from about 0.01% to about 0.02%. It is effective in both sulfuric and hydrochloric acid, the two most commonly used pickling bath acids.
- the 2,4,6-triphenylpyrylium tetrachloroferrate it is conveniently employed in the form of a concentrate formulation containing from about 10 to 20% of the inhibitor, about 20% of a detergent such as a alkyl-phenolpolyether-alcohol, about 1 to 2% of concentrated hydrochloric acid and about 69 to 58% water.
- a typical formulation is as follows in which the components are on a weight percent basis:
- the detergents used in pickling baths are not particularly critical and any number of types and kinds can be used.
- a pickling bath composition suitable for use with iron and steel consisting essentially of an aqueous solution of acid selected from the class consisting of sulfuric and hydrochloric and as a pickling inhibitor 2,4,6-triphenylpyrylium tetrachloroferrate in the concentration of 0.01% about 0.02% by weight.
- a method of inhibiting acid attack in steel and iron pickling baths which comprises exposing the fresh metal surface to the composition of claim 1.
- An inhibitor concentrate formulation consisting essentially of 2,4,6-triphenylpyrylium tetrachloroferrate of the following ingredients by weight:
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
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3,434,973 Patented Mar. 25, "1969 This invention relates to pyrylium salts as picking inhibitors for iron and steel. The invention also pertains to pickling compositions containing the aforesaid pyrylium salts.
In the pickling art various materials, commonly organic compounds, are dispersed in the acid cleaning solution in order to retard corrosion of the underlying metal while at the same time not materially afiecting the rate of attack on the scale. Inhibitors used in sulfuric acid pickling baths reduce metal attack substantially but not completely thereby permitting suliicient hydrogen evolution to effect dislodging of the scale and rust from the surface. In hydrochloric acid pickling and in all acid cleaning applications for that matter maximum inhibition of metal dissolution commensurate with reasonably effective scale removal is always a desideratum.
The theory generally advanced to explain the action of pickling inhibitors supposes formation of an adsorbed or chemisorbed layer on the newly bared metal surfaces thereby preventing attack -by the acid bath.
With a view to obtaining improvements in pickling inhibitors we have discovered that certain pyrylium salts are particularly effective in this capacity and the provision of such materials and their use as pickling agents con-= stitutes the principal objects and purposes of the invention. Other objects and purposes will become apparent subsequently.
'Pyrylium salts are known chemical entities the description and preparation of which are set forth in the chemical and technical literature. An especially detailed account on their synthesis can be found in U.S. Patent 3,250,615.
In practicing the invention we have achieved excellent corrosion inhibition when using triarylpyrylium salts wherein the structure admits of a planar configuration. Accordingly the triarylpyrylium salt should be free of large or bulky groups which might prevent the molecule from assuming a planar arrangement. It is our opinion that such substituents hinder adsorption of the inhibitor to the freshly exposed metal surface.
Triphenylpyrylium tetrachloroferrate is an example of a preferred arylpyrylium salt. It can be obtained by the reaction of benzaldehyde with acetophenone using an acidic condensing agent. For details of the preparation reference is made to the aforecited US. patent.
The 2,4,6-triphenylpyrylium tetrachloroferrate is unusual in that it provides practical inhibition at rem-arkably low concentrations. In fact it affords excellent protection when formulated in a pickling bath at concentrations as low as 0.02% by weight or less. The practical range for the additive is from about 0.01% to about 0.02%. It is effective in both sulfuric and hydrochloric acid, the two most commonly used pickling bath acids.
In using the 2,4,6-triphenylpyrylium tetrachloroferrate it is conveniently employed in the form of a concentrate formulation containing from about 10 to 20% of the inhibitor, about 20% of a detergent such as a alkyl-phenolpolyether-alcohol, about 1 to 2% of concentrated hydrochloric acid and about 69 to 58% water. A typical formulation is as follows in which the components are on a weight percent basis:
Addition of one part of the concentrate to 1,000 parts of the pickling bath provides a suitable concentration for pickling inhibition.
The detergents used in pickling baths are not particularly critical and any number of types and kinds can be used. Preferred species are the alkylaryl-polyether= alcohols although sodium alkylarylsulfonates also perform reasonably satisfactorily.
Pickling baths containing one part of the aforedescribed concentrate to 1,000 parts by weight of the pickling bath showed 80.6% inhibition of acid attack on iron in 30% HCl at 40 C. and 85.6% in 20% sulfuric acid at 60 C.
What is claimed is: e
1. A pickling bath composition suitable for use with iron and steel consisting essentially of an aqueous solution of acid selected from the class consisting of sulfuric and hydrochloric and as a pickling inhibitor 2,4,6-triphenylpyrylium tetrachloroferrate in the concentration of 0.01% about 0.02% by weight.
2. A method of inhibiting acid attack in steel and iron pickling baths which comprises exposing the fresh metal surface to the composition of claim 1.
3. An inhibitor concentrate formulation consisting essentially of 2,4,6-triphenylpyrylium tetrachloroferrate of the following ingredients by weight:
Percent 2,4,6-triphenylpyrylium tetrachloroferrate 10-20 Nonylphenol-polyether-alcohol 20-20 Concentrated hydrochloric acid (37%) l-2 Water 69-58 References Cited UNITED STATES PATENTS 1; United States Patent ()jfi
Claims (1)
1. A PICKLING BATH COMPOSITION SUITABLE FOR USE WITH IRON AND STEEL CONSISTING ESSENTIALLY OF AN AQUEOUS SOLULTION OF ACID SELECTED FROM THE CLASS CONSISTING OF SULFURIC AND HYDROCHLORIC AND AS A PICKLING INHIBITOR 2,4,6-TRIPHENYLPYRYLIUM TETRACHLOROFERRATE IN THE CONCENTRATION OF 0.01% ABOUT 0.02% BY WEIGHT.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56175866A | 1966-06-30 | 1966-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3434973A true US3434973A (en) | 1969-03-25 |
Family
ID=24243324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US561758A Expired - Lifetime US3434973A (en) | 1966-06-30 | 1966-11-30 | Pyrylium salts as pickling inhibitors |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3434973A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250615A (en) * | 1961-10-23 | 1966-05-10 | Eastman Kodak Co | Light-sensitive layers containing pyrylium and thiapyrylium salts |
-
1966
- 1966-11-30 US US561758A patent/US3434973A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250615A (en) * | 1961-10-23 | 1966-05-10 | Eastman Kodak Co | Light-sensitive layers containing pyrylium and thiapyrylium salts |
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