US1832781A - Inhibitor - Google Patents
Inhibitor Download PDFInfo
- Publication number
- US1832781A US1832781A US472481A US47248130A US1832781A US 1832781 A US1832781 A US 1832781A US 472481 A US472481 A US 472481A US 47248130 A US47248130 A US 47248130A US 1832781 A US1832781 A US 1832781A
- Authority
- US
- United States
- Prior art keywords
- pickling
- iron
- steel
- thiosulphate
- sulphuric 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
- 239000003112 inhibitor Substances 0.000 title description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 58
- 238000005554 pickling Methods 0.000 description 35
- 229910052742 iron Inorganic materials 0.000 description 29
- 229910000831 Steel Inorganic materials 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- 239000010959 steel Substances 0.000 description 28
- 239000001117 sulphuric acid Substances 0.000 description 28
- 235000011149 sulphuric acid Nutrition 0.000 description 28
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 17
- 230000009471 action Effects 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 10
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- AGFXBCWWVBWDNE-UHFFFAOYSA-M sodium;oxido-oxo-phenylmethoxy-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[O-]S(=O)(=S)OCC1=CC=CC=C1 AGFXBCWWVBWDNE-UHFFFAOYSA-M 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HLLMICMHTKJPJM-UHFFFAOYSA-M sodium;ethoxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].CCOS([O-])(=O)=S HLLMICMHTKJPJM-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
-
- 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
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
Definitions
- My invention relates to a new inhibitor and to the process of pickling iron and steel, and more particularly it relates to a new pickling solution which effectively remove scale and rust from the iron and steel without appreciably attacking the surface thereof.
- the principal object of my invention is to provide a solution of sulphuric acid or other pickling material in which the pitting and corrosive action of the acid on the iron and steel surface will be reduced to a minimum, and for all practical purposes will be precluded.
- a further object of my invention is to provide a solution of sulphuric acid which will be relatively inert toward ferrous metals and which, therefore, can be shipped in the standard iron or steel containers with assurance that the corrosion of the containers will be minimized, or prevented.
- Still another object is to provide a process of pickling and a pickling bath which effectively and efficiently removes the scale and rust from the iron and steel without attacking the surface thereof.
- My invention is characterized by the addition of a new compound to the sulphuric acid or other pickling material, which compound minimizes or prevents the acid from attacking the iron or steel surface.
- the effectiveness of the acid in removing the scale and rust is not reduced and, therefore, a pickling solution with marked advantages is available.
- Various compounds have previously been suggested for use, but the compounds of the present invention have many advantages over those heretofore known.
- the class of compounds of the present invention are effective, easy to handle, and stable in the pickling bath.
- My invention contemplates the addition of an or anic thiosglphate to the pickling bath. e addition of compounds of this class in relatively small amounts for all practical purposes prevents any pitting or corrosive action of the sulphuric acid on the iron and steelv tha .
- term ifo ganiathi sulphate I includ e the-compounds of the genera formula R.S.SO .OM, where R is an organic radical and where M is'a me al. It W1 e seen at in the formula for thiosulphuric acid (HS;SO Q,OH) the hydrogen of the SH group has been replaced by an organic radical, while the hydrogen of the OH group has been replaced by a metal.
- the or 'anic radical m be any one of a wide variety of groups, but it 1s preferably a carbon-hydrogen radical, such as anglkyl, an
- alkylene or an aryl group.
- aryl group for example, the
- the organic thiosulphates need not be chemically. pure, and may contain other compounds which may or may not also be inhibitors.
- the organic thiosulphate may be used in a crude form and need not be purified before use.
- the compound may be prepared in any desired manner, and the following method of preparation of sodium; b er 1 zyl thiosulpbate is given as one optional method and as illustrative.
- 3600 grams of sodium thiosulphate crystals are dissolved in 3600 cc. of water, and to this mixture is added 1660 cc. of benzyl chloride and 432 cc. of denatured alcohol. The mixture is agitated thoroughly and heated gradually to a temperature of 80 degrees centigrade. After a period of one hour at this temperature, 644 grams of common salt are added and the mixture allowed to cool. The crude sodium benzyl thiosulphate crystallizes out, is filtered, pressed and dried at room temperature.
- one-half pound of the sodium benzyl thiosulphate may be added to 1,000 pounds of 20% sulphuric acid.
- This pickling bath may be used effectively at about 160 degrees F. in the pickling of iron and steel. The oxide and scale are removed with only a very slight action on the metal surface.
- the percentage of the organic thiosulphate to be added to the sulphuric acid varies considerably, depending on the nature of the material being treated and the amount of scale or rust to be removed. In general, the amount added will be between 1 pound of compound to 3,000 pounds of dilute acid and 1 pound of compound to 1,000 pounds of dilute acid. The use of higher percentages of compound does not deleteriously effect the pickling action, but usually represents a loss of the thiosulphate.
- Sulp huric acid issps maen di h other pickling ⁇ itfiillizllsetl in its E3 1;.iiiillii lilibliili fiieiiiacidsor.the.Mid sulphate salts,
- sulphuric acid 5 sensed in the specification and claims is intended to cover such other pickling compounds.
- a pickling bath for removing scale and rust from iron and steel comprising a. relatively weak sulphuric acid solution and a small quantity of an or anic thiosulphate.
- a pickling bath or removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of 9.
- a pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of an aryl substituted thiosulphate.
- a pickling bath for removing scale and rust from iron and steel comprlsing a. relatively weak sulphuric acid solution to which has been added a small uantity of an alkali alkyl substituted thiosu phate.
- a pickling bath for removing scale and rust from iron and steel comprising a.
- a pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of sodium ethyl thiosulphate.
- a pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of sodium benzyl thiosulphate.
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
252. COMPOSITIONS,
'ratented Nov. 17, 1931 UNITED STATES Exam!" r PATENT OFFICE JOSEPH M. LEAPER, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO E. F. BOUGH- TON AND COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION 01 PENNSYLVANIA INHIBITOR No Drawing.
My invention relates to a new inhibitor and to the process of pickling iron and steel, and more particularly it relates to a new pickling solution which effectively remove scale and rust from the iron and steel without appreciably attacking the surface thereof.
The principal object of my invention is to provide a solution of sulphuric acid or other pickling material in which the pitting and corrosive action of the acid on the iron and steel surface will be reduced to a minimum, and for all practical purposes will be precluded.
A further object of my invention is to provide a solution of sulphuric acid which will be relatively inert toward ferrous metals and which, therefore, can be shipped in the standard iron or steel containers with assurance that the corrosion of the containers will be minimized, or prevented.
Still another object is to provide a process of pickling and a pickling bath which effectively and efficiently removes the scale and rust from the iron and steel without attacking the surface thereof. Other objects will appear from a consideration of the specification and claims.
In the so-called pickling processes sulphuric acid or other scale attacking compounds are used to remove the rust or scale from the surface of iron or steel. Great difficulty is encountered since the acid after removing the scale and rust pits and corrodes the metal below, which action is accompanied by the evolution of disagreeable gases.
It is not possible in commercial practice to remove the scale or rust without also attacking the metal, for there is no means of determining when the scale or rust has been removed. Furthermore, the rust and scale usually do not cover the metal surface uniformly, and, therefore, the acid while dissolving the scale at one point on the surface, attacks the metal itself at some adjacent point where the scale does not exist or has been removed. It is necessary that the surface of the iron and steel remain bright and smooth after treatment with the pickling solution, for otherwise the treated objects are unfit for galvanizing and other uses in the trade.
Application filed August 1, 1930. Serial No. 472,481.
Great difliculties are also encountered in shipping of sulphuric acid, due to the chemical reaction which takes place between the acid and the containers, which are usually made of iron or steel. The life of these containers is,therefore, relatively short and there is always present the hazard of leakage with its attending danger to property and life.
My invention is characterized by the addition of a new compound to the sulphuric acid or other pickling material, which compound minimizes or prevents the acid from attacking the iron or steel surface. The effectiveness of the acid in removing the scale and rust is not reduced and, therefore, a pickling solution with marked advantages is available. Various compounds have previously been suggested for use, but the compounds of the present invention have many advantages over those heretofore known. The class of compounds of the present invention are effective, easy to handle, and stable in the pickling bath.
My invention contemplates the addition of an or anic thiosglphate to the pickling bath. e addition of compounds of this class in relatively small amounts for all practical purposes prevents any pitting or corrosive action of the sulphuric acid on the iron and steelv tha .term ifo ganiathi sulphate I includ e the-compounds of the genera formula R.S.SO .OM, where R is an organic radical and where M is'a me al. It W1 e seen at in the formula for thiosulphuric acid (HS;SO Q,OH) the hydrogen of the SH group has been replaced by an organic radical, while the hydrogen of the OH group has been replaced by a metal. The or 'anic radical m be any one of a wide variety of groups, but it 1s preferably a carbon-hydrogen radical, such as anglkyl, an
alkylene, or an aryl group. For example, the
metals are the most satisfactory.
The organic thiosulphates need not be chemically. pure, and may contain other compounds which may or may not also be inhibitors. The organic thiosulphate may be used in a crude form and need not be purified before use. The compound may be prepared in any desired manner, and the following method of preparation of sodium; b er 1 zyl thiosulpbate is given as one optional method and as illustrative.
In an example, 3600 grams of sodium thiosulphate crystals are dissolved in 3600 cc. of water, and to this mixture is added 1660 cc. of benzyl chloride and 432 cc. of denatured alcohol. The mixture is agitated thoroughly and heated gradually to a temperature of 80 degrees centigrade. After a period of one hour at this temperature, 644 grams of common salt are added and the mixture allowed to cool. The crude sodium benzyl thiosulphate crystallizes out, is filtered, pressed and dried at room temperature.
In making up a pickling bath, one-half pound of the sodium benzyl thiosulphate may be added to 1,000 pounds of 20% sulphuric acid. This pickling bath may be used effectively at about 160 degrees F. in the pickling of iron and steel. The oxide and scale are removed with only a very slight action on the metal surface.
The percentage of the organic thiosulphate to be added to the sulphuric acid varies considerably, depending on the nature of the material being treated and the amount of scale or rust to be removed. In general, the amount added will be between 1 pound of compound to 3,000 pounds of dilute acid and 1 pound of compound to 1,000 pounds of dilute acid. The use of higher percentages of compound does not deleteriously effect the pickling action, but usually represents a loss of the thiosulphate. While in the specific example sodium benzyl thiosulphate is mentioned, corresponding proportions of the other organic thiosulphates, such as the alkyl thiosulphates, for example sodium ethyl thiosulphate, or other aryl thiosulphates, may be used in place thereof. Sulp huric acid issps maen di h other pickling {itfiillizllsetl in its E3 1;.iiiillii lilibliili fiieiiiacidsor.the.Mid sulphate salts, The term sulphuric acid 5 sensed in the specification and claims is intended to cover such other pickling compounds.
Other compounds may be used in combination with the organic thiosulphate and they may be inhibitors themselves, or added for other reasons, for instance, for the purpose of inc easing the foam. The addition of crud n I 1 11 cer an instances increases tie efiiciency of the bath. The amount of pyridine to be added depends on the circumstances under which the bath is to be used, but in general may be used in proportions equal to the organic thiosulphate added.
Considerable modification is possible in the choice of the organic thiosulphates and in the percentages used with the pickling compounds without departing from the essential features of the invention.
I claim:
l. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of an organic thiosulphate.
2. The process of pickling iron and steel objects which comprises subjecting said objects to the act-ion of a relatively weak sulphuric acid solution to which has been added a small quantity of a thiosulphate in which the hydrogen of the SH group has been replaced by a carbon-hydrogen organic radical.
3. The process of ickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of an aryl substituted thiosulphate.
4. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a smal quantity of an aryl substituted thiosulphate.
5. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of an alkali alkyl substituted thiosulphate.
6. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of an alkali aryl substituted thiosulphate.
7 The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added ahsmall quantity of sodium ethyl thiosulp ate.
8. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of sodium benzyl thiosulphate.
9. A pickling bath for removing scale and rust from iron and steel comprising a. relatively weak sulphuric acid solution and a small quantity of an or anic thiosulphate.
10. A pickling bath or removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of 9.
252. COMPOSITIONS, V
thiosulphate in which the hydrogen of the SH group has been replaced by a carbonhydrogen organic radical.
11. A pickling bath for removing scale and rust from iron and steel com using a relatively weak sulphuric acid so ution to which has been added a small quantity of an alkyl substituted thiosulphate.
12. A pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of an aryl substituted thiosulphate.
13. A pickling bath for removing scale and rust from iron and steel comprlsing a. relatively weak sulphuric acid solution to which has been added a small uantity of an alkali alkyl substituted thiosu phate.
14. A pickling bath for removing scale and rust from iron and steel comprising a.
relatively weak sulphuric acid solution to which has been added a small quantity of an alkali aryl substituted thiosulphate.
15. A pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of sodium ethyl thiosulphate.
16. A pickling bath for removing scale and rust from iron and steel comprising a relatively weak sulphuric acid solution to which has been added a small quantity of sodium benzyl thiosulphate.
17. The process of pickling iron and steel objects which comprises subjecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a small quantity of an organic thiosulphate and pyridine.
18. The process of pickling iron and steel objects which comprises subJecting said objects to the action of a relatively weak sulphuric acid solution to which has been added a. small quantity of sodium benzyl thiosulphate and pyridine.
-.- and a small quantity of pyridine.
JOSEPH M. LEAPER.
Exa
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US472481A US1832781A (en) | 1930-08-01 | 1930-08-01 | Inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US472481A US1832781A (en) | 1930-08-01 | 1930-08-01 | Inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1832781A true US1832781A (en) | 1931-11-17 |
Family
ID=23875656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US472481A Expired - Lifetime US1832781A (en) | 1930-08-01 | 1930-08-01 | Inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1832781A (en) |
-
1930
- 1930-08-01 US US472481A patent/US1832781A/en not_active Expired - Lifetime
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