US2010562A - Pickling restrainer and the manufacture thereof - Google Patents
Pickling restrainer and the manufacture thereof Download PDFInfo
- Publication number
- US2010562A US2010562A US652024A US65202433A US2010562A US 2010562 A US2010562 A US 2010562A US 652024 A US652024 A US 652024A US 65202433 A US65202433 A US 65202433A US 2010562 A US2010562 A US 2010562A
- Authority
- US
- United States
- Prior art keywords
- pickling
- bases
- restrainer
- homologues
- steel
- 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 description 19
- 239000000837 restrainer Substances 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 230000000452 restraining effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon 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
- 125000004429 atom Chemical group 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
Definitions
- This invention relates to the pickling of iron and steel and to the production 01 substances for use therein or for other purp ses.
- One object the present invention is to provide an improved restrainer. Another object is to provide a substance which can be employed in conjunction with acids and organic solvents for removing rust and grease from iron and steel prior to painting.
- Another object will be eilective with is to provide a restrainer which any 0! the acids commonly employed for pickling iron and steel.
- pickling practice sulphuric acid or hydrochloric acis is employed, but other acids, for example nitric acid and phosphoric acid, are sometimes used either alone or in conjunction with other acids ior pickling special steels, such as stainless steel, or in order to give a finish which is suitable ior some particular subsequent treatment. for example galvanizingmwhereas the restrainers used hitherto are in some cases not eflective in all acids.
- the invention aims at providing a restrainer which shall be eiiectlve with all aci
- a restrainer which shall be eiiectlve with all aci
- excellent restraining sub stances can be obtained by sulphurating a cyclic base having in the molecule at least one ring containing both carbon and nitrogen atoms and only such atoms in that ring and in which the carbon atoms are saturated with hydrogen or at least one hydrogen atom has been substituted by a hydrocarbon radical.
- the bases which it is preierred to use consist o! homologues of pyridine such as 'a-picoline and in particular the substances known in commerce as heavy pyridine bases.
- the piperidine bases corresponding to the above as well as piperidine itself are also articularly satisfactory.
- dipiperi- (CL 14H) dyls and homologues of qulnoline may be employed. A mixture of such bases may be employed.
- the sulphurated bases may also be used as ingredients in materials ior cleaning iron or steel 5 prior to painting.
- the bases may be sulphurated by beating them with sulphur. This heating may take place at temperatures of 130 C. and upwards for a period varying from a few minutes up to 25 to 30 hours. With a given class of base the period of heating can be reduced as more sulphur is used. Different classes of bases, however, require different periods of heating; thus the reduced bases such as piperidines and dipiperidyls require only a 5 few minutes while the heavy pyridine bases require to hours.
- the temperature of heating varies with the boiling point of the bases under amospheric pressure, although by increasing the pressure bases of low boiling point may be heatgo ed at higher temperatures.
- the bases may also be sulphurated by the action of sulphur monochloride.
- the action in this case is much more violent than with sulphur and can conveniently be modified by the use of 5 diluents such as benzene and paraifln hydrocarbon which do not react.
- 5 diluents such as benzene and paraifln hydrocarbon which do not react.
- the advantages of the use of sulphur chloride are that the duration of the reaction is considerably reduced, and no sulphurislostasinthecaseoiheating withsulo phur. about half or which is evolved as hydrogen sulphide.
- the reaction products may be added directly to the pickling baths, but are preferably first dissolved in sulphm'ic acid, in which state they may be purified. For this purpose they may be heated to about 105 C. to 120 C. and simultaneously blown with steam.
- the products obtained may either be added to the pickling baths alone or they may be mixed with a irothing agent, tor ex- 40 ample glue, sulphite cellulose waste liquor, casein, sine and the like. or, when used in conjunction with acids for removing rust and grease from iron and steel. they may be mixed with organic solvents.
- the irothing agent when used in coniimction with a irothing agent the restraining action of the product is not increased, but the irothing agent has the advantage that it renders the removal of dirt from the work easier when this is taken from the bath, and in addition the froth decreases to the nuisance of acid spray.
- the mixture is heated until there is a gentle reflux from the condenser.
- the temperature of the liquid at this stage is about 135 0., hydrogen sulphide is evolved, and the heating is continued for about 20 to 25 hours, when the temperature of the liquid will have risen to about 155 C.
- the product which amounts in volume to about of a gallon to each 1 gallon of heavy Py dine bases employed, and of which the specific gravity is about 1.164, is then allowed to cool.
- the sulphurated bases thus prepared may be added in this form to the pickling bath, but preferably they are mixed with an equal volume of sulphuric acid Sp. Gr. 1.45, care being taken to prevent undue rise in temperature. Scum and tarry matter then rise to the surface and are separated by any convenient method.
- the sulphate of the sulphurated bases still contains impurities having an oiiensive odour, and to remove these the liquid is heated to a temperature of from 105 to 120 C. and simultaneously blown with steam. On cooling.
- the product is rehdy'ior use with or without dilution or for mixiiigwith irothing agents.
- the said product is mixed with an equal volume of sulphuric acid of Sp. Gr. 1.45.
- This mixture when added in a concentration of 0.02% by volume to a pickling bath containing 4% of sulphuric acid gives with mild steel at 90 C. a restraint of 80% as measured by the percentage drop in the hydrogen evolution in comparison with the hydrogen evolution without the addition of a restrainer. By adding a greater quantity of the restrainer the degree oi restraint may be increased.
- the product may, for example, be mixed with an equal volume of sulphuric acid Sp. Gr. 1.45 containing 3 to 6% of casein, glue, or other suitable irothing agent, and is then added to the pickling bath in a small percent by volume.
- the sulphurated product obtained from the reaction may be added in small quantity directly to the pickling bath.
- a suitable material is made as iollows:-'-
- the step which comprises adding to the pickling bath a product obtained by heating with sulphur one or more of the substances contained in the group comprising piperidine or its homologues, homologues of pyridine, dipiperidyls, and homologues of quinoline.
- the step which comprises adding to the pickling bath a product obtained by treating with sulphur chloride one or more of the substances contained in the group comprising piperidine or its homologues, homologues of pyridine, dipiperidyls, and homologues of quinoline.
- the step which comprises subjecting the surface to be cleaned to the action of a material comprising an acid, at least one organic solvent, and a product obtained by sulphurating at least one o! the substances contained in the group comprising piperidine, homologues of piperidine, homologues of pyridine, dipiperidyls, and homologues of quinoline.
- the step which comprises adding to the pickling bath a product obtained by sulphurating at least one of the substances contained in the group comprising piperidine, homologues of piperidine, homologues of pyridine, dipiperidyls and homologues of quinoline.
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US684112A US1956248A (en) | 1933-01-16 | 1933-08-07 | Sulphurated base |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1795/32A GB396053A (en) | 1932-01-20 | 1932-01-20 | Improvements relating to the pickling of metals |
| GB3266532 | 1932-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2010562A true US2010562A (en) | 1935-08-06 |
Family
ID=26236990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US652024A Expired - Lifetime US2010562A (en) | 1932-01-20 | 1933-01-16 | Pickling restrainer and the manufacture thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2010562A (enrdf_load_stackoverflow) |
| BE (1) | BE393824A (enrdf_load_stackoverflow) |
| FR (1) | FR749246A (enrdf_load_stackoverflow) |
| GB (1) | GB396053A (enrdf_load_stackoverflow) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474179A (en) * | 1947-05-02 | 1949-06-21 | Dow Chemical Co | Acid cleaning composition |
| US2807585A (en) * | 1953-12-02 | 1957-09-24 | American Chem Paint Co | Inhibitor acid |
-
0
- BE BE393824D patent/BE393824A/xx unknown
-
1932
- 1932-01-20 GB GB1795/32A patent/GB396053A/en not_active Expired
-
1933
- 1933-01-16 US US652024A patent/US2010562A/en not_active Expired - Lifetime
- 1933-01-19 FR FR749246D patent/FR749246A/fr not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474179A (en) * | 1947-05-02 | 1949-06-21 | Dow Chemical Co | Acid cleaning composition |
| US2807585A (en) * | 1953-12-02 | 1957-09-24 | American Chem Paint Co | Inhibitor acid |
Also Published As
| Publication number | Publication date |
|---|---|
| BE393824A (enrdf_load_stackoverflow) | |
| FR749246A (fr) | 1933-07-20 |
| GB396053A (en) | 1933-07-20 |
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