US2087230A - Method for regenerating phosphoric pickling bath - Google Patents
Method for regenerating phosphoric pickling bath Download PDFInfo
- Publication number
- US2087230A US2087230A US67307D US6730736D US2087230A US 2087230 A US2087230 A US 2087230A US 67307 D US67307 D US 67307D US 6730736 D US6730736 D US 6730736D US 2087230 A US2087230 A US 2087230A
- Authority
- US
- United States
- Prior art keywords
- bath
- iron
- acid
- pickling
- phosphoric
- 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 29
- 238000000034 method Methods 0.000 title description 9
- 230000001172 regenerating effect Effects 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 36
- 229910052742 iron Inorganic materials 0.000 description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 25
- 235000011149 sulphuric acid Nutrition 0.000 description 25
- 239000001117 sulphuric acid Substances 0.000 description 23
- 235000011167 hydrochloric acid Nutrition 0.000 description 19
- 238000007792 addition Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- -1 ferrous metals Chemical class 0.000 description 5
- 239000010959 steel Substances 0.000 description 4
- 239000005569 Iron sulphate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000272201 Columbiformes Species 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002966 varnish 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
- C23G1/36—Regeneration of waste pickling liquors
Definitions
- My invention has for its object the regeneration of the pickling baths constituted by phosphoric acid, generally .used for ferrous metals.
- This pickling by means of phosphoric acid in a first bath is generally followed by an inimersion in a second bath of acid iron phosphate which deposits on the metal a film forming a yielding and resistant support for the paints or varnish to be applied subsequently.
- This process ensures a longer life for the painting of iron'worksthan any other process of pickling, sanding included.
- it is a known fact that such pickling leads to a very high consumption 01 phosphoric acid.
- the phosphoric pickling bath very active a the beginning of .its action, becomes soon sluggish, while still containing in the free state more than half of the Pros employed'
- a very small amount of iron in dissolution is suflicient for paralyzing the pickling action of the phosphoric acid, probably by reason of the rapid .and considerableincrease of the viscosity of the bath which increase of viscosity is due to Application March 5, 1936, Serial In France July 16, 1935 the presence of a compound of phosphoric acid and divalent iron.
- Part (about A) of this first bath may be used after dilution to 23% of free P205 for forming the second bath i. e. the bath of acid phosphate of iron. The remainder of the first bath is thrown away.
- the pickling is effected in this manner the efiiciency of the P205 employed is underneath 50%.
- solubility of the ferrous sulphate and iron chloride in the phosphoric bath is comparatively small, it is preferable not to add in all more than 100 kgs. of sulphuric acid at 60 B. or 200 kgs. of hydrochloric acid at 20-22 B. for 240 kgs. of phosphoric acid at 57 B. (50% of P205) employed. If this precaution were not observed I would risk producing in the phosphoric bath a crystallization of iron sulphate or chloride.
- As a. bath at 10-11% of P205 contains about 240 kgs. of phosphoric acid at 50% of P205 per cubic meter, it is easy to bear in mind that the amount of sulphuric acid at 60 B. to add into it should notrise beyond 100 kgs. per cubic meter of bath or that the amount of hydrochloric acid at 20-22 B. should not rise beyond 200 kgs. per cubic meter of bath.
- the phosphoric pickling bath regenerated by means of, sulphuric or hydrochloric acid should never serve for preparing the second bath or bath of iron phosphate.
- Example 1 (sulphuric acid) Using a first or phosphoric pickling bath of 10 cubic meters, containing originally 11% of P205 and kept at 0., the duration of pickling of a sheet iron which was at the beginnin 2 minutes had risen to 30 minutes after 8 days of working.
- this bath serves for the'duration of several pickling baths
- These figures correspond to a second bath of same volume as the first or phosphoric bath which is not compulsory.
- the phosphoric first bath is returned substantially to its original volume by an addition of about 600 kgs. of phosphoric acid containing 50% of P205 (corresponding to the 240 kgs. contained in each cubic meter of the phosphoric bath removed for reconstituting the second) and of the required volume of water.
- the pickling being then continued at the same rate analysis shows successively on the 10th, 12th and 14th days contents of iron of 26, 38 and 51 kgs. per cubic meter. On each of these days I add 250 kgs. of sulphuric acid at 60 B, i. e. in all 1000 kgs. After the fourth regeneration, the work may be continued up to the 15th day.
- Example 2 (hydrochloric acid) A pickling bath of 10' cubic meters containing originally 10.5% of P205 and'held at 50 C. is found to be too sluggish after an eight. days use. The measuring of the divalent iron by the permanganate method gives out contents of 12 kgs. per cubic meter with 7.5% of free P205.
- the step which consists in adding to the bath when the bath has lost part of its activity by combination of the phosphoric acid with iron, sulphuric acid in amounts not above that corresponding to saturation of the iron present in the bath.
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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR46846T | 1935-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2087230A true US2087230A (en) | 1937-07-20 |
Family
ID=8682414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US67307D Expired - Lifetime US2087230A (en) | 1935-12-27 | 1936-03-05 | Method for regenerating phosphoric pickling bath |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US2087230A (enrdf_load_stackoverflow) |
| BE (1) | BE410539A (enrdf_load_stackoverflow) |
| FR (2) | FR792440A (enrdf_load_stackoverflow) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428464A (en) * | 1945-02-09 | 1947-10-07 | Westinghouse Electric Corp | Method and composition for etching metal |
| US2476345A (en) * | 1946-09-03 | 1949-07-19 | Zavarella Arthur | Process for phosphating stainless steel surfaces |
| US3144361A (en) * | 1955-11-10 | 1964-08-11 | Klinghoffer Stefan | Pretreating iron or steel |
| US3932243A (en) * | 1973-07-20 | 1976-01-13 | Fremont Industries, Inc. | Cleaning and polishing compound for barrel and vibratory finishing of ferrous and non-ferrous metals |
| WO2015162604A1 (en) | 2014-04-22 | 2015-10-29 | Green Future Ltd. | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3010853A (en) * | 1959-05-14 | 1961-11-28 | Solvent Service Inc | Method of cleaning pipes and the like |
| US3281268A (en) * | 1959-08-24 | 1966-10-25 | Dow Chemical Co | Scale removal |
-
0
- BE BE410539D patent/BE410539A/xx unknown
-
1935
- 1935-07-16 FR FR792440D patent/FR792440A/fr not_active Expired
- 1935-12-27 FR FR46846D patent/FR46846E/fr not_active Expired
-
1936
- 1936-03-05 US US67307D patent/US2087230A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428464A (en) * | 1945-02-09 | 1947-10-07 | Westinghouse Electric Corp | Method and composition for etching metal |
| US2476345A (en) * | 1946-09-03 | 1949-07-19 | Zavarella Arthur | Process for phosphating stainless steel surfaces |
| US3144361A (en) * | 1955-11-10 | 1964-08-11 | Klinghoffer Stefan | Pretreating iron or steel |
| US3932243A (en) * | 1973-07-20 | 1976-01-13 | Fremont Industries, Inc. | Cleaning and polishing compound for barrel and vibratory finishing of ferrous and non-ferrous metals |
| WO2015162604A1 (en) | 2014-04-22 | 2015-10-29 | Green Future Ltd. | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process |
| US9752238B2 (en) | 2014-04-22 | 2017-09-05 | Green Future Ltd. | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process |
Also Published As
| Publication number | Publication date |
|---|---|
| BE410539A (enrdf_load_stackoverflow) | |
| FR792440A (fr) | 1935-12-31 |
| FR46846E (fr) | 1936-09-12 |
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