US3726637A - Zirconium tanning - Google Patents
Zirconium tanning Download PDFInfo
- Publication number
- US3726637A US3726637A US00192636A US3726637DA US3726637A US 3726637 A US3726637 A US 3726637A US 00192636 A US00192636 A US 00192636A US 3726637D A US3726637D A US 3726637DA US 3726637 A US3726637 A US 3726637A
- Authority
- US
- United States
- Prior art keywords
- tanning
- zirconium
- sulfate
- bath
- sodium
- 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 title abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 24
- JRQGFDPXVPTSJU-UHFFFAOYSA-L sodium zirconium(4+) sulfate Chemical compound [Na+].[Zr+4].[O-]S([O-])(=O)=O JRQGFDPXVPTSJU-UHFFFAOYSA-L 0.000 abstract description 23
- 241001465754 Metazoa Species 0.000 abstract description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000010985 leather Substances 0.000 description 11
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 11
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000283690 Bos taurus Species 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 150000003754 zirconium Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
Definitions
- the present invention relates to tanning with soluble zirconium salts and is particularly concerned with the acceleration of tanning processes in which silicated sodium zirconium sulfate is employed as the tanning agent.
- H80 further ionizes to H+ and SO;
- the sulfate ions (this term hereinafter being intended to include both S0 and HSO4 can be provided from a number of sources but, since the pH of the tanning bath is preferably maintained in the range from about 1.0 to about 2.5, it is p CC usually most convenient to provide the sulfate ions by adding sodium bisulfate (NaHSOQ to the bath. This addition is preferably made substantially simultaneously with the addition of the silicated sodium zirconium sulfate. Alternatively, the bath can be formed by adding silicated sodium zirconium sulfate to a bisulfate solution.
- sulfate ions in addition to the sulfate required to react with cations present in the hides or the bath which form sparingly soluble sulfates.
- the preliminady hide treatment procedures for example soaking, dehairing, lining, bating and pickling, may be conventional.
- zirconium tannage is quite tolerant as respects prior hide treatment and in many cases modified preliminary treatment can be used if desired.
- the leather may be fat liquored and dried in accordance with well known procedures.
- Example 1 Using an experimental tanning drum, a piece of cattle hide having a limed weight of 4.77 kg. was, after washing and bating, tanned. To approximately 1200 ml. of water in the drum there was added 477 g. of sodium bisulfate and 851 g. of silicated sodium zirconium sulfate and the drum was run for five hours during which time the pH in the wheel rose from 1.1 to 1.7. Neutralization was then acomplished by slowly adding to the drum 1750 ml. of a 5% solution of sodium hydroxide over a period of two hours. The tanned hide was left in the float overnight and the next day, after addition of another 250 ml.
- the drum was run for an additional hour.
- the final pH of the tanned hide was found to be 5.8 and it had a shrinkage temperature of over C. It was then drained, wrung, and split, the wet weight after trimming being 3.4 kg.
- Example 2 Pieces of a salt cured green cowhide were soaked in water for rehydration. After conventional treatment including liming and dehairing, the pieces were washed and delimed and bated, using a commercial bate, in an experimental drum. The tanning was then carried out, without removal of the bate solution, by adding to the drum sutlicient silicated sodium zirconium sulfate to provide 2% soluble ZrO and six mols of sodium bisulfate. Drumming was continued for about six hours and was followed by neutralization with sodium bicarbonate to a pH of 3.23. A sample of leather taken after neutralization was found to have a shrinkage temperature of 91 C.
- Example 3 Twenty-three pounds of green calfskin which had been put through conventional beamhouse procedures was placed in an experimental drum with a float containing suflicient silicated sodium zirconium sulfate to provide 6% soluble ZrO and 12% of sodium bisulfate. After operation of the drum for three hours, the pH of the hide was raised to 3.1 with sodium carbonate. The thus neutralized leather was found to have a shrinkage temperature of 91.5 C. and inspection showed no untanned streaks or layers.
- Example 4 Eight sides of brine-cured, fleshed cattle hide were given conventional washing, soaking and liming beamhouse processing. The washed sides were then placed, in a large drum, in a 25% float containing 1% ammonium persulfate and a commercial enzymatic bate containing the equivalent of 2% enzyme. After running the drum for 30 minutes, silicated sodium zirconium sulfate in an amount calculated to provide 5% soluble zirconium, and sodium bisulfate were added and drumming was continued for five hours. The pH of the leather was subsequently adjusted to 3.5 with sodium bicarbonate. Tannage was observed to be complete and the leather was white with a shrinkage temperature of 93 C.
- the following example illustrates the deleterious effect of aging on the tanning efiectiveness of a silicated sodium zirconium sulfate bath.
- Example 5 (a) Using an experimental drum, a beamhouse-processed hide was drummed for six hours in a tanning bath containing an amount of silicated sodium zirconium sulfate calculated to provide 6% soluble ZrO and 12% sodium bisulfate. The bath had been aged for a number of hours after preparation and before introduction of the hide. After neutralization, the hide was found to be well tanned.
- Tanning can in some cases be carried out with an amount of silicated sodium zirconium sulfate as low as about 2% (calculated as soluble Z102). Ordinarily, however, high quality tannage requires about 5% to 6% of soluble ZrO Additional tanning agent may, of course, be employed since the tanning process may thereby be accelerated and the leather obtained may be tougher and more opaque because of zirconium dioxide deposited therein.
- silicated sodium zirconium sulfates furnish sulfate ions
- additional sulfate ions required for the process of the invention need be provided from another source.
- the most convenient source is believed to be sodium bisulfate although other materials such, for example, as sulfuric acid, ammonium bisulfate, or normal sodium sulfate may be used.
- such other sources are not as desirable as sodium bisulfate since they will usually require a pH adjustment of the tanning bath to obtain the desired pH range for tanning.
- the present novel tanning process can be employed not only with calfskins and cattle hides, but also with other animal hides and skins such, for example, as horse hides and sheep skins. Consequently, the term hides herein is intended to include both hides and skins and the term leather includes both tanned hides and tanned skins.
- Percentages set forth herein are percentages by weight and the percentages of materials comprised in the tanning bath are based on the white weight of the hide or hides being tanned.
- a processfor tanning an animal hide which comprises treating such hide with an aqueous tanning bath comprising silicated sodium zirconium sulfate, while maintaining the pH of said bath between 1.0 and 2.5, said bath containing sufiicient silicated sodium zirconium sulfate to provide at least 2% soluble ZrO therein and containing sufficient soluble sulfate to provide, in solution, at least four sulfate ions per atom of zirconium in said bath in addition to sulfate ions required for formation of sparingly soluble sulfates of other cationic elements present in said hide and/ or bath, and neutralizing said hide to a pH of from about 3.0 to about 6.2.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19263671A | 1971-10-26 | 1971-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3726637A true US3726637A (en) | 1973-04-10 |
Family
ID=22710453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00192636A Expired - Lifetime US3726637A (en) | 1971-10-26 | 1971-10-26 | Zirconium tanning |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3726637A (enExample) |
| AU (1) | AU4813472A (enExample) |
| DE (1) | DE2252636A1 (enExample) |
| ES (1) | ES407964A1 (enExample) |
| FR (1) | FR2159003A5 (enExample) |
| IT (1) | IT975372B (enExample) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006067540A1 (en) * | 2004-12-22 | 2006-06-29 | Council Of Scientific And Industrial Research | A process for making wet-pink leather |
-
1971
- 1971-10-26 US US00192636A patent/US3726637A/en not_active Expired - Lifetime
-
1972
- 1972-10-25 AU AU48134/72A patent/AU4813472A/en not_active Expired
- 1972-10-25 ES ES407964A patent/ES407964A1/es not_active Expired
- 1972-10-26 DE DE2252636A patent/DE2252636A1/de active Pending
- 1972-10-26 IT IT70368/72A patent/IT975372B/it active
- 1972-10-26 FR FR7238067A patent/FR2159003A5/fr not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006067540A1 (en) * | 2004-12-22 | 2006-06-29 | Council Of Scientific And Industrial Research | A process for making wet-pink leather |
Also Published As
| Publication number | Publication date |
|---|---|
| IT975372B (it) | 1974-07-20 |
| AU4813472A (en) | 1974-04-26 |
| FR2159003A5 (enExample) | 1973-06-15 |
| ES407964A1 (es) | 1975-10-16 |
| DE2252636A1 (de) | 1973-05-03 |
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