CN1077227A - Process of zirconic tanning leather - Google Patents
Process of zirconic tanning leather Download PDFInfo
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- CN1077227A CN1077227A CN 92106877 CN92106877A CN1077227A CN 1077227 A CN1077227 A CN 1077227A CN 92106877 CN92106877 CN 92106877 CN 92106877 A CN92106877 A CN 92106877A CN 1077227 A CN1077227 A CN 1077227A
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- acid
- tanning
- leather
- benzene
- zirconates
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A kind of zirconium tanning process hides novel method, the soluble salt solution that it is characterized in that adopting the benzene polycarboxylic acid of zirconates and three carboxyls or three above carboxyls or its acid anhydrides is in conjunction with carrying out tanning.The leather that is obtained has good moisture-proof thermal stability, and its shrinkage temperature can reach 106-115 ℃.If with 0.2-2% chromic salts retanning, its shrinkage temperature can reach 115-130 ℃.The present invention have pollute little, cost is low, technology is simple, the characteristics of easy handling.
Description
The invention belongs to zirconates tan leather technology
Current leather industry generally adopts the chromic salt process for tanning, and the keratin amount of producing is good, and heat stability is better, but the trivalent chromic ion serious environment pollution in the chroming waste liquor.And chromium is the content rareness in the earth's crust, is the important strategic material, is the protection environment, reduces consuming, and selects for use other metal-salt to replace the chromic salts tan leather to have economic benefit and social benefit.About with the technology of zirconates, report there is external morning as the quid pro quo tan leather of chromic salts.United States Patent (USP) 3726637 zirconates tanning, the consumption of zirconates is (with Z
rO
2Meter) be the 10-15% of pickling tare weight, the pH value of owse is 0.8-1.9, and tanning time is 10-24 hour, can produce the white leather, but the shrinkage temperature of skin does not meet coctostabile requirement about 90 ℃.The complex compound tan leather of United States Patent (USP) 4049379 and United States Patent (USP) 3423162 employing zirconates and aluminium salt or zirconium, aluminium, chromic salts, the leather ability of production is boiled, and promptly wet-hot aging performance is good.But complicated operation, the cost height, the amount that contains trivalent chromic ion in the waste liquid is bigger, still can not eliminate the pollution of chromium.
The objective of the invention is and to reach good moisture-proof thermal stability by zirconium tanned leather, can reduce or eliminate the pollution of chromium again, reduce production costs environment.
The present invention uses the consumption of zirconates tan leather zirconates (with ZrO
2Meter) be pickling tare weight 2-10%, (no specified otherwise, per-cent are benchmark with the pickling tare weight all) optimum quantity is 4-8%, owse pH value 0.8-1.9, tanning time 10-16 hour.Use the benzene polycarboxylic acid of three or three above carboxyls or the further tan leather of soluble salt of its acid anhydrides then, 1,2, the 3-benzenetricarboxylic acid benzene polycarboxylic acid comprises:, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,4-benzene tetracarboxylic acid, 1,2,3,5-benzene tetracarboxylic acid, 1,2,4, the 5-benzene tetracarboxylic acid, 1,2,3,4,5,6-mellitic acid, the perhaps acid anhydrides of these carboxylic acids, be mixed with soluble salt solution, consumption is 0.5-5%, and optimum amount is 1-4%, and pH value is 1.9-5.5, best pH value 2.5-4.5, treatment time 1-6 hour.Through 106-115 ℃ of the leather shrinkage temperature after the soluble salt solution-treated of zirconium tanning and benzene polycarboxylic acid, color is pure white.If continue to improve the hydrothermal stability of leather, the further tanning of available chromic salts tanning agent, its consumption is (with Cr
2O
3Meter) be the 0.2-2% of pickling tare weight, the leather shrinkage temperature of last gained can reach 115-130 ℃.
The present invention tan leather not only color for white, the shrinkage temperature height be the more important thing is and can be eliminated the environmental pollution that chrome tanning brings fully, production cost is low, technology is simple, and is easy to operate.If with the further tanning of a small amount of chromic salts (with Cr
2O
3) consumption is 0.2-2%, pH value is 3.5-3.9, tanning time is 12 hours, can make shrinkage temperature bring up to 115-130 ℃, because the consumption of chromium is few, can adopt the waste liquid of general chrome tanning process, after tanning, chromium content in the waste liquid is low, handles easily, so environmental pollution is little.
The embodiment of the invention 1: the technology before the pickling is pressed general technology production and is handled, and puts into rotary drum after pickled skin is weighed, and presses 5%ZrO
2Add zirconium sulfate, and add 1% Trisodium Citrate, adding water, to make liquor ratio be 100%, after tanning 10 hours, standing over night, add the 1%PH value next day and be the ammonia salts solution (1,2,4,6-benzene tetracarboxylic acid ammonia) of 3.0 Pyromellitic Acid, liquor ratio is 100% to rotate 4 hours, after washing, surveying shrinkage temperature is 106-115 ℃, technology stuffing routinely after tanning is intact, drying, finished leather is a pure white.
The embodiment of the invention 2: cut three skins from pickled skin, put into rotary drum after weighing respectively, ZrO by 10%
2Add zirconium sulfate, 1% Trisodium Citrate, water 150% rotate tanning 12 hours, and standing over night behind the eliminating waste liquid, is taken out wherein one (A).Two remaining Pyromellitic Acid ammonia solutions (PH=4.0) with 5% were handled 5 hours, got rid of waste liquid, took out one (B).One (A) before having taken out put into rotary drum, add 1% chrome tanning agent (concentration 25%Cr
2O
3, basicity 33%), standing over night after tanning 12 hours is washed the back with A, B, three blocks of severe edema due to hypofunction of the spleens of C and is surveyed its shrinkage temperature.
Process for tanning shrinkage temperature ℃
Zirconium tanning+chrome tanning (A) 98-102
Zirconium tanning+Pyromellitic Acid ammonia solution (B) 105-112
Zirconium tanning+Pyromellitic Acid ammonia solution+chrome tanning (C) 115-128
3: one pickled skins of the embodiment of the invention are cut off from the spine line, open corresponding position at two halves and respectively cut 200 gram skins, are divided into two groups and carry out following operation.
A group: add 80 gram zirconium sulfates and (contain ZrO in the industrial goods
2About 20%), Trisodium Citrate 2 grams, 20 ℃ water 200ml rotates standing over night after 10 hours.
10 gram pyromellitic dianhydrides are dissolved in the ammoniacal liquor, add water and be made into the 300ml aqueous solution, regulate PH=2.5 with formic acid (or dilute sulphuric acid), add in the rotary drum, rotated 6 hours, water 300ml * 2 with 20 ℃ after finishing wash twice, dry, and are to be further processed.
The B group: the chrome tanning agent of adding 10% (contains Cr
2O
325%, basicity 33%), carrying out conventional chrome tanning operation, the afterwash of having tanned dries.
A, B carry out stuffing, dyeing for two groups, survey 105-110 ℃ of shrinkage temperature: A group behind the finished product, 108-112 ℃ of B group, other physico-chemical properties of two groups of leather are suitable, but the color of A group zirconium tanned leather is gorgeous, and that B organizes chrome-tanned color is gloomy.
Claims (7)
1, a kind of zirconium tanning leather-making technology is characterized in that the zirconates consumption is (with Z
rO
2Meter) be the 2-10% of pickling tare weight, with the further tanning of soluble salt of benzene polycarboxylic acid or its acid anhydrides of three or three above carboxyls, consumption is 0.5-5% behind the zirconium tanning, and pH value is 1.9-5.5, and the treatment time is 1-6 hour.
2, technology according to claim 1, the optimum amount that it is characterized in that zirconates is 4-8%.
3, technology according to claim 1, it is characterized in that the benzene polycarboxylic acid comprises 1,2, the 3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,4-benzenetricarboxylic acid, 1,2,3,4-benzene tetracarboxylic acid, 1,2,3, the 5-benzene tetracarboxylic acid, 1,2,4, the 5-benzene tetracarboxylic acid, 1,2,3,4,5,6-mellitic acid or their acid anhydrides.
4,, it is characterized in that it is 1-4% that benzene polycarboxylic acid or its acid anhydrides are made the optimum amount of soluble salt solution according to claim 1 and 3 described technologies.
5,, it is characterized in that the best 2.5-4.5 of being of pH value of the solubility solution that benzene polycarboxylic acid or its acid anhydrides are made according to claim 1 and 3 described technologies.
6, technology according to claim 1 is characterized in that available chromic salts tanning agent further carries out tanning.
7,, it is characterized in that chromic salts tanning agent consumption (Cr according to claim 1 and 6 described technologies
2O
3Meter) is the 0.2-2% of pickling tare weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106877 CN1077227A (en) | 1992-04-07 | 1992-04-07 | Process of zirconic tanning leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106877 CN1077227A (en) | 1992-04-07 | 1992-04-07 | Process of zirconic tanning leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1077227A true CN1077227A (en) | 1993-10-13 |
Family
ID=4942506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92106877 Pending CN1077227A (en) | 1992-04-07 | 1992-04-07 | Process of zirconic tanning leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1077227A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360686C (en) * | 2005-12-02 | 2008-01-09 | 四川大学 | Clean production method of chromium-free automobile cushion leather |
-
1992
- 1992-04-07 CN CN 92106877 patent/CN1077227A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360686C (en) * | 2005-12-02 | 2008-01-09 | 四川大学 | Clean production method of chromium-free automobile cushion leather |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |