CN103131803A - Tanning agent of non-chromium non-aldehyde multi-metal ecological leather and tanning method - Google Patents
Tanning agent of non-chromium non-aldehyde multi-metal ecological leather and tanning method Download PDFInfo
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- CN103131803A CN103131803A CN 201110372174 CN201110372174A CN103131803A CN 103131803 A CN103131803 A CN 103131803A CN 201110372174 CN201110372174 CN 201110372174 CN 201110372174 A CN201110372174 A CN 201110372174A CN 103131803 A CN103131803 A CN 103131803A
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Abstract
The invention discloses a tanning agent of non-chromium non-aldehyde multi-metal ecological leather and a tanning method; the tanning agent comprises an ecological tanning agent and a tanning stabilizing agent; the tanning method comprises the following steps: performing acidification processing of raw hide by the ecological tanning agent, the tanning stabilizing agent, water, salt, and acid, performing alkali regulation by slow neutralization with an alkali, finally draining, drying in the air, shoveling to soften the product so as to complete tanning; under a non-chromium non-aldehyde no-enzyme soaking, no-pickling condition, various kinds of leather can be processed by tanning; the finished leather is plump, white in color, and easy to dye, and various physical indexes reach the industrial standard. During processing production, no chromium or phosphorus pollution is caused by various preparations; no aldehyde substance is released; the process is simple; sludge obtained after leather production can be used as crop fertilizers after simple processing; the ecological tanning agent and the tanning stabilizing agent have no performance reduction after being used, and can be used repeatedly, which reduces production cost.
Description
Technical field
The present invention relates to the leather processing technical field, particularly relate to a kind of Chrome-free without tanning agent and the process for tanning of many metals of aldehyde Ecology Leather.
Background technology
Leather tanning is most important operation in the leather processing program, it is the process of leather that rawhide is transformed into, to utilize tannin to carry out chemistry and Physical Processing to the protein of intracutaneous, pass through series of process, and adopt some chemical agents, make the protein in the animal hides such as pig, ox, sheep that a series of variations occur, make collagen protein generation Denaturation.Tanned leather is both soft, firm, wear-resisting again, is not easy putrid and deteriorated.Tanned leather can be used for doing the daily living article of various leathers.
Now the process for tanning of leather adopts the tanning of chromium class or aldehydes tanning more, in tanning industry, makes the high-performance of leather due to chrome tannage, and chrome tanning has just occupied dominant position in the tanning field always since it is used.Due to chromic toxicity, the use of chromic salts causes very big harm to ecotope, people and animals, and mankind itself's survival and development have been consisted of great threat.In traditional chromic tanning, the chrome tanning aste chromium bit can't be utilized effectively, and has caused a large amount of losses of the waste collagen that produces in the tanning industry, but also has brought serious environmental pollution.On the other hand, the shortage of China chromium resource, process hides chromium used is almost entirely by import, and in recent years in national defence and some high technology industries the demand of chromium also more and more, cause the price of chrome ore to be climbed to a higher point year after year.Along with the raising of mankind's environmental consciousness, the pollution problem that solves leather industry is very urgent, especially pollution of chromium; Yet the basic way that solves pollution of chromium can only be thoroughly to abandon chrome tanning.The kind of aldehyde is a lot, and the tanning mechanism of aldehydes tanning agent is mainly because of the reactive groups such as protein amino in carbonyl and skin, forms the process of covalent cross-linking.At present, the applied research of aldehydes tanning agent in process hides mainly concentrates on aldehyde and plants in conjunction with tanning, the progress that aldehyde is used for separately tanning is slower, mainly to use separately aldehydes can't satisfy the process hides requirement, in general use separately the tanning of aldehydes tanning agent, the finished leather shrinkage temperature is not high, finished leather is more flat thin, and some also can produce xanthochromia.And the air ambient that aldehyde material causes pollutes very serious.In some western countries, the leather of chromium, aldehydes tanning has been done strict restriction already.
Therefore, in order to reduce chrome tanning, aldehyde tannage to the pollution of environment, and the objectionable impurities such as chromium aldehyde is sought Chrome-free extremely urgent without the leather tanning process of aldehyde to the infringement of human body.
Summary of the invention
Purpose of the present invention is exactly the deficiency that overcomes above-mentioned technology, thereby the process for tanning of a kind of Chrome-free without many metals of aldehyde Ecology Leather is provided, and the method adopts multiple safe and harmless metal-salt to carry out tanning, and environment is not polluted.
The object of the invention realizes by the following technical solutions: a kind of Chrome-free is first produced required tanning agent without tanning agent and the process for tanning of many metals of aldehyde Ecology Leather before tanning, utilizes tanning agent He Shui, salt, acid, the alkali made to carry out tanning to rawhide.
A kind of Chrome-free is comprised of ecological tanning agent and tanning stablizer without the tanning agent of many metals of aldehyde Ecology Leather.
Ecological tanning agent is first titanyl sulfate 20-30 part to be carried out acidification with acid solution, and acid solution is made into according to 5: 1 ratios by 65% dilute sulphuric acid and 45% hydrochloric acid; Get again zirconium sulfate 12-18 part, Tai-Ace S 150 8-12 part slowly adds, and the gained mixture is warming up to 85 ℃; Then add 2% tartrate, 1.5% hexanodioic acid, the add-on of 2% tartrate, 1.5% hexanodioic acid respectively accounts for the 0.3%-0.5% of solution quality; Promote pH value to 1.2-1.5 with sodium carbonate at last.
The tanning stablizer is that to be mixed with concentration by phthalic acid, acetic acid, tartrate according to 4: 3: 3 part by weight be the 40%-50% aqueous solution, and adding at last concentration is 1.5% ammonium molybdate, and add-on accounts for whole solution quality 0.2%-0.5%.
-kind of Chrome-free carries out according to following steps without the process for tanning of many metals of aldehyde Ecology Leather:
The first step: will add salt 800-900g, ecological tanning agent 200-260g, tanning stablizer 50-70g in 15-20L water, stir and with sulfuric acid or formic acid, solution is transferred to PH1.8-2.2 afterwards, then the immersion skin of 1 kilogram is put into solution, keep water temperature at 38-40 degree centigrade, soak 20h.
Second step: transfer the alkali neutralization in the solution after soaking 20h, transfer pH value to 2.9-3.1 with sodium bicarbonate for the first time, transfer for the second time the alkali neutralization after three hours, transfer pH value to 3.5-3.8 with sodium bicarbonate.
The 3rd step: solution is warming up to 41-42 degree centigrade, keeps going out the skin draining after 4 hours, dry after standing 24h, dry perching when becoming to 7-8, complete tanning and enter next procedure.
Chrome-free disclosed in this invention is without tanning agent and the process for tanning of many metals of aldehyde Ecology Leather, can be at Chrome-free, without aldehyde, do not soak under the condition of enzyme, not pickling, various leathers are carried out tanning processing, three kinds of metal-salt synergies of titanium, zirconium, aluminium in ecological tanning agent, can greatly improve the shrinkage temperature of leather, shrinkage temperature 〉=92 ℃, the plentiful white color of finished leather, be easy to dyeing, every physical index all reaches industry standard.Various preparation Chrome-frees in processing, phosphorus pollute, and discharge simple process without aldehyde material, but making farm crop fertilizer after the mud simple process after process hides uses, described ecological tanning agent and tanning stablizer performance after use can not descend, and can reuse, and has reduced production cost.The present invention can replace traditional chrome tanning, aldehyde tannage to produce the high quality Ecology Leather, is that China's leather industry is eliminated chromium, aldehyde pollutes, and improves the leather opening of performing, and contributes.Be suitable for promoting the use of.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment one
A kind of Chrome-free is comprised of ecological tanning agent and tanning stablizer without the tanning agent of many metals of aldehyde Ecology Leather.
Ecological tanning agent is first 22 parts of titanyl sulfates to be carried out acidification with acid solution, and acid solution is made into according to 5: 1 ratios by 65% dilute sulphuric acid and 45% hydrochloric acid; Get again 9 parts of 14 parts of zirconium sulfates, Tai-Ace S 150 and slowly add, the gained mixture is warming up to 85 ℃; Then add 2% tartrate, 1.5% hexanodioic acid, the add-on of 2% tartrate, 1.5% hexanodioic acid respectively accounts for 0.3% of solution quality; Promote pH value to 1.3 with sodium carbonate at last.
The tanning stablizer is that to be mixed with concentration by phthalic acid, acetic acid, tartrate according to 4: 3: 3 part by weight be 43% aqueous solution, and adding at last concentration is 1.5% ammonium molybdate, and add-on accounts for whole solution quality 0.3%.
A kind of Chrome-free carries out according to following steps without the process for tanning of many metals of aldehyde Ecology Leather:
The first step: will add salt 830g, ecological tanning agent 220g, tanning stablizer 55g in 18L water, stirring transfers to PH2.0 with sulfuric acid or formic acid with solution afterwards, then the immersion skin of 1 kilogram is put into solution, keeps water temperature at 38 degrees centigrade, soaks 20h.
Second step: transfer the alkali neutralization in the solution after soaking 20h, transfer pH value to 3.0 with sodium bicarbonate for the first time, transfer for the second time the alkali neutralization after three hours, transfer pH value to 3.7 with sodium bicarbonate.
The 3rd step: solution is warming up to 41 degrees centigrade, keeps going out the skin draining after 4 hours, dry after standing 24h, perching when drying to 7 one-tenth is completed tanning and is entered next procedure.
Embodiment two
A kind of Chrome-free is comprised of ecological tanning agent and tanning stablizer without the tanning agent of many metals of aldehyde Ecology Leather.
Ecological tanning agent is first 30 parts of titanyl sulfates to be carried out acidification with acid solution, and acid solution is made into according to 5: 1 ratios by 65% dilute sulphuric acid and 45% hydrochloric acid; Get again 12 parts of 18 parts of zirconium sulfates, Tai-Ace S 150 and slowly add, the gained mixture is warming up to 85 ℃; Then add 2% tartrate, 1.5% hexanodioic acid, the add-on of 2% tartrate, 1.5% hexanodioic acid respectively accounts for 0.5% of solution quality; Promote pH value to 1.5 with sodium carbonate at last.
The tanning stablizer is that to be mixed with concentration by phthalic acid, acetic acid, tartrate according to 4: 3: 3 part by weight be 50% aqueous solution, and adding at last concentration is 1.5% ammonium molybdate, and add-on accounts for whole solution quality 0.5%.
A kind of Chrome-free carries out according to following steps without the process for tanning of many metals of aldehyde Ecology Leather:
The first step: will add salt 900g, ecological tanning agent 260g, tanning stablizer 70g in 20L water, stirring transfers to PH2.2 with sulfuric acid or formic acid with solution afterwards, then the immersion skin of 1 kilogram is put into solution, keeps water temperature at 40 degrees centigrade, soaks 20h.
Second step: transfer the alkali neutralization in the solution after soaking 20h, transfer pH value to 3.1 with sodium bicarbonate for the first time, transfer for the second time the alkali neutralization after three hours, transfer pH value to 3.8 with sodium bicarbonate.
The 3rd step: solution is warming up to 42 degrees centigrade, keeps going out the skin draining after 4 hours, dry after standing 24h, perching when drying to 8 one-tenth is completed tanning and is entered next procedure.
Embodiment three
A kind of Chrome-free is comprised of ecological tanning agent and tanning stablizer without the tanning agent of many metals of aldehyde Ecology Leather.
Ecological tanning agent is first 25 parts of titanyl sulfates to be carried out acidification with acid solution, and acid solution is made into according to 5: 1 ratios by 65% dilute sulphuric acid and 45% hydrochloric acid; Get again 10 parts of 15 parts of zirconium sulfates, Tai-Ace S 150 and slowly add, the gained mixture is warming up to 85 ℃; Then add 2% tartrate, 1.5% hexanodioic acid, the add-on of 2% tartrate, 1.5% hexanodioic acid respectively accounts for 0.4% of solution quality; Promote pH value to 1.3 with sodium carbonate at last.
The tanning stablizer is that to be mixed with concentration by phthalic acid, acetic acid, tartrate according to 4: 3: 3 part by weight be 45% aqueous solution, and adding at last concentration is 1.5% ammonium molybdate, and add-on accounts for whole solution quality 0.3%.
A kind of Chrome-free carries out according to following steps without the process for tanning of many metals of aldehyde Ecology Leather:
The first step: will add salt 850g, ecological tanning agent 230g, tanning stablizer 60g in 18L water, stirring transfers to PH2.0 with sulfuric acid or formic acid with solution afterwards, then the immersion skin of 1 kilogram is put into solution, keeps water temperature at 39 degrees centigrade, soaks 20h.
Second step: transfer the alkali neutralization in the solution after soaking 20h, transfer pH value to 3.0 with sodium bicarbonate for the first time, transfer for the second time the alkali neutralization after three hours, transfer pH value to 3.6 with sodium bicarbonate.
The 3rd step: solution is warming up to 41 degrees centigrade, keeps going out the skin draining after 4 hours, dry after standing 24h, perching when drying to 8 one-tenth is completed tanning and is entered next procedure.
Claims (2)
1. a Chrome-free is without the tanning agent of many metals of aldehyde Ecology Leather, it is characterized in that: tanning agent is comprised of ecological tanning agent and tanning stablizer: ecological tanning agent is first titanyl sulfate 20-30 part to be carried out acidification with acid solution, acid solution is made into according to 5: 1 ratios by 65% dilute sulphuric acid and 45% hydrochloric acid, get again zirconium sulfate 12-18 part, Tai-Ace S 150 8-12 part slowly adds, the gained mixture is warming up to 85 ℃, then add 2% tartrate, 1.5% hexanodioic acid, 2% tartrate, the add-on of 1.5% hexanodioic acid respectively accounts for the 0.3%-0.5% of solution quality, promote pH value to 1.2-1.5 with sodium carbonate at last, the tanning stablizer is that to be mixed with concentration by phthalic acid, acetic acid, tartrate according to 4: 3: 3 part by weight be the 40%-50% aqueous solution, and adding at last concentration is 1.5% ammonium molybdate, and add-on accounts for whole solution quality 0.2%-0.5%.
2. a Chrome-free without the process for tanning of many metals of aldehyde Ecology Leather, is characterized in that: carry out according to following steps:
The first step: will add salt 800-900g, ecological tanning agent 200-260g, tanning stablizer 50-70g in 15-20L water, stir and with sulfuric acid or formic acid, solution is transferred to PH1.8-2.2 afterwards, then the immersion skin of 1 kilogram is put into solution, keep water temperature at 38-40 degree centigrade, soak 20h.
Second step: transfer the alkali neutralization in the solution after soaking 20h, transfer pH value to 2.9-3.1 with sodium bicarbonate for the first time, transfer for the second time the alkali neutralization after three hours, transfer pH value to 3.5-3.8 with sodium bicarbonate.
The 3rd step: solution is warming up to 41-42 degree centigrade, keeps going out the skin draining after 4 hours, dry after standing 24h, dry perching when becoming to 7-8, complete tanning and enter next procedure.
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| CN 201110372174 CN103131803A (en) | 2011-11-22 | 2011-11-22 | Tanning agent of non-chromium non-aldehyde multi-metal ecological leather and tanning method |
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| CN 201110372174 CN103131803A (en) | 2011-11-22 | 2011-11-22 | Tanning agent of non-chromium non-aldehyde multi-metal ecological leather and tanning method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105861763A (en) * | 2016-06-16 | 2016-08-17 | 温州大学 | Zirconium complex tanning agent and preparation method thereof |
| CN107201414A (en) * | 2017-06-05 | 2017-09-26 | 兴业皮革科技股份有限公司 | A kind of not pickling chrome-free tanning technique based on many metal combination tanning agents |
| CN111118234A (en) * | 2019-12-24 | 2020-05-08 | 温州大学 | Non-chrome leather tanning method |
| CN113234870A (en) * | 2021-06-29 | 2021-08-10 | 陕西科技大学 | Method for preparing silver-based conductive leather by adopting in-situ growth method |
-
2011
- 2011-11-22 CN CN 201110372174 patent/CN103131803A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105861763A (en) * | 2016-06-16 | 2016-08-17 | 温州大学 | Zirconium complex tanning agent and preparation method thereof |
| CN107201414A (en) * | 2017-06-05 | 2017-09-26 | 兴业皮革科技股份有限公司 | A kind of not pickling chrome-free tanning technique based on many metal combination tanning agents |
| CN107201414B (en) * | 2017-06-05 | 2019-11-12 | 兴业皮革科技股份有限公司 | A kind of not pickling chrome-free tanning technique based on more metal combination tanning agents |
| CN111118234A (en) * | 2019-12-24 | 2020-05-08 | 温州大学 | Non-chrome leather tanning method |
| CN113234870A (en) * | 2021-06-29 | 2021-08-10 | 陕西科技大学 | Method for preparing silver-based conductive leather by adopting in-situ growth method |
| CN113234870B (en) * | 2021-06-29 | 2022-03-29 | 陕西科技大学 | Method for preparing silver-based conductive leather by adopting in-situ growth method |
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Application publication date: 20130605 |