CN102719573B - Method for reducing content of hexavalent chromium in leather through synergistic effect of tannin and vitamin C - Google Patents
Method for reducing content of hexavalent chromium in leather through synergistic effect of tannin and vitamin C Download PDFInfo
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- CN102719573B CN102719573B CN201210215566.7A CN201210215566A CN102719573B CN 102719573 B CN102719573 B CN 102719573B CN 201210215566 A CN201210215566 A CN 201210215566A CN 102719573 B CN102719573 B CN 102719573B
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Abstract
The invention discloses a method for reducing the content of hexavalent chromium in leather through the synergistic effect of tannin and vitamin C. The method is characterized by comprising the following steps of: soaking 5 to 10 parts of blue leather powder by using distilled water, preparing 1 to 10 parts of vitamin C into a solution, adding the soaked blue leather powder into the solution, reacting at the temperature of 10 to 40 DEG C for 12 to 24h, standing for 6 to 12h, and filtering; adding filter residue into 300 to 500 parts of distilled water, adding 0.5 to 2 parts of tannin, reacting at room temperature for 12 to 24h, standing for 6 to 12h, and filtering; adding 50 to 100 parts of glutaraldehyde or oxazolidine water solution at the concentration of 3 percent, reacting at the temperature of 40 to 60 DEG C for 4 to 8h, standing for 8 to 12h, and filtering; and drying for 6 to 12h under the condition that the temperature is 30 to 50 DEG C and the vacuum degree is 0.1Mpa, adding an obtained product into 40 to 100 parts of oleic acid water solution in which the ratio of oleic acid to water is 1:200, regulating the pH value to be 4.0 to 6.0 by using acid, putting into a constant-temperature water bath oscillator, reacting for 4 days under the condition that the temperature is 30 to 50 DEG C and the rotating speed is 50 to 100rpm, and testing the content of the hexavalent chromium in the blue leather powder.
Description
Technical field
The present invention relates to the method that tannin and vitamins C synergy reduce content of 6-valence Cr ions in leather, belong to clean process hides field.
Background technology
In process hides process, chrome tanning is the current the most ripe and most popular method for leather-making of research, adds wet processing and multiple operations such as ornamenting after preparing, tan before tanning, and the sexavalent chrome of different content often can be detected in leatherware.But chromic toxicity is very large, organism and environment are had to great harm, if direct and skin contact can cause allergic dermatitis; In vivo, sexavalent chrome is very easy to be absorbed by organism, thereby accumulation in vivo, there is obvious carcinogenesis (Akira N, Yoshinari B. Mechanism of hexavalent chromium adsorption by persimmon tannin gel[J] .Water Research, 2004,38:2859 – 2864.).Therefore, every country has very strict limitation standard to content of 6-valence Cr ions in leather, general requirement remains in content of 6-valence Cr ions in leather lower than 5mg/kg, and European Union requires lower than 3mg/kg, requires in glove leather goods content of 6-valence Cr ions lower than 2mg/kg in European standards in 1994.
At present, the main method that reduces content of 6-valence Cr ions in leather has: (1) replaces traditional chrome tanning agent with chrome-free tanning agent, (Di Y, Shi B, Song L J, et al. Oxidizing degradation of valonia extract and utilisation of the products. Part 2. Combination tannages of degraded product using 10% H
2o
2with Cr (III) and Al (III) [J]. Journal of the Society of Leather Technologists and Chemists, 2001,85 (1): 19-23.), this method can be controlled from source chromic generation, but the product that the performance of the leather products obtaining obtains far away from chrome tanning.(2) improve leather-making technology flow process, adopt in conjunction with novel procesies such as tanner skill, high-absorption chrome tanning technique or circulations, make Cr
2o
3usage quantity can drop to 1.4% even lower, finished product keratin amount can remain unchanged (Liao Longli. the preparation of tanning chemistry and technology (first volume)---process hides and tanning [M]. Beijing: education of science press, 2001:149-152.), but new technical process cost is higher, be difficult for extensive use.(3) in process hides process, use reductive agent or antioxidant, for example, in process hides process, select the antioxidants such as Sulfothiorine, S-WAT, tea-polyphenol and xitix to process leather, (Gao Hongchao, Ding Zhiwen, Tang Keyong, Deng. chromic effect research [J] in antioxidant prevention leather. Chinese leather, 2007,36(11): 12-14.), this kind of method has good restraining effect to the sexavalent chrome in leather, but it is not very obvious only taking single reductive agent, its effect.
Summary of the invention
The present invention seeks to provide for the deficiencies in the prior art a kind of vegatable tannin and vitamins C synergy to reduce the method for content of 6-valence Cr ions in leather, be characterized in adopting blue skin powder as starting raw material, representative using oleic acid as fatting agent, simulation leather greasing process, tests chromic content in final blue skin powder.In its inhibition leather, sexavalent chrome tells on obviously, can not impact, and cost is lower to leather products performance.
Object of the present invention is realized by following technical measures, and wherein said raw material umber is parts by weight except specified otherwise.
The method that tannin and vitamins C synergy reduce content of 6-valence Cr ions in leather comprises the following steps:
(1). by 5-10 part, be preferably the blue skin powder of 6-8 part, fully soak with distilled water, get 1-10 part, be preferably 3-8 part vitamins C and add wiring solution-forming in 400-600 part distilled water, again soaked blue skin powder is joined in above-mentioned solution, in temperature 10-40 ℃ of stirring reaction 12-24h, standing 6-12h, filters, and obtains intermediate product A;
(2). the intermediate product A that step (1) is obtained adds in 300-500 part distilled water, add again 0.5-2 part, be preferably 1-1.5 part tannin, stirring reaction 12-24h under room temperature condition, standing 6-12h, filter, wash away unreacted tannin with distilled water, adding concentration is glutaraldehyde or oxazolidine aqueous solution 50-100 part of 3%, in temperature 40-60 ℃ of reaction 4-8h, standing 8-12h, filters, and washes away unreacted glutaraldehyde or oxazolidine with distilled water, in temperature, be that 30-50 ℃, vacuum tightness are dry 6-12h under 0.1Mpa condition, obtain intermediate product B;
(3). the intermediate product B that step (2) is obtained joins oleic acid: water=1: in oleic acid aqueous solution 40-100 part of 200, with acid for adjusting pH=4.0-6.0, fully shake up, be placed in water bath with thermostatic control vibrator, under the condition that is 50-100rpm at temperature 30-50 ℃, rotating speed, react 4 days, test in blue skin powder content of 6-valence Cr ions lower than 1.0mg/kg.
Tannin is any in Baybery tannin, larch tannin or Black Wattle tannin.
Acid is any in hydrochloric acid, sulfuric acid or acetic acid.
Performance test:
Above-mentioned blue skin powder after treatment is extracted with dipotassium hydrogen phosphate solution, at 540nm place, with the content of ultraviolet-visible spectrophotometer determination of hexavalent chromium.Result shows: in blue skin powder, content of 6-valence Cr ions is lower than 1.0mg/kg.
The present invention compared with prior art, has the following advantages:
1. technological operation is simple, and resistance of oxidation is strong, can effectively reduce chromic content in leather;
2. the antioxidant relating in experimentation is vegatable tannin and vitamins C, is polyphenolic compound, compared with general reductive agent, on the one hand, cheap, has reduced production cost; On the other hand, polyphenolic compound is to not injury on human body basic, remains in and in leather, can not cause bad impact.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can content according to the present invention make some nonessential improvement and adjustment.
Embodiment 1
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 5 parts of blue skin powder, fully soak with distilled water, get 1 part of vitamins C and join wiring solution-forming in 400 parts of distilled water, more soaked blue skin powder is joined in above-mentioned solution, in 10 ℃ of stirring reaction 24h of temperature, standing 6h, filters, and obtains intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 300 parts of distilled water, then add 0.5 part of Baybery tannin, stirring reaction 12h under room temperature condition, standing 6h, filter, wash away unreacted Baybery tannin with distilled water, adding concentration is 50 parts of 3% glutaraldehyde water solutions, at 40 ℃ of temperature, react 8h, standing 8h, filters, and washes away unreacted glutaraldehyde with distilled water, in temperature, be that 30 ℃, vacuum tightness are dry 12h under 0.1Mpa condition, obtain intermediate product B;
(3). the intermediate product B obtaining in step (2) is joined to oleic acid: water=1: in 40 parts of 200 the oleic acid aqueous solution, regulate pH=4.0 with dilute hydrochloric acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 30 ℃, the rotating speed condition that is 50rpm, test content of 6-valence Cr ions in blue skin powder.In this indigo plant skin powder, content of 6-valence Cr ions is 0.16mg/kg.
Embodiment 2
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 10 parts of blue skin powder, fully soak with distilled water, get 5 parts of vitamins Cs and join wiring solution-forming in 400 parts of distilled water, again soaked blue skin powder is joined in above-mentioned solution, in 10 ℃ of stirring reaction 12h of temperature, standing 6h, filter, obtain intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 300 parts of distilled water, then add 1 part of Black Wattle tannin, stirring reaction 12h under room temperature condition, standing 6h, filter, wash away unreacted Black Wattle tannin with distilled water, add 50 parts of 3% glutaraldehyde water solutions, at 40 ℃ of temperature, react 4h, standing 8h, filters, and washes away unreacted glutaraldehyde with distilled water, in temperature, be that 30 ℃, vacuum tightness are dry 6h under 0.1Mpa condition, obtain intermediate product B;
(3). the intermediate product B obtaining in step (2) is joined to oleic acid: water=1: in 40 parts of 200 the oleic acid aqueous solution, regulate pH=4.0 with dilute sulphuric acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 30 ℃, the rotating speed condition that is 50rpm, test content of 6-valence Cr ions in blue skin powder.In blue skin powder, do not detect and contain sexavalent chrome.
Embodiment 3
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 10 parts of blue skin powder, fully soak with distilled water, get 8 parts of vitamins Cs and join wiring solution-forming in 400 parts of distilled water, again soaked blue skin powder is joined in above-mentioned solution, in 10 ℃ of stirring reaction 24h of temperature, standing 12h, filter, obtain intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 300 parts of distilled water, then add 1.5 parts of larch tannins, stirring reaction 24h under room temperature condition, standing 6h, filter, wash away unreacted larch tannin with distilled water, add 50 parts of 3% the oxazolidine aqueous solution, at 40 ℃ of temperature, react 4h, standing 8h, filters, and washes away unreacted oxazolidine with distilled water, in temperature, be that 30 ℃, vacuum tightness are dry 6h under 0.1Mpa condition, obtain intermediate product B;
(3). the intermediate product B obtaining in step (2) is joined to oleic acid: water=1: in 40 parts of 200 the oleic acid aqueous solution, regulate pH=4.0 with acetic acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 40 ℃, the rotating speed condition that is 80rpm, content of 6-valence Cr ions in test system skin powder.In blue skin powder, do not detect and contain sexavalent chrome.
Embodiment 4
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 10 parts of blue skin powder, fully soak with distilled water, get 10 parts of vitamins Cs and join wiring solution-forming in 600 parts of distilled water, again soaked blue skin powder is joined in above-mentioned solution, in 40 ℃ of stirring reaction 12h of temperature, standing 12h, filter, obtain intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 500 parts of distilled water, then add 2 parts of Baybery tannins, stirring reaction 24h under room temperature condition, standing 12h, filter, wash away unreacted Baybery tannin with distilled water, add 100 parts of 3% the oxazolidine aqueous solution, under temperature 60 C, react 4h, standing 12h, filters, and washes away unreacted oxazolidine with distilled water, in temperature, be that 50 ℃, vacuum tightness are dry 6h under 0.1Mpa condition, obtain intermediate product B;
(3). the product B obtaining in step (2) is joined to oleic acid: water=1: in 100 parts of 200 the oleic acid aqueous solution, regulate pH=6.0 with dilute sulphuric acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 50 ℃, the rotating speed condition that is 100rpm, content of 6-valence Cr ions in the blue skin powder of test system.In this indigo plant skin powder, content of 6-valence Cr ions is 0.92mg/kg.
Embodiment 5
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 6 parts of blue skin powder, fully soak with distilled water, get 8 parts of vitamins Cs and join wiring solution-forming in 500 parts of distilled water, soaked blue skin powder is joined in above-mentioned solution, in 20 ℃ of stirring reaction 24h of temperature, standing 12h, filters, and obtains intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 500 parts of distilled water, then add 1.5 parts of Black Wattle tannin, stirring reaction 24h under room temperature condition, standing 12h, filter, wash away unreacted Black Wattle tannin with distilled water, add 100 parts of 3% the oxazolidine aqueous solution, under temperature 60 C, react 4h, standing 12h, filters, and washes away responseless oxazolidine with distilled water, in temperature, be that 50 ℃, vacuum tightness are dry 6h under 0.1Mpa condition, obtain intermediate product B;
(3). the product B obtaining in step (2) is joined to oleic acid: water=1: in 60 parts of 200 the oleic acid aqueous solution, regulate pH=6.0 with acetic acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 40 ℃, the rotating speed condition that is 100rpm, content of 6-valence Cr ions in the blue skin powder of test system.In blue skin powder, do not detect and contain sexavalent chrome.
Embodiment 6
The method that reduces content of 6-valence Cr ions in leather comprises the steps:
(1). by 8 parts of blue skin powder, fully soak with distilled water, get 5 parts of vitamins Cs and join wiring solution-forming in 600 parts of distilled water, again soaked blue skin powder is joined in above-mentioned solution, in 30 ℃ of stirring reaction 24h of temperature, standing 12h, filter, obtain intermediate product A;
(2). the intermediate product A obtaining in step (1) is joined in 500 parts of distilled water, then add 2 parts of larch tannins, stirring reaction 24h under room temperature condition, standing 12h, filter, wash away unreacted larch tannin with distilled water, add 100 parts of 3% glutaraldehyde water solutions, under temperature 50 C, react 6h, standing 12h, filters, and washes away unreacted glutaraldehyde with distilled water, in temperature, be that 40 ℃, vacuum tightness are dry 6h under 0.1Mpa condition, obtain intermediate product B;
(3). the intermediate product B obtaining in step (2) is joined to oleic acid: water=1: in 100 parts of 200 the oleic acid aqueous solution, regulate pH=4.0 with dilute hydrochloric acid, after fully shaking up, be placed in water bath with thermostatic control vibrator, in temperature, be to react 4 days under 40 ℃, the rotating speed condition that is 60rpm, content of 6-valence Cr ions in the blue skin powder of test system.In blue skin powder, do not detect and contain sexavalent chrome.
Claims (3)
1. tannin and vitamins C synergy reduce a method for content of 6-valence Cr ions in leather, it is characterized in that the method comprises the following steps: count by weight:
(1). by blue 5-10 part skin powder, fully soak with distilled water, get 1-10 part vitamins C and add wiring solution-forming in 400-600 part distilled water, again soaked blue skin powder is joined in above-mentioned solution, in temperature 10-40 ℃ of stirring reaction 12-24h, standing 6-12h, filter, obtain intermediate product A;
(2). the intermediate product A that step (1) is obtained adds in 300-500 part distilled water, add again 0.5-2 part tannin, stirring reaction 12-24h under room temperature condition, standing 6-12h, filter, wash away unreacted tannin with distilled water, adding concentration is glutaraldehyde or oxazolidine aqueous solution 50-100 part of 3%, in temperature 40-60 ℃ of reaction 4-8h, standing 8-12h, filters, and washes away unreacted glutaraldehyde or oxazolidine with distilled water, in temperature, be that 30-50 ℃, vacuum tightness are dry 6-12h under 0.1MPa condition, obtain intermediate product B;
(3). the intermediate product B that step (2) is obtained joins oleic acid: water=1: in oleic acid aqueous solution 40-100 part of 200, with acid for adjusting pH=4.0-6.0, fully shake up, be placed in water bath with thermostatic control vibrator, under the condition that is 50-100rpm at temperature 30-50 ℃, rotating speed, react 4 days, test in blue skin powder content of 6-valence Cr ions lower than 1.0mg/kg.
2. tannin and vitamins C synergy reduces the method for content of 6-valence Cr ions in leather as claimed in claim 1, it is characterized in that tannin is any in Baybery tannin, larch tannin or Black Wattle tannin.
3. tannin and vitamins C synergy reduces the method for content of 6-valence Cr ions in leather as claimed in claim 1, it is characterized in that acid is for any in hydrochloric acid, sulfuric acid or acetic acid.
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| CN103352092A (en) * | 2012-12-24 | 2013-10-16 | 山东华升化工科技有限公司 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
| US10358686B2 (en) * | 2014-08-04 | 2019-07-23 | Citizen Watch Co., Ltd. | Leather or leather article and method for producing same, hexavalent chromium treatment agent, method for treating hexavalent chromium in crude leather or crude leather article |
| ES2887730T3 (en) * | 2017-03-10 | 2021-12-27 | Citizen Watch Co Ltd | Powdered composition for the treatment of hexavalent chromium, compressed and method for producing leather |
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| CN101100696A (en) * | 2007-07-26 | 2008-01-09 | 浙江远东皮革有限公司 | Technique for preparing lining leather of pigskin shoes |
| WO2009000962A1 (en) * | 2007-06-25 | 2008-12-31 | Consejo Superior De Investigaciones Científicas | Method for recycling of chrome and bioproducts from fur waste, installation for performing same and products obtained therefrom |
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Patent Citations (3)
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|---|---|---|---|---|
| CN1112162A (en) * | 1994-05-16 | 1995-11-22 | 丁德太 | Method for processing domestic fowls' skin with feather |
| WO2009000962A1 (en) * | 2007-06-25 | 2008-12-31 | Consejo Superior De Investigaciones Científicas | Method for recycling of chrome and bioproducts from fur waste, installation for performing same and products obtained therefrom |
| CN101100696A (en) * | 2007-07-26 | 2008-01-09 | 浙江远东皮革有限公司 | Technique for preparing lining leather of pigskin shoes |
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| 抗氧化剂预防皮革中六价铬的作用研究;高鸿超等;《中国皮革》;20070630;第36卷(第11期);第13页第1.4.3和1.4.4节 * |
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