CN1597993A - Treatment process for reducing content of hexavalence chromate in leather - Google Patents
Treatment process for reducing content of hexavalence chromate in leather Download PDFInfo
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- CN1597993A CN1597993A CN 200410040490 CN200410040490A CN1597993A CN 1597993 A CN1597993 A CN 1597993A CN 200410040490 CN200410040490 CN 200410040490 CN 200410040490 A CN200410040490 A CN 200410040490A CN 1597993 A CN1597993 A CN 1597993A
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Abstract
The invention provides a treating method of reducing the content of the hexavalent chrome in fur. Its features that: spray the solution of the reducing agent with mass percent of 0.5% to 3.0% onto the leather and the semi-manufactured fur operated in damp environment or treat the semi-manufactured fur operated in damp environment in the drum. The inducing agent is once of the ferrous sulphate, ferrous chloride, amine ferrous sulphate, sodium sulfite, potassium sulfite and sodium thiosulfate. The invention can not only be used to treat the leather with the superscale hexavalent chrome, but also treat the semi-manufactured leather during the processing and prevent the formation of the hexavalent chrome in the leather. The invention simple technique and operation, richful resource of inducing agent, low cost, and no influence to the later procedure and quality of the fur.
Description
One, technical field
The invention belongs to the tanning technology field, be specifically related to a kind of treatment process that reduces content of 6-valence Cr ions in the leather.
Two, background technology
Chromium Chang Yizheng trivalent and two kinds of valency forms of positive sexavalence exist, and its valence state difference is different with biological effect to the influence of environment.It is believed that: trivalent chromium is a kind of trace metal element of biological and needed by human, and the sexavalent chrome carcinogenic and mutagenic incitant that is intensive, its toxicity is bigger 100 times than trivalent chromium, it can influence the oxidation of cell, reduction, can combine with nucleic acid, to respiratory tract, digestive tube has stimulation, carcinogenic, mutagenesis, and, sexavalent chrome has very strong damaging action to skin, even if the low dose of sexavalent chrome of skin exposure portion contact all dermatitis and eczema can occur, and long-term delay do not heal (Zhu Jianhua, Wang Lili. the toxicity of different valence state chromium and to the influence [J] of human body. environment and exploitation, 1997,12 (3): 46～48).Therefore, countries in the world are to chromate waste water and waste, and chromic content control all has strict regulation in other Industrial products and the daily necessities.
In leather industry, because the leather more than 80% is all used chrome tanning system, the operation of process hides is more in addition, relates to many different materials, different working conditions and different water quality again, therefore, in the leather finished product, often can detect the different sexavalent chrome of content.These chromic generations according to bibliographical information, mainly contain the reason of the following aspects: 1. used the halfway chromium powder of reduction; 2. used chromate pigments; 3. used the fatting agent that contains unsaturated link(age); 4. the high pH value of body lotion in the process hides process; 5. uviolizing; 6. heating; Relative humidity of air or the like when 7. leather is stored (Yu Congzheng, Sun Genhang, Peng Xiaoling etc. the generation reason of Cr in the leather (VI) and Prevention Research [J]. Shaanxi Tech Univ's journal, 2003,21 (2): 1～5).
In recent years, along with the mankind's environmental consciousness constantly strengthens, the cry of green consumption is strong day by day, and countries in the world require more and more stricter to the control of the objectionable impurities in the leather, therefore, the chromic control in the leather also becomes the focus that current China and foreign countries leather circle is paid close attention to.It is reported, countries in the world are stipulated very lowly to the highest chromic limiting the quantity of in the leather now, generally below 5mg/kg, and in the European standard in 1994 the highest chromic limiting the quantity of in the glove leather is defined as (Sun Genhang below the 2mg/kg, Yu Congzheng. chromic progress [J] in the leather. Chinese leather, 2002,31 (7): 35～39), the European market requires the interior chromic content of finished product leather to be no more than 3mg/kg.This has proposed a higher requirement to leather industry beyond doubt.Along with the increase of China joined WTO and leather export trade volume, chromic problem also more and more causes people's attention in the leather.According to sampling statistics, in China leather manufacturer, have in the leather finished product of 28.4% manufacturer chromic content be higher than 3mg/kg (content of 6-valence Cr ions level [J] in China's leather. leather chemical industry, 2003,20 (3): 16).Therefore, chromic content is imperative in the control leather.
At present, reduce chromic content in the leather, treating method commonly used has: 1. add the plant retanning agent sexavalent chrome in the leather is prevented, its principle is to utilize phenolic hydroxyl group in the vegetable tannin molecule can catch the ability of free radical, prevent the formation of peroxylradicals and super oxyradical, make the not oxidized one-tenth sexavalent chrome of trivalent chromium (Yu Congzheng, Sun Genhang, Peng Xiaoling etc. the generation reason of Cr in the leather (VI) and Prevention Research [J]. Shaanxi Tech Univ's journal, 2003,21 (2): 1～5).But because tannin kind difference, difference on effect is very big, therefore to different types of leather, does not have general applicability.2. in the stuffing operation, add stuffing auxiliary agent (Sun Genhang with anti-oxidant function, Yu Congzheng. chromic progress [J] in the leather. Chinese leather, 2002,31 (7): 35～39), also can prevent chromic generation, but its cost is higher, and the stuffing auxiliary agent of available this kind also seldom.3. control chromic content in the finished product leather by the technology of adjusting process hides processing, for example, use and put forward alkali speed more slowly with calcium oxide, magnesium oxide the base material of carrying as main body, use cationic materials, and reduction drying temperature etc. (Yuan Ximing. the control [J] of Cr (VI) content in the finished product leather. Chinese leather, 2003,32 (15): 29～30), this method is more loaded down with trivial details, difficult control, and effect is also uncertain.4. adopt chrome-free tanning (stone is green, Lu Zhongbing. process hides clearer production technology [M]. Beijing: Chemical Industry Press, 2004,249～285).Though this method can thoroughly be eliminated the sexavalent chrome in the leather, because technical qualification are immature, the performance of finished leather can't satisfy people's requirement fully, and is also distant from practice.
Three, summary of the invention
Task of the present invention is the problem that exists at prior art, and the treatment process of content of 6-valence Cr ions in a kind of new reduction leather is provided.
The treatment process of content of 6-valence Cr ions in the reduction leather provided by the invention is characterized in that this method is to handle the work in-process leather that is obtained the back with the finished product leather or through wet practice, handles by following processing step and condition:
(1) with reductive agent preparation mass percent concentration is 0.5～3.0% the aqueous solution;
(2) the reductive agent aqueous solution with configuration evenly is sprayed on the flesh noodles of the work in-process leather that is obtained after finished product leather or the processing of process wet practice, sprays 1～3 time;
(3) to be deposited in a relative humidity be in 50～80% the normal temperature wind sheltering environment to the leather that will spray the reductive agent aqueous solution, 2～15 days time, and then handle by follow-up conventional process conditions and to get final product, maybe will handle the work in-process leather that is obtained the back, handle by following processing step and condition through wet practice:
(1) adding temperature in rotary drum is that work in-process that 20～50 ℃ water will be pending are removed from office and flooded;
(2) reductive agent is added in the rotary drum, it is 0.5～3.0% that its add-on should make the mass percent concentration of this reductive agent aqueous solution, rotates rotary drum then and handles after 0.25～2.0 hour, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.
Used reductive agent is at least a in ferrous sulfate, iron protochloride, ferrous ammonium sulphate, S-WAT, potassium sulfite, the Sulfothiorine in the aforesaid method.
The mass percent concentration of the used reductive agent aqueous solution is preferably 1.0～2.0% in the aforesaid method; The relative humidity that the wind sheltering environment of reductive agent aqueous solution leather has been sprayed in stacking is preferably 55～65%; Pilling up time is preferably 5～7 days; The water temperature that adds rotary drum is preferably 25～35 ℃; The rotary drum rotation treatment time is preferably 0.5～1.0 hour.
The work in-process leather through wet practice obtained in the aforesaid method is meant through operations such as retanning, dyeing, stuffings handles the work in-process leather that is obtained.
As everyone knows, the chromium element in acid-alkali medium, the mutual transforming relationship shown in its trivalent chromium and the sexavalent chrome drawings attached (inorganic chemistry teaching and research room of Chengdu Univ. of Science ﹠ Technology. inorganic chemistry (second edition) [M]. Chengdu: press of Chengdu Univ. of Science ﹠ Technology, 1991).
The treatment process of content of 6-valence Cr ions in the above-mentioned reduction leather provided by the invention, be exactly the character of utilizing the finished product leather dexterously and being in acidic conditions through the work in-process leather after the wet practice processing, the selective reduction agent is a trivalent chromium with hexavalent chrome reduction, and contain excessive reductive agent in the maintenance leather, prevent that the free trivalent chromium is oxidized to sexavalent chrome in the leather, thereby guarantee in the finished product leather that non-hexavalent chromium or content of 6-valence Cr ions do not exceed standard.
The present invention has the following advantages:
1, the treatment process of content of 6-valence Cr ions in the reduction leather provided by the invention is skillfully constructed, and technology and operation are all very simple, do not need special equipment yet, the processing that it not only can be used for the finished product leather can also be used for the processing of the work in-process leather behind wet practice, and is applied widely.
2, reduce chromic content in the leather with method provided by the invention, effect is very obvious, content of 6-valence Cr ions in the leather after the processing all below 3mg/kg, can reach the requirement that on the present world market content of 6-valence Cr ions in the finished product leather is no more than 3mg/kg fully.
3, handle leather with method provided by the invention after, not only can reduce or eliminate the sexavalent chrome that has produced in the leather, but also can effectively prevent chromic generation in the leather.
4, the treatment process of content of 6-valence Cr ions in the reduction leather provided by the invention, the reductive agent source of its use is very extensive, abundant, cheap, and to use vegetable tanning agent, stuffing auxiliary agent and adjust the process hides complete processing and reduce in the leather method of chromic content and compare, processing cost is low.
5, behind the disposal methods leather with content of 6-valence Cr ions in the reduction leather provided by the invention, all can not make a difference to the operation of subsequent handling and the physical and mechanical properties and the appearance property of finished leather, therefore, this method is as safe as a house, reliable.
Four, appended drawings is trivalent chromium and the mutual transforming relationship figure of sexavalent chrome in acid-alkali medium.
Five, embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
At first taking by weighing Sulfothiorine and it is mixed with mass percent concentration is 0.5% the aqueous solution, then the sodium thiosulfate solution of configuration evenly is sprayed on the flesh noodles of brown cow leather upper leather finished product that a collection of (100) content of 6-valence Cr ions is 15mg/kg with spray gun, spray 3 times, it is in 55～60% the normal temperature wind sheltering environment that the flesh side of a belt that will spray the Sulfothiorine reductive agent aqueous solution at last is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 2 days, handled getting final product again by follow-up conventional process conditions.Do not detect in this finished product leather and contain sexavalent chrome.
Embodiment 2
At first taking by weighing ferrous sulfate and it is mixed with mass percent concentration is 1.0% the aqueous solution, ferrous sulfate aqueous solution with configuration evenly is sprayed on the flesh noodles of light coffee color pig leather for making garment finished product that a collection of (100) content of 6-valence Cr ions is 20mg/kg with spray gun then, spray 2 times, it is in 50～55% the normal temperature wind sheltering environment that the flesh side of a belt that will spray the ferrous sulfate reductive agent aqueous solution at last is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 5 days, handled getting final product again by follow-up conventional process conditions.Do not detect in this finished product leather and contain sexavalent chrome.
Embodiment 3
At first take by weighing S-WAT and ferrous ammonium sulphate at 2: 1 by mass ratio, and it is mixed with mass percent concentration is 2.5% mixed aqueous solution, S-WAT and ferrous ammonium sulphate mixed aqueous solution with configuration evenly is sprayed on the flesh noodles of black ash rupelo sheepskin garment leather finished product that a collection of (100) content of 6-valence Cr ions is 30mg/kg with spray gun then, spray 2 times, it is in 55～65% the normal temperature wind sheltering environment that the flesh side of a belt that will spray the S-WAT and the ferrous ammonium sulphate reductive agent aqueous solution at last is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 7 days, handled getting final product again by follow-up conventional process conditions.Detect that chromic content is 0.21mg/kg in this finished product leather.
Embodiment 4
At first taking by weighing iron protochloride and it is mixed with mass percent concentration is 2.0% the aqueous solution, then the ferrous chloride aqueous solution of configuration evenly to be sprayed at a collection of (100) content of 6-valence Cr ions with spray gun be 25mg/kg, handle through wet practice on the flesh noodles of black pigskin clothes work in-process leather of after drying, spray 3 times, it is in 60～70% the normal temperature wind sheltering environment that the flesh side of a belt that will spray the iron protochloride reductive agent aqueous solution at last is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 12 days, handled getting final product again by follow-up conventional process conditions.Do not detect in this work in-process leather and contain sexavalent chrome.
Embodiment 5
At first take by weighing potassium sulfite at 1: 1: 3 by mass ratio, Sulfothiorine and ferrous sulfate, and it is mixed with mass percent concentration is 3.0% mixed aqueous solution, then with the potassium sulfite that disposes, it is 40mg/kg that Sulfothiorine and ferrous sulfate mixed aqueous solution evenly are sprayed at a collection of (100) content of 6-valence Cr ions with spray gun, handle through wet practice on the half-finished flesh noodles of yellowish brown cow leather upper of after drying, spray 1 time, to spray potassium sulfite at last, it is in 65～75% the normal temperature wind sheltering environment that the flesh side of a belt of the Sulfothiorine and the ferrous sulfate reductive agent aqueous solution is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 15 days, handled getting final product again by follow-up conventional process conditions.Do not detect in this work in-process leather and contain sexavalent chrome.
Embodiment 6
At first taking by weighing S-WAT and it is mixed with mass percent concentration is 1.5% the aqueous solution, then the sodium sulfite aqueous solution of configuration evenly to be sprayed at a collection of (100) content of 6-valence Cr ions with spray gun be 32mg/kg, handle through wet practice on the flesh noodles of red goat upper work in-process leather of after drying, spray 1 time, it is in 70～80% the normal temperature wind sheltering environment that the flesh side of a belt that will spray the S-WAT reductive agent aqueous solution at last is deposited in a relative humidity to flesh noodles, wind sheltering was placed after 10 days, handled getting final product again by follow-up conventional process conditions.Do not detect in this work in-process leather and contain sexavalent chrome.
Embodiment 7
A collection of (100) through the cream-coloured cow leather upper work in-process leather of wet practice after finishing dealing with, are drained the body lotion in the rotary drum, and the water that adds temperature again and be 20 ℃ floods it; Then reductive agent Sulfothiorine is added in the rotary drum, it is 2.0% that its add-on should make the mass percent concentration of this sodium thiosulfate solution, rotates rotary drum again and handles after 2.0 hours, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
Embodiment 8
A collection of (100) through the reddish-brown goat upper work in-process leather of wet practice after finishing dealing with, are drained the body lotion in the rotary drum, and the water that adds temperature again and be 25 ℃ floods it; Then the reductive agent ferrous ammonium sulphate is added in the rotary drum, it is 2.5% that its add-on should make the mass percent concentration of this ferrous sulfate aqueous ammonium, rotates rotary drum again and handles after 1.5 hours, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
Embodiment 9
A collection of (100) through the grey pigskin clothes work in-process leather of wet practice after finishing dealing with, are drained the body lotion in the rotary drum, and the water that adds temperature again and be 35 ℃ floods it; Be that 5: 2 the reductive agent S-WAT and the mixture of iron protochloride add in the rotary drum then with mass ratio, it is 3.0% that its add-on should make the mass percent concentration of this S-WAT and iron protochloride mixed aqueous solution, rotating rotary drum again handled after 0.25 hour, drain body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
Embodiment 10
With a collection of (100) through wet practice handle after drying, content of 6-valence Cr ions is that the black pigskin clothes work in-process leather of 20mg/kg is put into rotary drum, the water that adds temperature again and be 40 ℃ floods it; Then the reductive agent ferrous sulfate is added in the rotary drum, it is 0.5% that its add-on should make the mass percent concentration of this ferrous sulfate aqueous solution, rotates rotary drum again and handles after 0.5 hour, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
Embodiment 11
With a collection of (100) through wet practice handle after drying, content of 6-valence Cr ions is that the brown cow leather upper work in-process leather of 32mg/kg is put into rotary drum, the water that adds temperature again and be 30 ℃ floods it; The mixture that with mass ratio is 1: 2: 3 reductive agent Sulfothiorine, ferrous sulfate and potassium sulfite then adds in the rotary drum, it is 1.0% that its add-on should make the mass percent concentration of this Sulfothiorine, ferrous sulfate and potassium sulfite mixed aqueous solution, rotating rotary drum again handled after 2.0 hours, drain body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
Embodiment 12
With a collection of (100) through wet practice handle after drying, content of 6-valence Cr ions is that the black pigskin clothes work in-process leather of 35mg/kg is put into rotary drum, the water that adds temperature again and be 50 ℃ floods it; Then the reductive agent ferrous sulfate is added in the rotary drum, it is 1.5% that its add-on should make the mass percent concentration of this ferrous sulfate aqueous solution, rotates rotary drum again and handles after 1.0 hours, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.After treating that these work in-process revolutionary cadre is dry, do not detect and wherein contain sexavalent chrome, and the finished product leather does not detect yet and contains sexavalent chrome.
The measuring method of content of 6-valence Cr ions is to adopt the bioassay standard to content of 6-valence Cr ions in the leather commonly used in the world at present, i.e. De Guo DIN53314 standard in the leather of above embodiment.
Claims (10)
1, a kind of treatment process that reduces content of 6-valence Cr ions in the leather is characterized in that this method is to handle the work in-process leather that is obtained the back with the finished product leather or through wet practice, handles by following processing step and condition:
(1) with reductive agent preparation mass percent concentration is 0.5～3.0% the aqueous solution;
(2) the reductive agent aqueous solution with configuration evenly is sprayed on the flesh noodles of the work in-process leather that is obtained after finished product leather or the processing of process wet practice, sprays 1～3 time;
(3) to be deposited in a relative humidity be in 50～80% the normal temperature wind sheltering environment to the leather that will spray the reductive agent aqueous solution, 2～15 days time, and then handle by follow-up conventional process conditions and to get final product, maybe will handle the work in-process leather that is obtained the back, handle by following processing step and condition through wet practice:
(1) adding temperature in rotary drum is that work in-process that 20～50 ℃ water will be pending are removed from office and flooded;
(2) reductive agent is added in the rotary drum, it is 0.5～3.0% that its add-on should make the mass percent concentration of this reductive agent aqueous solution, rotates rotary drum then and handles after 0.25～2.0 hour, drains body lotion, taking-up work in-process leather handles getting final product again by follow-up conventional process conditions.
2, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 1, the mass percent concentration that it is characterized in that the used reductive agent aqueous solution is 1.0～2.0%.
3, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 1 and 2 is characterized in that used reductive agent is at least a in ferrous sulfate, iron protochloride, ferrous ammonium sulphate, S-WAT, potassium sulfite, the Sulfothiorine.
4, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 1 and 2, the relative humidity that it is characterized in that stacking the wind sheltering environment that has sprayed reductive agent aqueous solution leather is 55～65%.
5, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 3, the relative humidity that it is characterized in that stacking the wind sheltering environment that has sprayed reductive agent aqueous solution leather is 55～65%.
6, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 1 and 2 is characterized in that pilling up time is 5～7 days.
7, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 5 is characterized in that pilling up time is 5～7 days.
8, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 1 and 2, the water temperature that it is characterized in that adding rotary drum is 25～35 ℃.
9, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 3, the water temperature that it is characterized in that adding rotary drum is 25～35 ℃.
10, the treatment process of content of 6-valence Cr ions in the reduction leather according to claim 9 is characterized in that it is 0.5～1.0 hour that rotary drum rotates the treatment time.
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| CN 200410040490 CN1256444C (en) | 2004-08-20 | 2004-08-20 | Treatment process for reducing content of hexavalence chromate in leather |
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| CN 200410040490 CN1256444C (en) | 2004-08-20 | 2004-08-20 | Treatment process for reducing content of hexavalence chromate in leather |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333084C (en) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | Adjuvant for preventing hexavalent chromium in leather and its preparation method |
| CN1333085C (en) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | Production method of leather in which hexavalent chromium content reaches the standard |
| CN101525674B (en) * | 2009-04-02 | 2012-08-15 | 西藏自治区拉萨皮革厂 | Method for stabilizing content of trivalent chromium and minimum hexavalent chrome in leather |
| CN102719572A (en) * | 2012-06-15 | 2012-10-10 | 福建出入境检验检疫局检验检疫技术中心 | Hexavalent chromium elimination agent and application thereof |
| CN101316938B (en) * | 2005-11-29 | 2013-03-27 | Tfl皮革技术有限责任公司 | Leather treatment and agent |
| CN103272362A (en) * | 2013-05-11 | 2013-09-04 | 乐山师范学院 | Method for detoxicating hexavalent chromium in chromium slag by using silicon tetrachloride |
| CN103374634A (en) * | 2012-04-19 | 2013-10-30 | 咸阳银河无机材料有限公司 | Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient |
| CN104450996A (en) * | 2014-09-22 | 2015-03-25 | 王晓锦 | Effective method for preventing hexavalent chromium in leather materials and leather products |
| CN111747593A (en) * | 2020-07-01 | 2020-10-09 | 河北东明皮革有限公司 | Segmented circulating system for waste liquid of tanning preparation and tanning section and using method thereof |
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2004
- 2004-08-20 CN CN 200410040490 patent/CN1256444C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101316938B (en) * | 2005-11-29 | 2013-03-27 | Tfl皮革技术有限责任公司 | Leather treatment and agent |
| CN1333084C (en) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | Adjuvant for preventing hexavalent chromium in leather and its preparation method |
| CN1333085C (en) * | 2006-02-20 | 2007-08-22 | 陕西科技大学 | Production method of leather in which hexavalent chromium content reaches the standard |
| CN101525674B (en) * | 2009-04-02 | 2012-08-15 | 西藏自治区拉萨皮革厂 | Method for stabilizing content of trivalent chromium and minimum hexavalent chrome in leather |
| CN103374634A (en) * | 2012-04-19 | 2013-10-30 | 咸阳银河无机材料有限公司 | Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient |
| CN102719572A (en) * | 2012-06-15 | 2012-10-10 | 福建出入境检验检疫局检验检疫技术中心 | Hexavalent chromium elimination agent and application thereof |
| CN102719572B (en) * | 2012-06-15 | 2014-04-30 | 福建出入境检验检疫局检验检疫技术中心 | Hexavalent chromium elimination agent and application thereof |
| CN103272362A (en) * | 2013-05-11 | 2013-09-04 | 乐山师范学院 | Method for detoxicating hexavalent chromium in chromium slag by using silicon tetrachloride |
| CN104450996A (en) * | 2014-09-22 | 2015-03-25 | 王晓锦 | Effective method for preventing hexavalent chromium in leather materials and leather products |
| CN111747593A (en) * | 2020-07-01 | 2020-10-09 | 河北东明皮革有限公司 | Segmented circulating system for waste liquid of tanning preparation and tanning section and using method thereof |
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| CN1256444C (en) | 2006-05-17 |
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