CN1333084C - Adjuvant for preventing hexavalent chromium in leather and its preparation method - Google Patents
Adjuvant for preventing hexavalent chromium in leather and its preparation method Download PDFInfo
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- CN1333084C CN1333084C CNB2006100418003A CN200610041800A CN1333084C CN 1333084 C CN1333084 C CN 1333084C CN B2006100418003 A CNB2006100418003 A CN B2006100418003A CN 200610041800 A CN200610041800 A CN 200610041800A CN 1333084 C CN1333084 C CN 1333084C
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Abstract
The present invention relates to an auxiliary agent for preventing hexavalent chromium in leather and a preparation method thereof. The method includes the steps that 3 portions to 4 portions of bayberry extract is homogeneously mixed with 6 portions to 7 portions of water according to weight percentage; the pH value of mixture adjusted by formic acid is 3 to 3.5, and the mixture is heated to the temperature of 70 DEG C to 75 DEG C under the protection of nitrogen; 0.5 portion to 0.6 portion of sodium bisulfite is added after constant temperature of 3 hours to 3.5 hours; a powdery bayberry extract modified product is obtained after spray drying for 1 hour to 1.5 hours at the constant temperature of 60 DEG C to 65 DEG C; 2 portions to 4 portions of sodium thiosulfate, 2 portions to 4 portions of bayberry extract modified product, 1 portion to 3 portions of sodium sulfite and 1 portion to 2 portions of hydroquinone are mixed homogeneously according to weight percentage. The sodium thiosulfate and the sodium sulfite of the present invention can reduce the hexavalent chrome produced in the leather in the process of leather making, the modified bayberry extract and the hydroquinone can efficiently block the generation of hydroperoxyl radicals, the oxidizer of oxidation trivalent chromium is eliminated radically, and accordingly the present invention ensures that the hexavalent chrome is not generated in the process of storing and using the finished leather.
Description
Technical field
The present invention relates to the leather production method in light industry field, chromic auxiliary agent and preparation method thereof in particularly a kind of prevention leather.
Background technology
The basic technology route of process hides is: the preceding preparation of at first the raw material skin being tanned, and then carry out chrome tanning, basket wet pelt after washing, degreasing, carry out (chromium) retanning again, carry alkali and in and poststaining, stuffing, carry out fixation at last, cover with paint, lacquer, colour wash, etc. and make the finished product leather.
The used tanning agent of the present tanning of China (comprising retanning) is mainly chrome tanning agent [its main component is chromium sulphate (III)], and it is chromic oxidized that sexavalent chrome derives from free in the chrome tanned leather (not cooperating) in the leather.According to the principles of chemistry, under alkalescence or neutrallty condition, trivalent chromium is oxidized to sexavalent chrome easily, is contained the compound institute oxidation of peroxy especially easily.Leather-making technology propose alkali and neutralization (chemical that is adopted is a soda ash, sodium-acetate etc.) after, chrome-tanned pH is near 7, generally contains peroxy in the used fatting agent of stuffing subsequently.Therefore, in China's chrome tanned leather content of 6-valence Cr ions to exceed standard be very general.Sexavalent chrome toxicity is very big, in the world especially American-European countries to content of 6-valence Cr ions in the leather require very strict (clothing leather, automobile cushion leather etc. are the highest limits the quantity of and is≤5mg/kg, glove leather is the highest limit the quantity of into≤2mg/kg).As a light industry that export share is bigger, sexavalent chrome exceeds standard and will seriously hinder the export trade of China's leatherware.In view of the complicacy that sexavalent chrome in the leather forms, still there is not comparatively effective means employing for making content of 6-valence Cr ions reach standard at present.One of main root that sexavalent chrome produces in the leather is that higher degree of unsaturation grease is the use of raw material fatting agent such as sulfited fish oil etc., the engineering technical personnel of enterprise therefore few with or simply without this type of fatting agent.This method has reduced chromic content in the leather to a certain extent, but does not tackle the problem at its root as yet, and to be performance of leather reduce as feel such as soft, plentiful the problem that another one causes thus greatly.Therefore it is imperative to develop the leather sexavalent chrome systems technology up to standard of limiting the quantity of.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and can make chromic auxiliary agent and preparation method thereof in content of 6-valence Cr ions in the leather prevention leather up to standard.
For achieving the above object, the technical solution used in the present invention is: at first by mass fraction 3～4 parts myrica extract and 6～7 parts water are mixed, the pH value of regulating mixed solution with formic acid is 3～3.5, under nitrogen protection, be heated to 70～75 ℃, behind the constant temperature 3～3.5 hours, add the sodium bisulfite of 0.5～0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1～1.5 hour spraying drying of 60～65 ℃ of following constant temperature; By mass fraction the Resorcinol of 2～4 parts Sulfothiorine, 2～4 parts myrica extract modified product, 1～3 part S-WAT and 1～2 part is mixed and to get final product.
Chromic auxiliary agent is that 2～4 parts Sulfothiorine, 2～4 parts myrica extract modified product, 1～3 part S-WAT and 1～2 part Resorcinol are formed by mass fraction in the prevention leather that makes according to preparation method of the present invention.
In the prevention leather of the present invention in the chromic auxiliary agent, Sulfothiorine and S-WAT can reduce the sexavalent chrome that produces in the process hides process in leather, secondly modification myrica extract and Resorcinol are a kind of radical scavengers, can effectively block the generation of peroxy radical, fundamentally eliminate the chromic oxygenant of oxidation, thereby ensure that finished leather can not produce sexavalent chrome in storage and use.
Embodiment
Embodiment 1, at first 4 parts myrica extract and 6 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3, under nitrogen protection, be heated to 75 ℃, behind the constant temperature 3 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1 hour spraying drying of 60 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 2 parts of 400 purposes, 4 parts myrica extract modified product, 3 parts S-WAT and 1 part and to get final product, the auxiliary agent that obtains is that 2 parts Sulfothiorine, 4 parts myrica extract modified product, 3 parts S-WAT and 1 part Resorcinol are formed by mass fraction.
Embodiment 2, at first 3 parts myrica extract and 6.5 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.2, under nitrogen protection, be heated to 72 ℃, behind the constant temperature 3.2 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.5 hours spraying dryings of 63 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 4 parts of 400 purposes, 2 parts myrica extract modified product, 1 part S-WAT and 2 parts and to get final product, the auxiliary agent that obtains is that 4 parts Sulfothiorine, 2 parts myrica extract modified product, 1 part S-WAT and 2 parts Resorcinol are formed by mass fraction.
Embodiment 3, at first 3.6 parts myrica extract and 6.3 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.4, under nitrogen protection, be heated to 74 ℃, behind the constant temperature 3.4 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.2 hours spraying dryings of 65 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 3 parts of 400 purposes, 3 parts myrica extract modified product, 2 parts S-WAT and 1.5 parts and to get final product, the auxiliary agent that obtains is that 3 parts Sulfothiorine, 3 parts myrica extract modified product, 2 parts S-WAT and 1.5 parts Resorcinol are formed by mass fraction.
Embodiment 4, at first 3.2 parts myrica extract and 7 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.1, under nitrogen protection, be heated to 71 ℃, behind the constant temperature 3.1 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.4 hours spraying dryings of 62 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 4 parts of 400 purposes, 3 parts myrica extract modified product, 2 parts S-WAT and 1.8 parts and to get final product, the auxiliary agent that obtains is that 4 parts Sulfothiorine, 3 parts myrica extract modified product, 2 parts S-WAT and 1.8 parts Resorcinol are formed by mass fraction.
Embodiment 5, at first 3.8 parts myrica extract and 6.8 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.3, under nitrogen protection, be heated to 73 ℃, behind the constant temperature 3.3 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.3 hours spraying dryings of 64 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 2 parts of 400 purposes, 4 parts myrica extract modified product, 1 part S-WAT and 1.2 parts and to get final product, the auxiliary agent that obtains is that 2 parts Sulfothiorine, 4 parts myrica extract modified product, 1 part S-WAT and 1.2 parts Resorcinol are formed by mass fraction.
Embodiment 6, at first 3.5 parts myrica extract and 6.7 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.5, under nitrogen protection, be heated to 70 ℃, behind the constant temperature 3.5 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.1 hours spraying dryings of 61 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 3 parts of 400 purposes, 2 parts myrica extract modified product, 3 parts S-WAT and 2 parts and to get final product, the auxiliary agent that obtains is that 3 parts Sulfothiorine, 2 parts myrica extract modified product, 3 parts S-WAT and 2 parts Resorcinol are formed by mass fraction.
The product appearance that makes by preparation method of the present invention is light powder, this product can use in the painted stuffing process of process hides, general consumption is 0.8～1.2% of a wet blue leather quality, adding the leather that auxiliary agent of the present invention makes detects in strict accordance with the IUC-18 methods analyst, can guarantee that content of 6-valence Cr ions is not more than 5mg/kg (5 milligrams of chromium of every kilogram of leather sample) in the chrome tanned leather, sometimes not even greater than 2mg/kg, meet international standard.
Claims (9)
1, a kind of preparation method who prevents chromic auxiliary agent in the leather is characterized in that:
1) at first 3～4 parts myrica extract and 6～7 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3～3.5, under nitrogen protection, be heated to 70～75 ℃, behind the constant temperature 3～3.5 hours, add the sodium bisulfite of 0.5～0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1～1.5 hour spraying drying of 60～65 ℃ of following constant temperature;
2) by mass fraction the Resorcinol of 2～4 parts Sulfothiorine, 2～4 parts myrica extract modified product, 1～3 part S-WAT and 1～2 part is mixed and get final product.
2, the preparation method of sexavalent chrome auxiliary agent in the prevention leather according to claim 1, it is characterized in that: the granularity of said Sulfothiorine, myrica extract modified product, S-WAT and Resorcinol is less than 400 orders.
3, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 4 parts myrica extract and 6 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3, under nitrogen protection, be heated to 75 ℃, behind the constant temperature 3 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1 hour spraying drying of 60 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 2 parts of 400 purposes, 4 parts myrica extract modified product, 3 parts S-WAT and 1 part and to get final product.
4, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 3 parts myrica extract and 6.5 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.2, under nitrogen protection, be heated to 72 ℃, behind the constant temperature 3.2 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.5 hours spraying dryings of 63 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 4 parts of 400 purposes, 2 parts myrica extract modified product, 1 part S-WAT and 2 parts and to get final product.
5, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 3.6 parts myrica extract and 6.3 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.4, under nitrogen protection, be heated to 74 ℃, behind the constant temperature 3.4 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.2 hours spraying dryings of 65 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 3 parts of 400 purposes, 3 parts myrica extract modified product, 2 parts S-WAT and 1.5 parts and to get final product.
6, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 3.2 parts myrica extract and 7 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.1, under nitrogen protection, be heated to 71 ℃, behind the constant temperature 3.1 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.4 hours spraying dryings of 62 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 4 parts of 400 purposes, 3 parts myrica extract modified product, 2 parts S-WAT and 1.8 parts and to get final product.
7, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 3.8 parts myrica extract and 6.8 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.3, under nitrogen protection, be heated to 73 ℃, behind the constant temperature 3.3 hours, add the sodium bisulfite of 0.5 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.3 hours spraying dryings of 64 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 2 parts of 400 purposes, 4 parts myrica extract modified product, 1 part S-WAT and 1.2 parts and to get final product.
8, the preparation method of chromic auxiliary agent in the prevention leather according to claim 1, it is characterized in that: at first 3.5 parts myrica extract and 6.7 parts water are mixed by mass fraction, the pH value of regulating mixed solution with formic acid is 3.5, under nitrogen protection, be heated to 70 ℃, behind the constant temperature 3.5 hours, add the sodium bisulfite of 0.6 part of mixed solution quality, obtain Powdered myrica extract modified product in 1.1 hours spraying dryings of 61 ℃ of following constant temperature; By mass fraction granularity is mixed less than the Resorcinol of the Sulfothiorine of 3 parts of 400 purposes, 2 parts myrica extract modified product, 3 parts S-WAT and 2 parts and to get final product.
9, chromic auxiliary agent in a kind of prevention leather is characterized in that: by mass fraction is that 2～4 parts Sulfothiorine, 2～4 parts myrica extract modified product, 1～3 part S-WAT and 1～2 part Resorcinol are formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100418003A CN1333084C (en) | 2006-02-20 | 2006-02-20 | Adjuvant for preventing hexavalent chromium in leather and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100418003A CN1333084C (en) | 2006-02-20 | 2006-02-20 | Adjuvant for preventing hexavalent chromium in leather and its preparation method |
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| Publication Number | Publication Date |
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| CN1807654A CN1807654A (en) | 2006-07-26 |
| CN1333084C true CN1333084C (en) | 2007-08-22 |
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| CNB2006100418003A Expired - Fee Related CN1333084C (en) | 2006-02-20 | 2006-02-20 | Adjuvant for preventing hexavalent chromium in leather and its preparation method |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104946821B (en) * | 2015-05-29 | 2017-03-08 | 兴业皮革科技股份有限公司 | A kind of method of Cr VI excessive problem in solution natural leather |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19860610A1 (en) * | 1998-12-29 | 2000-07-06 | Schill & Seilacher | Chrome-tanned leather for e.g. gloves, shoes, furniture or car seats is treated with dubbing containing antioxidant to reduce hexavalent chromium release potential |
| DE19906190A1 (en) * | 1999-02-15 | 2000-08-17 | Boehme Chem Fab Kg | Tanning process |
| CN1597993A (en) * | 2004-08-20 | 2005-03-23 | 四川大学 | Treatment process for reducing content of hexavalence chromate in leather |
-
2006
- 2006-02-20 CN CNB2006100418003A patent/CN1333084C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19860610A1 (en) * | 1998-12-29 | 2000-07-06 | Schill & Seilacher | Chrome-tanned leather for e.g. gloves, shoes, furniture or car seats is treated with dubbing containing antioxidant to reduce hexavalent chromium release potential |
| DE19906190A1 (en) * | 1999-02-15 | 2000-08-17 | Boehme Chem Fab Kg | Tanning process |
| CN1597993A (en) * | 2004-08-20 | 2005-03-23 | 四川大学 | Treatment process for reducing content of hexavalence chromate in leather |
Non-Patent Citations (3)
| Title |
|---|
| 六价铬专用防治PC助剂的应用研究 马兴元 等，中国皮革，第34卷第9期 2005 * |
| 荆树皮栲胶对皮革中六价铬预防作用的研究 孙根行 等，皮革化工，第19卷第6期 2002 * |
| 荆树皮栲胶对皮革中六价铬预防作用的研究 孙根行 等，皮革化工，第19卷第6期 2002;六价铬专用防治PC助剂的应用研究 马兴元 等，中国皮革，第34卷第9期 2005 * |
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