CN1333085C - Production method of leather in which hexavalent chromium content reaches the standard - Google Patents
Production method of leather in which hexavalent chromium content reaches the standard Download PDFInfo
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Abstract
The present invention relates to a production method of leather in which hexavalent chromium content reaches the standard. The method comprises the following steps: chrome leather is placed in a barrate to be washed; water and degreaser peregal are added; formic acid solution is added for liquor drainage; water and modified glutaraldehyde are added, and chromium powder and hyposulfite of soda are added for liquor drainage; water, sodium bisulfite, hyposulfite of soda and neutralizing retanning agents PAK-N are added for liquor drainage; water, synthetic tanning agents, acrylic resin tanning agents ART-1, waxberry extract, dye, sulphitation modified wool ester fat-liquoring agents, synthetic fat-liquoring agents SES201, SCF synthetic fat-liquoring agents, DF composite fat-liquoring agents, gallic acid, solution of hydroquinone and formic acid solution and formic acid are added for liquor drainage; water is added for liquor drainage. Each link in which hexavalent chrome is easily generated is prevented by the present invention, and meanwhile, the performance of finished leather is not influenced. According to the method provided by the present invention, the production of chrome tanning leather can ensure that the hexavalent chromium content in the finished leather is less than 5 mg/kg or equal to 5 mg/kg (5 milligram chromium per kilogram leather sample), which accords with the international standard.
Description
Technical field
The present invention relates to the leather production method in light industry field, particularly a kind of content of 6-valence Cr ions leather production method up to standard.
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, wet blue 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.
At present the used tanning agent of tanning (comprising retanning) is mainly chrome tanning agent, and its main component is chromium sulphate (III), and it is not oxidized that sexavalent chrome derives from the chrome tanned leather the free trivalent chromium that promptly cooperates 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, be soda ash and carry the chemical that alkali and neutralization adopted, sodium-acetates etc., chrome-tanned pH are near 7, generally contain 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, a kind of content of 6-valence Cr ions production method up to standard that can make in the leather is provided.
For achieving the above object, the technical solution used in the present invention is: water Xian, wet blue leather is placed rotary drum, and add the water of wet blue leather weight 200～300%, under the normal temperature, with 3 rev/mins rotational speed 10～15 minutes, discharge opeing; Degreasing places rotary drum with the wet blue leather after the washing, adds the water of wet blue leather weight 150～200% and 0.3%～1% non-ionic type grease-removing agent peregal, at 35～40 ℃, with 3 rev/mins rotational speed 20～60 minutes; The concentration that adds wet blue leather weight 0.2%～0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 10～15 minutes, and discharge opeing; Retanning places rotary drum with the wet blue leather after the degreasing, adds the water of wet blue leather weight 100% and 1～4% modified glutaraldehyde, at 40 ℃～45 ℃, with 3 rev/mins rotational speed 40～60 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 40～60 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 20～30 minutes, discharge opeing; The water that adds wet blue leather weight 200～300% subsequently, with 3 rev/mins rotational speed 10～15 minutes, discharge opeing; Neutralization places rotary drum with the wet blue leather after the retanning, adds the water of wet blue leather weight 100～150% and 0.2% sodium bisulfite, at 30 ℃～35 ℃, with 3 rev/mins rotational speed 15～30 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 40～60 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1～1.5% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 20～30 minutes, and discharge opeing; Retanning/dyeing/stuffing, wet blue leather after the neutralization is placed rotary drum, add the water of wet blue leather weight 100～150% and 2～4% synthetic tanning agent R-6 or R-7, at 40～45 ℃, with 3 rev/mins rotational speed 30～40 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2～4% and 0～4% myrica extract again, with 3 rev/mins rotational speed 40～60 minutes, the dyestuff that adds wet blue leather weight 2～5% again, with 3 rev/mins rotational speed after 40～60 minutes, the concentration that adds wet blue leather weight 0.3～0.5% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 15～20 minutes, the last concentration that adds wet blue leather weight 0.5～1.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 15～20 minutes, discharge opeing; The water that adds wet blue leather weight 200～300% subsequently, with 3 rev/mins rotational speed 10～15 minutes, discharge opeing got final product in rotary drum.
One of the tanning agent that the present invention at first adopts in retanning operation modified glutaraldehyde, its purpose are to prevent to greatest extent the generation of free chromium, fundamentally stop trivalent chromium and are oxidized to sexavalent chrome; The material sodium thiosulfate purpose that adds reductibility in later stage of retanning operation is to reduce the sexavalent chrome that produces in inferior operation in addition.Secondly adopt reductibility neutralizing agent sodium bisulfite and sodium thiosulfate in and in the operation, neutralizing agent sodium bisulfite and sodium thiosulfate are except neutralizing effect, also has the effect of reduction of hexavalent chromium, cooperate the use of retanning neutralizing agent PAK-N, further strengthen chromic cooperation, reduce free chromic generation; At last in retanning/dyeing/stuffing operation, in order to remedy fatting agent without raising finished leather softnesses such as sulfited fish oil (producing chromic one of the main reasons), fullness, adding multiple fatting agent is used, both ensured and prevented from chromic generation from can ensure not reducing of leather softness, fullness etc. again.
Embodiment
Embodiment 1, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 300%, and under the normal temperature, with 3 rev/mins rotational speed 13 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 180% and 0.5% non-ionic type grease-removing agent peregal, at 40 ℃, with 3 rev/mins rotational speed 20 minutes; The concentration that adds wet blue leather weight 0.3% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 13 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 4% modified glutaraldehyde, at 45 ℃, with 3 rev/mins rotational speed 60 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 40 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 20 minutes, discharge opeing; The water that adds wet blue leather weight 260% subsequently, with 3 rev/mins rotational speed 15 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 100% and 0.2% sodium bisulfite, at 35 ℃, with 3 rev/mins rotational speed 26 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 48 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.2% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 30 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 150% and 4% synthetic tanning agent R-6, at 42 ℃, with 3 rev/mins rotational speed 40 minutes, the acrylate resin tanning agent ART-1 that adds wet blue leather weight 4% again, with 3 rev/mins rotational speed 45 minutes, the dyestuff that adds wet blue leather weight 5% again, with 3 rev/mins rotational speed after 48 minutes, the concentration that adds wet blue leather weight 0.3% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with the rotational speed of 3 rev/mins of kinds 15 minutes, the last concentration that adds wet blue leather weight 1.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 15 minutes, discharge opeing; The water that adds wet blue leather weight 300% subsequently, with 3 rev/mins rotational speed 10 minutes, discharge opeing got final product in rotary drum.
Embodiment 2, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 200%, and under the normal temperature, with 3 rev/mins rotational speed 11 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 1 50% and 0.3% non-ionic type grease-removing agent peregal, at 38 ℃, with 3 rev/mins rotational speed 45 minutes; The concentration that adds wet blue leather weight 0.2% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 11 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 2% modified glutaraldehyde, at 42 ℃, with 3 rev/mins rotational speed 40 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 45 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 26 minutes, discharge opeing; The water that adds wet blue leather weight 250% subsequently, with 3 rev/mins rotational speed 12 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 120% and 0.2% sodium bisulfite, at 32 ℃, with 3 rev/mins rotational speed 18 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 52 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.4% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 26 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 100% and 3% synthetic tanning agent R-7, at 44 ℃, with 3 rev/mins rotational speed 30 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2% and 2% myrica extract again, with 3 rev/mins rotational speed 50 minutes, the dyestuff that adds wet blue leather weight 3% again, with 3 rev/mins rotational speed after 52 minutes, the concentration that adds wet blue leather weight 0.5% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 17 minutes, the last concentration that adds wet blue leather weight 0.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 18 minutes, discharge opeing; The water that adds wet blue leather weight 200% subsequently, with 3 rev/mins rotational speed 13 minutes, discharge opeing got final product in rotary drum.
Embodiment 3, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 280%, and under the normal temperature, with 3 rev/mins rotational speed 15 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 200% and 0.8% non-ionic type grease-removing agent peregal, at 35 ℃, with 3 rev/mins rotational speed 55 minutes; The concentration that adds wet blue leather weight 0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 15 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 1% modified glutaraldehyde, 44, with 3 rev/mins rotational speed 45 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 55 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 23 minutes, discharge opeing; The water that adds wet blue leather weight 300% subsequently, with 3 rev/mins rotational speed 14 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 140% and 0.2% sodium bisulfite, at 30 ℃, with 3 rev/mins rotational speed 15 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 40 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.0% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 23 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 120% and 2% synthetic tanning agent R-6, at 40 ℃, with 3 rev/mins rotational speed 36 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 3% and 4% myrica extract again, with 3 rev/mins rotational speed 55 minutes, the dyestuff that adds wet blue leather weight 2% again, with 3 rev/mins rotational speed after 40 minutes, the concentration that adds wet blue leather weight 0.4% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 19 minutes, the last concentration that adds wet blue leather weight 0.8% again is 10% formic acid solution, with 3 rev/mins rotational speed 16 minutes, discharge opeing; The water that adds wet blue leather weight 280% subsequently, with 3 rev/mins rotational speed 15 minutes, discharge opeing got final product in rotary drum.
Embodiment 4, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 250%, and under the normal temperature, with 3 rev/mins rotational speed 12 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 170% and 1.0% non-ionic type grease-removing agent peregal, at 37 ℃, with 3 rev/mins rotational speed 30 minutes; The concentration that adds wet blue leather weight 0.4% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 12 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 3% modified glutaraldehyde, at 40 ℃, with 3 rev/mins rotational speed 55 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 60 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 30 minutes, discharge opeing; The water that adds wet blue leather weight 200% subsequently, with 3 rev/mins rotational speed 10 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 130% and 0.2% sodium bisulfite, at 34 ℃, with 3 rev/mins rotational speed 30 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 56 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.3% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 20 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 140% and 2% synthetic tanning agent R-7, at 45 ℃, with 3 rev/mins rotational speed 38 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 3% and 3% myrica extract again, with the rotational speed of 3 rev/mins of kinds 40 minutes, the dyestuff that adds wet blue leather weight 4% again, with 3 rev/mins rotational speed after 56 minutes, the concentration that adds wet blue leather weight 0.3% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 16 minutes, the last concentration that adds wet blue leather weight 1.2% again is 10% formic acid solution, with 3 rev/mins rotational speed 19 minutes, discharge opeing; The water that adds wet blue leather weight 250% subsequently, with 3 rev/mins rotational speed 11 minutes, discharge opeing got final product in rotary drum.
Embodiment 5, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 230%, and under the normal temperature, with 3 rev/mins rotational speed 10 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 190% and 0.7% non-ionic type grease-removing agent peregal, at 36 ℃, with 3 rev/mins rotational speed 60 minutes; The concentration that adds wet blue leather weight 0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 10 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 4% modified glutaraldehyde, at 43 ℃, with 3 rev/mins rotational speed 43 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 43 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 28 minutes, discharge opeing; The water that adds wet blue leather weight 230% subsequently, with 3 rev/mins rotational speed 13 minutes, discharge opeing; In: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 110% and 0.2% sodium bisulfite, at 31 ℃, with 3 rev/mins rotational speed 20 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 60 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.5% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 25 minutes, and discharge opeing; Retanning/dyeing/stuffing: the back wet blue leather that will neutralize places rotary drum, add the water of wet blue leather weight 130% and 4% synthetic tanning agent R-6, at 43 ℃, with 3 rev/mins rotational speed 32 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2% and 2% myrica extract again, with 3 rev/mins rotational speed 60 minutes, the dyestuff that adds wet blue leather weight 2% again, with 3 rev/mins rotational speed after 60 minutes, the concentration that adds wet blue leather weight 0.4% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 18 minutes, the last concentration that adds wet blue leather weight 1.0% again is 10% formic acid solution, with 3 rev/mins rotational speed 20 minutes, discharge opeing; The water that adds wet blue leather weight 230% subsequently, with 3 rev/mins rotational speed 14 minutes, discharge opeing got final product in rotary drum.
Embodiment 6, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 260%, and under the normal temperature, with 3 rev/mins rotational speed 14 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 160% and 0.4% non-ionic type grease-removing agent peregal, at 39 ℃, with 3 rev/mins rotational speed 26 minutes; The concentration that adds wet blue leather weight 0.2% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 14 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 1% modified glutaraldehyde, at 41 ℃, with 3 rev/mins rotational speed 57 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 57 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 25 minutes, discharge opeing; The water that adds wet blue leather weight 280% subsequently, with 3 rev/mins rotational speed 11 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 150% and 0.2% sodium bisulfite, at 33 ℃, with 3 rev/mins rotational speed 23 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 50 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.1% with 3 rev/mins rotational speed again, with the rotational speed in 3 rev/mins 28 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 110% and 3% synthetic tanning agent R-7, at 41 ℃, with 3 rev/mins rotational speed 35 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 4% and 4% myrica extract again, with 3 rev/mins rotational speed 48 minutes, the dyestuff that adds wet blue leather weight 5% again, with 3 rev/mins rotational speed after 50 minutes, the concentration that adds wet blue leather weight 0.5% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 20 minutes, the last concentration that adds wet blue leather weight 1.1% again is 10% formic acid solution, with 3 rev/mins rotational speed 17 minutes, discharge opeing; The water that adds wet blue leather weight 260% subsequently, with 3 rev/mins rotational speed 12 minutes, discharge opeing got final product in rotary drum.
The present invention is prevented on each link that sexavalent chrome is easy to generate, and does not influence the performance of finished leather simultaneously again.Carry out chrome-tanned production according to method provided by the present invention, and detect 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 finished leather, sometimes not even greater than 2mg/kg (2 milligrams of chromium of every kilogram of leather sample), meet international standard.
Claims (7)
1, the production method of content of 6-valence Cr ions leather up to standard is characterized in that:
1) washing places rotary drum with wet blue leather, adds the water of wet blue leather weight 200～300%, under the normal temperature, and with 3 rev/mins rotational speed 10～15 minutes, discharge opeing;
2) degreasing places rotary drum with the wet blue leather after the washing, adds the water of wet blue leather weight 150～200% and 0.3%～1% non-ionic type grease-removing agent peregal, at 35～40 ℃, with 3 rev/mins rotational speed 20～60 minutes; The concentration that adds wet blue leather weight 0.2%～0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 10～15 minutes, and discharge opeing;
3) retanning places rotary drum with the wet blue leather after the degreasing, adds the water of wet blue leather weight 100% and 1～4% modified glutaraldehyde, at 40 ℃～45 ℃, with 3 rev/mins rotational speed 40～60 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 40～60 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 20～30 minutes, discharge opeing; The water that adds wet blue leather weight 200～300% subsequently, with 3 rev/mins rotational speed 10～15 minutes, discharge opeing;
4) neutralization places rotary drum with the wet blue leather after the retanning, adds the water of wet blue leather weight 100～150% and 0.2% sodium bisulfite, at 30 ℃～35 ℃, with 3 rev/mins rotational speed 15～30 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 40～60 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1～1.5% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 20～30 minutes, and discharge opeing;
5) retanning/dyeing/stuffing, wet blue leather after the neutralization is placed rotary drum, add the water of wet blue leather weight 100～150% and 2～4% synthetic tanning agent R-6 or R-7, at 40～45 ℃, with 3 rev/mins rotational speed 30～40 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2～4% and 0～4% myrica extract again, with 3 rev/mins rotational speed 40～60 minutes, the dyestuff that adds wet blue leather weight 2～5% again, with 3 rev/mins rotational speed after 40～60 minutes, the concentration that adds wet blue leather weight 0.3～0.5% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 15～20 minutes, the last concentration that adds wet blue leather weight 0.5～1.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 15～20 minutes, discharge opeing; The water that adds wet blue leather weight 200～300% subsequently, with 3 rev/mins rotational speed 10～15 minutes, discharge opeing got final product in rotary drum.
2, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 300%, and under the normal temperature, with 3 rev/mins rotational speed 13 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 180% and 0.5% non-ionic type grease-removing agent peregal, at 40 ℃, with 3 rev/mins rotational speed 20 minutes; The concentration that adds wet blue leather weight 0.3% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 13 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 4% modified glutaraldehyde, at 45 ℃, with 3 rev/mins rotational speed 60 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 40 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 20 minutes, discharge opeing; The water that adds wet blue leather weight 260% subsequently, with 3 rev/mins rotational speed 15 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 100% and 0.2% sodium bisulfite, at 35 ℃, with 3 rev/mins rotational speed 26 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 48 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.2% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 30 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 150% and 4% synthetic tanning agent R-6, at 42 ℃, with 3 rev/mins rotational speed 40 minutes, the acrylate resin tanning agent ART-1 that adds wet blue leather weight 4% again, with 3 rev/mins rotational speed 45 minutes, the dyestuff that adds wet blue leather weight 5% again, with 3 rev/mins rotational speed after 48 minutes, the concentration that adds wet blue leather weight 0.3% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution with 3 rev/mins rotational speed 15 minutes, the last concentration that adds wet blue leather weight 1.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 15 minutes, discharge opeing; The water that adds wet blue leather weight 300% subsequently, with 3 rev/mins rotational speed 10 minutes, discharge opeing got final product in rotary drum.
3, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: at first, washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 200%, under the normal temperature, with 3 rev/mins rotational speed 11 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 150% and 0.3% non-ionic type grease-removing agent peregal, at 38 ℃, with 3 rev/mins rotational speed 45 minutes; The concentration that adds wet blue leather weight 0.2% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 11 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 2% modified glutaraldehyde, at 42 ℃, with 3 rev/mins rotational speed 40 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 45 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 26 minutes, discharge opeing; The water that adds wet blue leather weight 250% subsequently, with 3 rev/mins rotational speed 12 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 120% and 0.2% sodium bisulfite, at 32 ℃, with 3 rev/mins rotational speed 18 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 52 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.4% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 26 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 100% and 3% synthetic tanning agent R-7, at 44 ℃, with 3 rev/mins rotational speed 30 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2% and 2% myrica extract again, with 3 rev/mins rotational speed 50 minutes, the dyestuff that adds wet blue leather weight 3% again, with 3 rev/mins rotational speed after 52 minutes, the concentration that adds wet blue leather weight 0.5% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 17 minutes, the last concentration that adds wet blue leather weight 0.5% again is 10% formic acid solution, with 3 rev/mins rotational speed 18 minutes, discharge opeing; The water that adds wet blue leather weight 200% subsequently, with 3 rev/mins rotational speed 13 minutes, discharge opeing got final product in rotary drum.
4, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 280%, and under the normal temperature, with 3 rev/mins rotational speed 15 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 200% and 0.8% non-ionic type grease-removing agent peregal, at 35 ℃, with 3 rev/mins rotational speed 55 minutes; The concentration that adds wet blue leather weight 0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 15 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 1 00% and 1% modified glutaraldehyde, 44, with 3 rev/mins rotational speed 45 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 55 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 23 minutes, discharge opeing; The water that adds wet blue leather weight 300% subsequently, with 3 rev/mins rotational speed 14 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 140% and 0.2% sodium bisulfite, at 30 ℃, with 3 rev/mins rotational speed 15 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 40 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.0% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 23 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 120% and 2% synthetic tanning agent R-6, at 40 ℃, with 3 rev/mins rotational speed 36 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 3% and 4% myrica extract again, with 3 rev/mins rotational speed 55 minutes, the dyestuff that adds wet blue leather weight 2% again, with 3 rev/mins rotational speed after 40 minutes, the concentration that adds wet blue leather weight 0.4% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 19 minutes, the last concentration that adds wet blue leather weight 0.8% again is 10% formic acid solution, with 3 rev/mins rotational speed 16 minutes, discharge opeing; The water that adds wet blue leather weight 280% subsequently, with 3 rev/mins rotational speed 15 minutes, discharge opeing got final product in rotary drum.
5, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 250%, and under the normal temperature, with 3 rev/mins rotational speed 12 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 170% and 1.0% non-ionic type grease-removing agent peregal, at 37 ℃, with 3 rev/mins rotational speed 30 minutes; The concentration that adds wet blue leather weight 0.4% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 12 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 3% modified glutaraldehyde, at 40 ℃, with 3 rev/mins rotational speed 55 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 60 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 30 minutes, discharge opeing; The water that adds wet blue leather weight 200% subsequently, with 3 rev/mins rotational speed 10 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 130% and 0.2% sodium bisulfite, at 34 ℃, with 3 rev/mins rotational speed 30 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 56 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.3% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 20 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 140% and 2% synthetic tanning agent R-7, at 45 ℃, with 3 rev/mins rotational speed 38 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 3% and 3% myrica extract again, with 3 rev/mins rotational speed 40 minutes, the dyestuff that adds wet blue leather weight 4% again, with 3 rev/mins rotational speed after 56 minutes, the concentration that adds wet blue leather weight 0.3% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 16 minutes, the last concentration that adds wet blue leather weight 1.2% again is 10% formic acid solution, with 3 rev/mins rotational speed 19 minutes, discharge opeing; The water that adds wet blue leather weight 250% subsequently, with 3 rev/mins rotational speed 11 minutes, discharge opeing got final product in rotary drum.
6, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 230%, and under the normal temperature, with 3 rev/mins rotational speed 10 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 190% and 0.7% non-ionic type grease-removing agent peregal, at 36 ℃, with 3 rev/mins rotational speed 60 minutes; The concentration that adds wet blue leather weight 0.5% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 10 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 4% modified glutaraldehyde, at 43 ℃, with 3 rev/mins rotational speed 43 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 43 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 28 minutes, discharge opeing; The water that adds wet blue leather weight 230% subsequently, with 3 rev/mins rotational speed 13 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 110% and 0.2% sodium bisulfite, at 31 ℃, with 3 rev/mins rotational speed 20 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 60 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.5% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 25 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 130% and 4% synthetic tanning agent R-6, at 43 ℃, with 3 rev/mins rotational speed 32 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 2% and 2% myrica extract again, with 3 rev/mins rotational speed 60 minutes, the dyestuff that adds wet blue leather weight 2% again, with 3 rev/mins rotational speed after 60 minutes, the concentration that adds wet blue leather weight 0.4% was 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 18 minutes, the last concentration that adds wet blue leather weight 1.0% again is 10% formic acid solution, with 3 rev/mins rotational speed 20 minutes, discharge opeing; The water that adds wet blue leather weight 230% subsequently, with 3 rev/mins rotational speed 14 minutes, discharge opeing got final product in rotary drum.
7, the production method of content of 6-valence Cr ions according to claim 1 leather up to standard is characterized in that: washing: wet blue leather is placed rotary drum, add the water of wet blue leather weight 260%, and under the normal temperature, with 3 rev/mins rotational speed 14 minutes, discharge opeing; Degreasing: the wet blue leather after will washing places rotary drum, adds the water of wet blue leather weight 160% and 0.4% non-ionic type grease-removing agent peregal, at 39 ℃, with 3 rev/mins rotational speed 26 minutes; The concentration that adds wet blue leather weight 0.2% subsequently again is 10% formic acid solution, with 3 rev/mins rotational speed 14 minutes, and discharge opeing; Retanning: the wet blue leather after the degreasing is placed rotary drum, add the water of wet blue leather weight 100% and 1% modified glutaraldehyde, at 41 ℃, with 3 rev/mins rotational speed 57 minutes; The chromium powder that adds wet blue leather weight 4% again was with 3 rev/mins rotational speed 57 minutes; The sodium thiosulfate that adds wet blue leather weight 0.4% again, with 3 rev/mins rotational speed 25 minutes, discharge opeing; The water that adds wet blue leather weight 280% subsequently, with 3 rev/mins rotational speed 11 minutes, discharge opeing; Neutralization: the wet blue leather after the retanning is placed rotary drum, add the water of wet blue leather weight 150% and 0.2% sodium bisulfite, at 33 ℃, with 3 rev/mins rotational speed 23 minutes; The sodium thiosulfate that adds wet blue leather weight 1.5% again after 50 minutes, adds the neutralizing retanning agent PAK-N of wet blue leather weight 1.1% with 3 rev/mins rotational speed again, with 3 rev/mins rotational speed 28 minutes, and discharge opeing; Retanning/dyeing/stuffing: the wet blue leather after will neutralizing places rotary drum, add the water of wet blue leather weight 110% and 3% synthetic tanning agent R-7, at 41 ℃, with 3 rev/mins rotational speed 35 minutes, add the acrylate resin tanning agent ART-1 of wet blue leather weight 4% and 4% myrica extract again, with 3 rev/mins rotational speed 48 minutes, the dyestuff that adds wet blue leather weight 5% again, with 3 rev/mins rotational speed after 50 minutes, add wet blue leather weight 0.5% concentration and be 10% formic acid solution, with 3 rev/mins rotational speed 30 minutes; Add sulphiting modified wool fat fatting agent, 5% synthetic fat liquor SES201,5% SCF synthetic fat liquor, 4% the compound fatting agent of DF, 0.1% gallic acid, 0.1% the Resorcinol of wet blue leather weight 1% and 1% concentration again and be 10% formic acid solution, with 3 rev/mins rotational speed 20 minutes, the last concentration that adds wet blue leather weight 1.1% again is 10% formic acid solution, with 3 rev/mins rotational speed 17 minutes, discharge opeing; The water that adds wet blue leather weight 260% subsequently, with 3 rev/mins rotational speed 12 minutes, discharge opeing got final product in rotary drum.
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| CN101985668A (en) * | 2010-05-04 | 2011-03-16 | 张壮斗 | Leather making process for retanning by indefinitely recycling waste liquid |
| CN102534059B (en) * | 2010-12-14 | 2015-12-09 | 张壮斗 | A kind of recycle waste liquid carries out the leather-making technology of retanning |
| CN102732649B (en) * | 2012-06-15 | 2014-08-20 | 海宁森德皮革有限公司 | Production process of automobile interior decorative leather with ultralow total carbon emission |
| CN103469312B (en) * | 2013-08-19 | 2016-03-02 | 佛山捷利再生科技有限公司 | A kind of environment-friendlyleather leather pulp belt material and production technology thereof |
| WO2017131139A1 (en) * | 2016-01-29 | 2017-08-03 | シチズン時計株式会社 | Hexavalent chromium treatment agent, and leather or leather product using same |
| CN106350618B (en) * | 2016-08-30 | 2018-06-29 | 晋江市永建皮革制品有限公司 | The production method of breathable environment-protective leather |
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|---|---|---|---|---|
| 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 |
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| 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 |
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| 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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Assignee: Ruixin Group Co., Ltd. Assignor: Shaanxi University of Science and Technology Contract fulfillment period: 2007.8.22 to 2014.8.21 contract change Contract record no.: 2009330001556 Denomination of invention: Production method of leather in which hexavalent chromium content reaches the standard Granted publication date: 20070822 License type: Exclusive license Record date: 2009.7.3 |
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