CN109439810B - Process for preparing high-grade sheep garment fur leather by using chromium-free multi-metal tanning agent - Google Patents
Process for preparing high-grade sheep garment fur leather by using chromium-free multi-metal tanning agent Download PDFInfo
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- 239000010985 leather Substances 0.000 title claims abstract description 78
- 241001494479 Pecora Species 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000002184 metal Substances 0.000 title claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 122
- 238000012545 processing Methods 0.000 claims abstract description 10
- 210000002268 wool Anatomy 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 238000005554 pickling Methods 0.000 claims description 59
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 25
- 235000019253 formic acid Nutrition 0.000 claims description 25
- 230000003472 neutralizing effect Effects 0.000 claims description 25
- 239000004902 Softening Agent Substances 0.000 claims description 21
- 238000006386 neutralization reaction Methods 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 235000013372 meat Nutrition 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000001238 wet grinding Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 235000021110 pickles Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 36
- 238000005516 engineering process Methods 0.000 abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000003889 chemical engineering Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Abstract
The invention relates to the technical field of fur leather processing, in particular to a process for preparing high-grade sheep clothing fur leather by using a chromium-free polymetallic tanning agent. The invention relates to a processing technology of white fur leather, and a finished product finally obtained is full and soft in hand feeling, white in fur color and leather board color, short and thin in board surface wool, washable and yellowing-resistant, and is particularly suitable for manufacturing high-grade natural color and light color fur leather products. The technology does not use a chrome tanning agent, can avoid the pollution of three wastes containing chromium and completely eradicate the harm of hexavalent chromium; can effectively reduce COD in the wastewater in the tanning process and simultaneously control volatile organic compounds in the fur leather.
Description
Technical Field
The invention relates to the technical field of fur leather processing, in particular to a process for preparing high-grade sheep garment fur leather by using a chromium-free multi-metal tanning agent.
Background
Chrome tanning always occupies an absolutely leading position in the field of tanning wool leather of sheep leather clothing, but with the improvement and the limitation of the state on the discharge standard of the wool leather industry, the cost for treating chromium-containing wastewater is multiplied, and the development of the wool leather industry is seriously limited. Therefore, the research of the method for tanning which can replace chrome tanning is a focus in recent years, and the main research directions of the chrome-free tanning of the leather currently include methods such as aldehyde tanning, aluminum tanning, vegetable tanning, modified organic tanning and the like, but the methods all have defects of different degrees. The leather obtained by the aldehyde tanning method has the phenomena of yellowing, tanning removal and the like after being stored for a long time, and can slowly release free formaldehyde to cause harm to human bodies. The aluminum tanning method is easy to remove the tanning after washing. The hides obtained by the vegetable tanning method and the modified organic tanning method have low shrinkage temperature and poor hide hand feeling, and simultaneously, the requirements of subsequent high-temperature fatliquoring for a long time and dyeing of the fur and the quilt are difficult to meet.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a technology for preparing high-grade sheep clothing fur leather by using a chromium-free polymetallic tanning agent, so as to solve the problems of high harm of waste chromium, poor water washing resistance of aluminum tanning, poor storage resistance of aldehyde tanning, poor hand feeling of vegetable tanning and organic tanning and the like in the prior art. The process can effectively reduce COD in the tanning wastewater, and the produced fur leather is white in color and can not be subjected to the phenomena of tanning and yellowing after being placed for a long time.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, carrying out rewetting,
step two, spin-drying the mixture,
step three, shearing the wool,
step four, the main soaking step is to soak water,
step five, removing the meat,
step six, degreasing the mixture,
step seven, softening and pickling the mixture,
firstly, adding fur into a softening pickling solution, wherein the using amount of the softening pickling solution is 20-40% of the mass ratio of water to the fur in the softening pickling solution, the temperature is adjusted to be 30-40 ℃, the fur is treated for 10-24h, and the fur is rotated for 5-10min per hour along with intermittent rotation;
then, 1.0-5.0g/l of pickling fatting agent CP-996 (Smit & zonon), 10-20 g/l of fur pickling agent MN (Deshel chemical engineering) or 5-15 g/l of pickling auxiliary agent PA (Desri leather technology) are added into the mixture, the pH is adjusted to 2.4-2.9, the temperature is adjusted to 20-30 ℃, the mixture is treated for 48-72 h and rotates for 40-60 min every 4h along with intermittent rotation, and then the mixture is taken out and kept stand for more than 7 days;
step eight, tanning the raw materials,
step nine, wet grinding is carried out,
step ten, retanning the mixture,
step eleven, neutralizing the mixture,
step twelve, adding grease,
step thirteen, dry finishing,
and step fourteen, obtaining a finished product.
Preferably, the ratio of the softening pickle liquor in the seventh step is as follows:
1-2 g/l of weak organic acid Bascal S (BSAF),
1-4 g/l of acid softening enzyme DVP (Delhi leather technology) or acid softening enzyme WB (Delhi leather technology),
20-30 g/l of industrial salt,
the balance of water.
The softening pickling of the invention does not adopt the conventional formic acid or sulfuric acid pickling mode, but uses weak organic acid such as polybasic alcohol acid and polybasic carboxylic acid to carry out the pickling and the mild softening.
Preferably, the step eight tanning step is as follows:
firstly, regulating the pH value of tanning liquid to be 2.4-2.9 and the temperature to be 30-40 ℃, adding the fur treated in the last step, and treating for 30-60 min; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20-40;
the tanning liquor comprises the following components: 50-80 g/L of industrial salt, 1-3 g/L of industrial formic acid and the balance of water;
then, adding 2.0-4.0 g/l of tanning fatting agent EG-60 (Smit & zonon) and 2.0-12.0 g/l of softening agent TL (Smit & zonon), and treating for 30-60 min;
then, 2.0-7.0 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon) is added for processing for 30-60 min,
then adding 2.0-7.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 30-60 min,
then adding 15-30 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), treating for 60-120 min,
then adding 0.05-0.5 g/l of acid softening enzyme ABL (Murphy & Son), intermittently rotating for 20 min per hour, treating for 10-24h,
finally, adding 0.5-1.5 g/l of sodium carbonate, adding the sodium carbonate by 3-4 times, adjusting the pH to 3.9-4.4, intermittently rotating for 30 min per hour, and treating for 5-8 h.
Preferably, the step ten retanning steps are as follows:
firstly, adjusting the pH value of the retanning liquid to 3.0-3.5 and the temperature to 30-40 ℃, adding the fur after the last step of treatment, and treating for 30-60 min, wherein the using amount of the retanning liquid is added according to the mass ratio of water in the retanning liquid to the fur of 20-40;
the retanning liquid comprises the following components: 0.5-1.5 g/L of industrial formic acid, and the balance of water;
then adding tanning fatting agent EG-60 (Smit & zon) 1.0-2.0 g/l and softening agent TL (Smit & zon) 1.0-4.0 g/l, treating for 30-60 min,
then adding 1.0-4.0 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon), treating for 30-60 min,
then adding 1.0-4.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 30-60 min,
then adding 5-15 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), treating for 60-120 min,
then adding 0.05-0.5 g/l of acid softening enzyme ABL (Murphy & Son), treating for 2-4 h,
then adding 1-2 g/l baking soda, adding 3-4 times, adjusting pH to 3.9-4.4, intermittently rotating for 30 min per hour for 10-24 h.
Preferably, in the step eleven of neutralizing,
firstly, adjusting the pH value of the neutralization solution to 5.5-6.5, and adding the fur treated in the previous step; the dosage of the neutralizing liquid is added according to the mass ratio of water to fur in the neutralizing liquid of 20-40;
the neutralizing solution comprises the following components: 1-4 g/L industrial sodium acetate, 1.0-4.0 g/L neutralization auxiliary agent NN-555 (Smit & zonon), 0.05-0.5 g/L acid softening enzyme ABL (Murphy & Son), and the balance of water
Then, the treatment is carried out for 120-180 min at the temperature of 30-40 ℃.
Preferably, the step twelve fat adding steps are as follows:
firstly, adding the fur treated in the last step into a fatliquoring solution, wherein the using amount of the fatliquoring solution is added according to the mass ratio of water to the fur in the fatliquoring solution of 20-40; then, adjusting the pH value to 3.8-4.0 at the temperature of 50-60 ℃, treating for 120-180 min,
the fat liquor comprises the following components:
1.0-4.0 g/l of softening agent TL (Smit & zon),
fatting agent GF (Delauer leather technology) 1.0-4.0 g/l,
1.0-4.0 g/l of fatting agent PD-990 (Smit & zon),
fatting agent YY-707 (Smit & zon) 1.0-4.0 g/l,
fatting agent DPF (Deshel chemical industry) 1.0-4.0 g/l,
filler DR-686 (Smit & zon) 1.0-4.0 g/l,
0.5-1.5 g/l of industrial formic acid.
Preferably, in the step eight, the step ten and the step eleven, the pH activity of the acid softening enzyme ABL ranges from 1 to 7.
The invention aims to develop a technology for preparing high-grade sheep clothing fur leather by using a chromium-free polymetallic tanning agent, obtains a fur leather product which is soft and plump and has the same hand feeling as the existing high-grade sheep clothing fur leather through a whole set of process adjustment, has the advantages of white fur color and leather plate color, water washing resistance and yellowing resistance, and is particularly suitable for preparing high-grade natural color and light color fur leather products. The technology does not use a chrome tanning agent, can avoid the pollution of three wastes containing chromium and completely eradicate the harm of hexavalent chromium; the COD in the wastewater can be effectively reduced in the tanning process, and meanwhile, the volatile organic compounds in the fur leather are controlled; does not contain aldehyde tanning agent and does not generate free formaldehyde; the tanning effect is good, the shrinkage temperature can reach more than 90 ℃, and the requirement of normal fur leather production on the shrinkage temperature is completely met. The technology has wide application prospect and can completely replace the normal production of the fur leather.
Compared with the prior art, the invention has the beneficial effects that:
the sheep clothing fur leather produced by ZT601 tanning and the matched process has low COD content of the waste water of the tanning process, is easy to treat, does not use substances containing aldehyde tanning agents in the tanning process, and does not have free formaldehyde in the product. The process is safe and environment-friendly, and meanwhile, the produced sheep fur leather product is resistant to water washing, the leather plate is soft and full, the hand feeling is consistent with that of the product on the market at present, the leather plate and the fur color are white, the phenomena of tanning, yellowing and the like can not occur even if the sheep fur leather product is stored for a long time, and the method is suitable for manufacturing white and light-color top-grade fur leather clothing products.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1:
a process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, carrying out rewetting,
step two, spin-drying the mixture,
step three, shearing the wool,
step four, the main soaking step is to soak water,
step five, removing the meat,
step six, degreasing the mixture,
the steps from the first step to the sixth step are conventional processes.
Step seven, softening pickling acid, wherein the ratio of the softening pickling acid is as follows:
weak organic acid Bascal S (BSAF) 1.2 g/l,
4 g/l of acid softening enzyme DVP (Deri leather technology) or acid softening enzyme WB (Deri leather technology),
20 g/l of industrial salt is added,
the balance of water.
The method comprises the following steps:
firstly, adding fur into a softening pickling solution, wherein the using amount of the softening pickling solution is 30 according to the mass ratio of water to the fur in the softening pickling solution, the temperature is adjusted to be 40 ℃, the fur is treated for 10 hours, and the fur is rotated for 6min per hour along with intermittent rotation;
then, 5.0g/l of pickling fatliquor CP-996 (Smit & zonon), 10 g/l of fur pickling agent MN (Deshel chemical engineering) or 10 g/l of pickling auxiliary agent PA (Delhi leather technology) are added into the mixture, the pH is adjusted to 2.9, the temperature is adjusted to 20 ℃, the mixture is treated for 60 hours and rotates intermittently for 60 minutes every 4 hours, and then the mixture is taken out and kept stand for 7 days;
step eight, tanning, which comprises the following steps:
firstly, regulating the pH value of tanning liquid to be 2.4 and the temperature to be 35 ℃, adding the fur treated in the last step, and treating for 60 min; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20;
the tanning liquor comprises the following components: 560 g/L of industrial salt, 3g/L of industrial formic acid and the balance of water;
then, 2.0 g/l of tanning fatting agent EG-60 (Smit & zon) and 8.0 g/l of softening agent TL (Smit & zon) are added for treatment for 60 min;
then, 2.0 g/l of acrylic acid syntan RS-540 (Smit & zonon) is added for 50 min of treatment,
then adding 7.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 30 min,
then adding 20 g/l of chrome-free multi-metal tanning agent ZT-601 (Jinkun chemical industry), treating for 120 min,
then adding 0.05 g/l of acid softening enzyme ABL (Murphy & Son), intermittently rotating for 20 min per hour, treating for 15 h,
finally, 1.5 g/l of soda ash is added and added for 3 times, the pH value is adjusted to 4.0, the batch rotation is carried out, the rotation is carried out for 30 min per hour, and the treatment is carried out for 8 h.
Step nine, wet grinding is carried out,
step ten, retanning, wherein the retanning step is as follows:
firstly, adjusting the pH value of the retanning liquid to 3.0 and the temperature to 35 ℃, adding the fur treated in the last step, and treating for 60 min, wherein the using amount of the retanning liquid is added according to the mass ratio of water in the retanning liquid to the fur of 20;
the retanning liquid comprises the following components: 1 g/L of industrial formic acid, and the balance of water;
then, 2.0 g/l of tanning fatting agent EG-60 (Smit & zon) and 1.0g/l of softening agent TL (Smit & zon) are added, the treatment time is 40 min,
then adding 4.0 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon), treating for 30 min,
then adding 3.0g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 60 min,
then adding 5g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), treating for 80 min,
then adding 0.5 g/l of acid softening enzyme ABL (Murphy & Son), treating for 2 h,
then, 1.5 g/l sodium bicarbonate was added, and added in 4 portions, the pH was adjusted to 3.9, and the batch was rotated for 30 min per hour for 12 hours.
Step eleven, neutralizing, and comprising the following steps:
firstly, adjusting the pH value of a neutralization solution to 6.5, and adding the fur treated in the previous step; the dosage of the neutralizing liquid is added according to the mass ratio of water in the neutralizing liquid to the fur of 20;
the neutralizing solution comprises the following components: 3g/L of industrial sodium acetate, 4.0 g/L of a neutralization auxiliary agent NN-555 (Smit & zon), 0.05 g/L of acid softening enzyme ABL (Murphy & Son), and the balance of water
Then, the treatment was carried out at a temperature of 36 ℃ for 180 min.
Step twelve, fat-liquoring, which comprises the following steps:
firstly, adding the fur treated in the last step into a fatliquoring solution, wherein the using amount of the fatliquoring solution is added according to the mass ratio of water to the fur in the fatliquoring solution of 20; then, adjusting the pH value to 4.0 at the temperature of 56 ℃, treating for 120 min,
the fat liquor comprises the following components:
softener TL (Smit & zon) 2.0 g/l,
fatting agent GF (Delauer leather technology) 4.0 g/l,
fatting agent PD-990 (Smit & zon) 1.0g/l,
fatting agent YY-707 (Smit & zon) 3.0g/l,
fatting agent DPF (Deshel chemical industry) 4.0 g/l,
filler DR-686 (Smit & zon) 1.0g/l,
1.0g/l of industrial formic acid.
Step thirteen, dry finishing,
and step fourteen, obtaining a finished product.
Example 2:
a process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, carrying out rewetting,
step two, spin-drying the mixture,
step three, shearing the wool,
step four, the main soaking step is to soak water,
step five, removing the meat,
step six, degreasing the mixture,
the steps from the first step to the sixth step are conventional processes.
Step seven, softening pickling acid, wherein the ratio of the softening pickling acid is as follows:
2 g/l of weak organic acid Bascal S (BSAF),
1 g/l of acid softening enzyme DVP (Deri leather technology) or acid softening enzyme WB (Deri leather technology),
23 g/l of industrial salt,
the balance of water.
The method comprises the following steps:
firstly, adding fur into a softening pickling solution, wherein the using amount of the softening pickling solution is carried out according to the mass ratio of water to the fur in the softening pickling solution of 40, the temperature is adjusted to be 30 ℃, the fur is treated for 14 hours, and the fur is rotated for 10min per hour along with intermittent rotation;
then, 1.0g/l of pickling fatliquor CP-996 (Smit & zonon), 15 g/l of fur pickling agent MN (Deshel chemical engineering) or 15 g/l of pickling auxiliary agent PA (Delaier leather technology) are added into the mixture, the pH is adjusted to 2.4, the temperature is adjusted to 25 ℃, the mixture is treated for 72 hours and rotates for 40 min every 4 hours along with intermittent rotation, and then the mixture is taken out and kept stand for 9 days;
step eight, tanning, which comprises the following steps:
firstly, regulating the pH value of tanning liquid to be 2.5 and the temperature to be 40 ℃, adding the fur treated in the last step, and treating for 30 min; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 30;
the tanning liquor comprises the following components: 80 g/L of industrial salt, 1 g/L of industrial formic acid and the balance of water;
then, adding 3.0g/l of tanning fatting agent EG-60 (Smit & zon) and 12.0 g/l of softening agent TL (Smit & zon), and treating for 30 min;
then, 5.0g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon) is added for 60 min of treatment,
then 2.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon) is added for 40 min of treatment,
then adding 30 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), treating for 60 min,
then adding 0.1 g/l of acid softening enzyme ABL (Murphy & Son), intermittently rotating for 20 min per hour, treating for 24h,
finally, 0.5 g/l of soda ash is added and added for 4 times, the pH value is adjusted to 4.4, the batch rotation is carried out, the rotation is carried out for 30 min per hour, and the treatment is carried out for 5 h.
Step nine, wet grinding is carried out,
step ten, retanning, wherein the retanning step is as follows:
firstly, adjusting the pH value of the retanning liquid to 3.2 and the temperature to 40 ℃, adding the fur treated in the last step, and treating for 30 min, wherein the using amount of the retanning liquid is added according to the mass ratio of water in the retanning liquid to the fur of 30;
the retanning liquid comprises the following components: 1.5 g/L of industrial formic acid, and the balance of water;
then adding 1.0g/l of tanning fatting agent EG-60 (Smit & zon) and 3.0g/l of softening agent TL (Smit & zon), treating for 60 min,
then adding 1.0g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon), treating for 40 min,
then adding 4.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 30 min,
then adding 10 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry) for processing for 120 min,
then adding 0.05 g/l of acid softening enzyme ABL (Murphy & Son), treating for 3 h,
then, 2 g/l of sodium bicarbonate was added, and the addition was carried out in 3 portions, the pH was adjusted to 4, and the batch rotation was carried out for 30 min per hour for 24 hours.
Step eleven, neutralizing, and comprising the following steps:
firstly, adjusting the pH value of the neutralization solution to 5.5, and adding the fur treated in the last step; the dosage of the neutralizing liquid is added according to the mass ratio of water to fur in the neutralizing liquid of 30;
the neutralizing solution comprises the following components: 4 g/L of industrial sodium acetate, 1.0g/L of neutralizing aid NN-555 (Smit & zon), 0.1 g/L of acid softening enzyme ABL (Murphy & Son), and the balance of water
Then, the treatment was carried out at a temperature of 40 ℃ for 120 min.
Step twelve, fat-liquoring, which comprises the following steps:
firstly, adding the fur treated in the last step into a fatliquoring solution, wherein the using amount of the fatliquoring solution is added according to the mass ratio of water to the fur in the fatliquoring solution being 30; then, adjusting the pH value to 3.8 at the temperature of 60 ℃, treating for 160 min,
the fat liquor comprises the following components:
4.0 g/l of softening agent TL (Smit & zon),
fatting agent GF (Delauer leather technology) 1.0g/l,
fatting agent PD-990 (Smit & zon) 2.0 g/l,
fatting agent YY-707 (Smit & zon) 4.0 g/l,
fatting agent DPF (Deshel chemical industry) 1.0g/l,
3.0g/l of filler DR-686 (Smit & zon),
1.5 g/l of industrial formic acid.
Step thirteen, dry finishing,
and step fourteen, obtaining a finished product.
Example 3:
a process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, carrying out rewetting,
step two, spin-drying the mixture,
step three, shearing the wool,
step four, the main soaking step is to soak water,
step five, removing the meat,
step six, degreasing the mixture,
the steps from the first step to the sixth step are conventional processes.
Step seven, softening pickling acid, wherein the ratio of the softening pickling acid is as follows:
weak organic acid Bascal S (BSAF) 1 g/l,
Acid softening enzyme DVP (Deri leather technology) or acid softening enzyme WB (Deri leather technology) 2 g/l,
30 g/l of industrial salt,
the balance of water.
The method comprises the following steps:
firstly, adding fur into a softening pickling solution, wherein the using amount of the softening pickling solution is carried out according to the mass ratio of water to the fur in the softening pickling solution of 20, the temperature is adjusted to be 35 ℃, the fur is treated for 24 hours, and the fur is rotated for 5min per hour along with intermittent rotation;
then 3.0g/l of pickling fatliquor CP-996 (Smit & zonon), 20 g/l of fur pickling agent MN (Deshel chemical engineering) or 5g/l of pickling auxiliary agent PA (Delaier leather technology) are added into the mixture, the pH is adjusted to 2.5, the temperature is adjusted to 30 ℃, the mixture is treated for 48 hours and rotates for 50 min every 4 hours along with intermittent rotation, and then the mixture is taken out and kept stand for 10 days;
step eight, tanning, which comprises the following steps:
firstly, regulating the pH value of tanning liquid to be 2.9 and the temperature to be 30 ℃, adding the fur treated in the last step, and treating for 40 min; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 40;
the tanning liquor comprises the following components: 50 g/L of industrial salt, 2 g/L of industrial formic acid and the balance of water;
then, 4.0 g/l of tanning fatting agent EG-60 (Smit & zon) and 2.0 g/l of softening agent TL (Smit & zon) are added for processing for 40 min;
then, 7.0 g/l of acrylic acid syntan RS-540 (Smit & zonon) is added for 30 min,
then adding 3.0g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 60 min,
then adding 15 g/l of chrome-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), treating for 80 min,
then adding 0.5 g/l of acid softening enzyme ABL (Murphy & Son), intermittently rotating for 20 min per hour, treating for 10h,
finally, 1 g/l of soda ash is added and added for 4 times, the pH value is adjusted to 3.9, the intermittent rotation is carried out, the rotation is carried out for 30 min per hour, and the treatment is carried out for 6 h.
Step nine, wet grinding is carried out,
step ten, retanning, wherein the retanning step is as follows:
firstly, adjusting the pH value of the retanning liquid to 3.5 and the temperature to 30 ℃, adding the fur treated in the last step, and treating for 40 min, wherein the using amount of the retanning liquid is added according to the mass ratio of water in the retanning liquid to the fur of 40;
the retanning liquid comprises the following components: 0.5 g/L of industrial formic acid, and the balance of water;
then adding 1.5 g/l of tanning fatting agent EG-60 (Smit & zonon) and 4.0 g/l of softening agent TL (Smit & zonon), treating for 30 min,
then, 3.0g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zonon) is added for treatment for 60 min,
then adding 1.0g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zonon), treating for 40 min,
then adding 15 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry) for treating for 60 min,
then adding 0.2 g/l of acid softening enzyme ABL (Murphy & Son), treating for 4h,
then, 1 g/l sodium bicarbonate was added, and the addition was carried out in 4 portions, the pH was adjusted to 4.4, and the batch rotation was carried out for 30 min per hour for 10 hours.
Step eleven, neutralizing, and comprising the following steps:
firstly, adjusting the pH value of a neutralization solution to 6, and adding the fur treated in the previous step; the dosage of the neutralizing liquid is added according to the mass ratio of water to the fur in the neutralizing liquid of 40;
the neutralizing solution comprises the following components: 1 g/L of industrial sodium acetate, 2.0 g/L of a neutralization auxiliary agent NN-555 (Smit & zon), 0.5 g/L of acid softening enzyme ABL (Murphy & Son), and the balance of water
Then, the treatment was carried out at 30 ℃ for 150 min.
Step twelve, fat-liquoring, which comprises the following steps:
firstly, adding the fur treated in the last step into a fatliquoring solution, wherein the using amount of the fatliquoring solution is added according to the mass ratio of water to the fur in the fatliquoring solution being 40; then, adjusting the pH value to 3.9 at the temperature of 50 ℃, treating for 180 min,
the fat liquor comprises the following components:
1.0g/l of softening agent TL (Smit & zon),
fatting agent GF (Delauer leather technology) 2.0 g/l,
fatting agent PD-990 (Smit & zon) 4.0 g/l,
fatting agent YY-707 (Smit & zon) 1.0g/l,
fatting agent DPF (Deshel chemical industry) 2.0 g/l,
filler DR-686 (Smit & zon) 4.0 g/l,
industrial formic acid 0.5 g/l.
Step thirteen, dry finishing,
and step fourteen, obtaining a finished product.
Example 4
A process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, rewetting: the same as the conventional process;
step two, spin-drying;
step three, shearing;
step four, main soaking: the same as the conventional process;
step five, removing meat;
step six, degreasing: the same as the conventional process;
step seven, softening and pickling: the softening pickling solution comprises the following components: 1.2 g/l of weak organic acid Bascal S (BSAF), 3g/l of acid softening enzyme DVP (Delhi leather technology), 20 g/l of industrial neutral salt and the balance of water; the dosage of the softening pickling liquor is added according to the mass ratio of water to fur in the softening pickling liquor of 20; adjusting the temperature to 30 ℃, adding hide, intermittently rotating for 10h, rotating for 5min every hour, then adding 1.5 g/l of pickling fatting agent CP-996 (Smit & zonon), 10 g/l of fur pickling agent MN (Deshel chemical industry), adjusting the pH to 2.5, reducing the temperature to 25 ℃, intermittently rotating for 40 min every 4 hours, and then taking out the hide and standing for more than 7 days;
step eight, tanning: the tanning liquor comprises the following components: 50 g/L of industrial neutral salt, 1.5 g/L of industrial formic acid and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20; adjusting pH to 2.9, adjusting temperature to 30 ℃, adding the leather for 60 min, then adding 2.0 g/l of tanning fatting agent EG-60 (Smit & zon), 6 g/l of softening agent TL (Smit & zon), 60 min, 2.0 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), 60 min, 2 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), 60 min, 20 g/l of chrome-free polymetallic tanning agent ZT-601 (gold chemical industry), 120 min, 0.05 g/l of acid softening enzyme ABL (Murphy & Son), intermittent rotation, 20 min per hour, 15 h, 1.5 g/l of soda, adding 4 times, adjusting pH to 4.4, intermittent rotation, 30 min per hour, 8 h;
step nine, wet grinding;
step ten, retanning: the retanning liquid comprises the following components: 0.8 g/L of industrial formic acid, and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20; adjusting pH to 3.3, adjusting temperature to 30 ℃, adding the leather for 30 min, then adding 1 g/l of tanning fatting agent EG-60 (Smit & zon), 1 g/l of softening agent TL (Smit & zon), 60 min, 1 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), 60 min, 1 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), 60 min, 15 g/l of chromium-free multi-metal tanning agent ZT-601 (gold Kun chemical industry), 120 min, 0.05 g/l of acid softening enzyme ABL (Murphy & Son), 4h, 1 g/l of baking soda, adding 4 times, adjusting pH to 3.9, intermittently rotating for 30 min per hour, and 10 h;
step eleven, neutralizing: the neutralization solution comprises the following components: the dosage of the neutralization solution is added according to the mass ratio of water to fur in tanning of 20; 4 g/L of industrial sodium acetate, 4 g/L of a neutralization auxiliary agent NN-555 (Smit & zon) and 0.1 g/L of acid softening enzyme ABL (Murphy & Son), adjusting the pH to 6.5, and keeping the temperature at 35 ℃ for 180 min;
step twelve, fat adding: the fat liquor comprises the following components: the dosage of the fat liquor is added according to the mass ratio of water to fur in tanning of 20; 3g/l of softener TL (Smit & zon), 4 g/l of fatting agent GF (Delry leather technology), 4 g/l of fatting agent PD-990 (Smit & zon), 2 g/l of fatting agent YY-707 (Smit & zon), 2 g/l of fatting agent DPF (Deshel chemical industry), 4 g/l of filler DR-686 (Smit & zon), and the pH value is adjusted to 3.8 by 1.8 g/l of industrial formic acid at the temperature of 55 ℃ for 180 min;
step thirteen, dry finishing: the same as the conventional process;
and step fourteen, obtaining a finished product.
Example 5
A process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, rewetting: the same as the conventional process;
step two, spin-drying;
step three, shearing;
step four, main soaking: the same as the conventional process;
step five, removing meat;
step six, degreasing: the same as the conventional process;
step seven, softening and pickling: the softening pickling solution comprises the following components: 2 g/l of weak organic acid Bascal S (BSAF), 4 g/l of acid softening enzyme WB (Delry leather technology), 25 g/l of industrial neutral salt and the balance of water; the dosage of the softening pickling liquor is added according to the mass ratio of water to fur in the softening pickling liquor of 25; adjusting the temperature to 35 ℃, adding the hide, intermittently rotating for 15 h, rotating for 10min every hour, then adding 2.5 g/l of pickling fatting agent CP-996 (Smit & zonon), 10 g/l of pickling aid PA (Delhi leather technology), adjusting the pH to 2.4, reducing the temperature to 20 ℃, intermittently rotating for 60 h every 4 hours for 50 min, and then taking out the hide and standing for more than 7 days;
step eight, tanning: the tanning liquor comprises the following components: 60 g/L of industrial neutral salt, 1 g/L of industrial formic acid and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 25; adjusting pH to 2.7, adjusting temperature to 35 ℃, adding the leather for 40 min, then adding 3g/l of tanning fatting agent EG-60 (Smit & zon), 8 g/l of softening agent TL (Smit & zon), adjusting time to 40 min, 3.0g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), adjusting time to 40 min, 4.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), adjusting time to 40 min, 30 g/l of chrome-free polymetallic tanning agent ZT-601 (gold chemical industry), adjusting time to 90 min, 0.1 g/l of acid softening enzyme ABL (Murphy & Son), intermittently rotating for 20 min, adjusting time to 15 h, 1.5 g/l of soda, adding 4 times, adjusting pH to 4.4, intermittently rotating for 30 min, and 8 h;
step nine, wet grinding;
step ten, retanning: the retanning liquid comprises the following components: 1.5 g/L of industrial formic acid, and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 30; adjusting pH to 3.0, adjusting temperature to 33 ℃, adding the leather for 50 min, then adding 1.5 g/l of tanning fatting agent EG-60 (Smit & zon), 1.5 g/l of softening agent TL (Smit & zon), 50 min, 1.5 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), 50 min, 1.5 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), 50 min, 5g/l of chrome-free polymetallic tanning agent ZT-601 (gold Kun chemical industry), 90 min, 0.1 g/l of acid softening enzyme ABL (Murphy & Son), 4h, 2 g/l of baking soda, adding in 3 times, adjusting pH to 4.4, intermittently rotating for 30 min per hour and 20 h;
step eleven, neutralizing: the neutralization solution comprises the following components: the dosage of the neutralization solution is added according to the mass ratio of tanning reclaimed water to fur of 25; 4 g/L of industrial sodium acetate, 2 g/L of a neutralization auxiliary agent NN-555 (Smit & zon) and 0.1 g/L of acid softening enzyme ABL (Murphy & Son), adjusting the pH to 6, and keeping the temperature at 33 ℃ for 150 min;
step twelve, fat adding: the fat liquor comprises the following components: the dosage of the fat liquor is added according to the mass ratio of water to fur in tanning of 25; 1.5 g/l of softening agent TL (Smit & zon), 1.5 g/l of fatting agent GF (Delry leather technology), 3g/l of fatting agent PD-990 (Smit & zon), 3g/l of fatting agent YY-707 (Smit & zon), 3g/l of fatting agent DPF (Desel chemical industry), 1 g/l of filling agent DR-686 (Smit & zon), at the temperature of 50 ℃, the time is 150 min, 1.5 g/l of industrial formic acid, and the pH is adjusted to 3.8;
step thirteen, dry finishing: the same as the conventional process;
and step fourteen, obtaining a finished product.
Example 6
A process for preparing high-grade sheep clothing fur leather by using a chromium-free multi-metal tanning agent comprises the following steps:
step one, rewetting: the same as the conventional process;
step two, spin-drying;
step three, shearing;
step four, main soaking: the same as the conventional process;
step five, removing meat;
step six, degreasing: the same as the conventional process;
step seven, softening and pickling: the softening pickling solution comprises the following components: 2 g/l of weak organic acid Bascal S (BSAF), 2.5 g/l of acid softening enzyme DVP (Delhi leather technology), 30 g/l of industrial neutral salt and the balance of water; the dosage of the softening pickling liquor is added according to the mass ratio of water to fur in the softening pickling liquor of 40; adjusting the temperature to 36 ℃, adding hide, intermittently rotating for 24 hours for 10min per hour, adding pickling fatting agent CP-996 (Smit & zonon) 4 g/l and fur pickling agent MN (Deshel chemical) 20 g/l, adjusting the pH to 2.4, reducing the temperature to 20 ℃, intermittently rotating for 72 hours for 60 min per 4 hours, and then taking out the hide and standing for more than 7 days;
step eight, tanning: the tanning liquor comprises the following components: 80 g/L of industrial neutral salt, 3g/L of industrial formic acid and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20; adjusting pH to 2.4, the temperature to 40 ℃, adding the leather for 60 min, then adding 4 g/l of tanning fatting agent EG-60 (Smit & zon), 8 g/l of softening agent TL (Smit & zon), 60 min, 7 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), 60 min, 7.0 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), 60 min, 15 g/l of chromium-free polymetallic tanning agent ZT-601 (Jinkun chemical industry), 120 min, 0.15 g/l of acid softening enzyme ABL (Murphy & Son), intermittent rotation for 20 min, 24h, 1.5 g/l of soda, adding in 4 times, adjusting pH to 4.2, intermittent rotation for 30 min, 6 h;
step nine, wet grinding;
step ten, retanning: the retanning liquid comprises the following components: 1.5 g/L of industrial formic acid, and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20; adjusting pH to 3.0, adjusting temperature to 40 ℃, adding the leather for 60 min, then adding 2 g/l of tanning fatting agent EG-60 (Smit & zon), 4 g/l of softening agent TL (Smit & zon), 60 min, 4 g/l of acrylic acid synthetic tanning agent RS-540 (Smit & zon), 60 min, 4 g/l of phenolsulfonic acid synthetic tanning agent S (Smit & zon), 60 min, 5g/l of chromium-free multi-metal tanning agent ZT-601 (gold Kun chemical), 120 min, 0.15 g/l of acid softening enzyme ABL (Murphy & Son), 4h, 2 g/l of baking soda, adding 4 times, adjusting pH to 4.2, intermittently rotating for 30 min per hour, and 22 h;
step eleven, neutralizing: the neutralization solution comprises the following components: the dosage of the neutralization solution is added according to the mass ratio of water to fur in tanning of 20; 3g/L industrial sodium acetate, 3g/L neutralization auxiliary agent NN-555 (Smit & zon), 0.15 g/L acid softening enzyme ABL (Murphy & Son), adjusting pH to 6.5, and keeping the temperature at 40 ℃ for 180 min;
step twelve, fat adding: the fat liquor comprises the following components: the dosage of the fat liquor is added according to the mass ratio of water to fur in tanning of 20; 4 g/l of softener TL (Smit & zon), 4 g/l of fatting agent GF (Delry leather technology), 4 g/l of fatting agent PD-990 (Smit & zon), 4 g/l of fatting agent YY-707 (Smit & zon), 4 g/l of fatting agent DPF (Deshel chemical industry), 4 g/l of filler DR-686 (Smit & zon), at the temperature of 56 ℃, the time is 180 min, 1.5 g/l of industrial formic acid, and the pH is adjusted to 3.9;
step thirteen, dry finishing: the same as the conventional process;
and step fourteen, obtaining a finished product.
COD content measurements of the waste waters of examples 1-6 showed COD levels of 50-80 mg/L.
The formaldehyde content was 0.
After the sheep fur leather products were washed with water for a plurality of times (5 times or more), no quality problems occurred in the products of examples 1 to 6. After washing, the leather plate is still soft and full, and the hand feeling is not obviously reduced. The fur remained white and the color of the fur remained white, and after simulated storage, the phenomena of tanning, yellowing and the like did not occur after 3 years.
The detection shows that the shrinkage temperature of each product can reach more than 90 ℃, and the requirements of normal fur leather production on the shrinkage temperature are completely met.
The results show that the fur treated by the invention has high quality and solves the technical problems proposed by the application to a certain extent.
Other test data were as follows:
the detection data of the decomposable harmful aromatic amine dye are as follows:
"not detected" means that the measured value is less than or equal to 30 mg/kg;
| free formaldehyde | mg/kg | ≤300 | 11.1 |
Other project index data
The above test was based on the following criteria:
GB/T19941-2005 determination of Formaldehyde content in leather and fur chemistry tests
GB/T19942-2005 determination of azo dyes forbidden in leather and fur chemistry tests
QB/T2536-2007 Mao leather
QB/TI 269-2012 determination of the tensile Strength and elongation of the physical and mechanical tests of the skins
QB/T1271-2012 determination of shrinkage temperature in physical and mechanical tests of skins
QB/T1327-1991 leather surface color rubbing fastness test method
The judgment is based on the following criteria:
QB/T2536-2007 Mao leather
The data show that the woolen clothes leather products prepared by the process reach the advanced quality level of the industry.
Claims (1)
1. The process for preparing the high-grade sheep clothing fur leather by using the chromium-free multi-metal tanning agent is characterized by comprising the following steps of:
step one, carrying out rewetting,
step two, spin-drying the mixture,
step three, shearing the wool,
step four, the main soaking step is to soak water,
step five, removing the meat,
step six, degreasing the mixture,
step seven, softening and pickling the mixture,
firstly, adding fur into a softening pickling solution, wherein the using amount of the softening pickling solution is 20-40% of the mass ratio of water to the fur in the softening pickling solution, the temperature is adjusted to be 30-40 ℃, the fur is treated for 10-24h, and the fur is rotated for 5-10min per hour along with intermittent rotation;
then, adding pickling fatliquor CP-9961.0-5.0 g/l, fur pickling agent MN 10-20 g/l or pickling auxiliary agent PA 5-15 g/l, adjusting pH to 2.4-2.9, adjusting temperature to 20-30 ℃, treating for 48-72 h, rotating for 40-60 min every 4 hours with intermittent rotation, and then taking out and standing for more than 7 days;
the ratio of the softening pickle liquor is as follows:
weak organic acid Bascal S1-2 g/l,
Acid softening enzyme DVP or acid softening enzyme WB 1-4 g/l,
20-30 g/l of industrial neutral salt,
the balance of water;
step eight, tanning, wherein the tanning step is as follows:
firstly, regulating the pH value of tanning liquid to be 2.4-2.9 and the temperature to be 30-40 ℃, adding the fur treated in the last step, and treating for 30-60 min; the amount of the tanning liquid is added according to the mass ratio of water to fur in tanning of 20-40;
the tanning liquor comprises the following components: 50-80 g/L of industrial neutral salt, 1-3 g/L of industrial formic acid and the balance of water;
then, adding tanning fatting agent EG-602.0-4.0 g/l and softening agent TL 2.0-12.0 g/l, processing for 30-60 min;
then adding acrylic acid synthetic tanning agent RS-5402.0-7.0 g/l, processing for 30-60 min,
then adding 2.0-7.0 g/l of phenolsulfonic acid synthetic tanning agent S, treating for 30-60 min,
then adding 15-30 g/l of chromium-free polymetallic tanning agent ZT-60115 to 120 min for treatment,
then adding 0.05-0.5 g/l of acid softening enzyme ABL, intermittently rotating for 20 min per hour, treating for 10-24h,
finally, adding 0.5-1.5 g/l of sodium carbonate, adding the sodium carbonate by 3-4 times, adjusting the pH to 3.9-4.4, intermittently rotating for 30 min per hour, and treating for 5-8 h;
step nine, wet grinding is carried out,
step ten, retanning, wherein the retanning step is as follows:
firstly, adjusting the pH value of the retanning liquid to 3.0-3.5 and the temperature to 30-40 ℃, adding the fur after the last step of treatment, and treating for 30-60 min, wherein the using amount of the retanning liquid is added according to the mass ratio of water in the retanning liquid to the fur of 20-40;
the retanning liquid comprises the following components: 0.5-1.5 g/L of industrial formic acid, and the balance of water;
then, tanning fatting agent EG-601.0-2.0 g/l and softening agent TL 1.0-4.0 g/l are added, the treatment time is 30-60 min,
then adding acrylic acid synthetic tanning agent RS-5401.0-4.0 g/l, processing for 30-60 min,
then adding 1.0-4.0 g/l of phenolsulfonic acid synthetic tanning agent S, treating for 30-60 min,
then adding 5-15 g/l of chromium-free polymetallic tanning agent ZT-6015 to 120 min for treatment,
then adding 0.05-0.5 g/l of acid softening enzyme ABL, processing for 2-4 h,
then adding 1-2 g/l of baking soda, adding 3-4 times, adjusting pH to 3.9-4.4, intermittently rotating for 30 min per hour for 10-24 h;
step eleven, neutralization, wherein in the neutralization step,
firstly, adjusting the pH value of the neutralization solution to 5.5-6.5, and adding the fur treated in the previous step; the dosage of the neutralizing liquid is added according to the mass ratio of water to fur in the neutralizing liquid of 20-40;
the neutralizing solution comprises the following components: 1-4 g/L of industrial sodium acetate, 4.0 g/L of neutralizing auxiliary agent NN-5551.0, 0.05-0.5 g/L of acid softening enzyme ABL and the balance of water
Then, treating for 120-180 min at the temperature of 30-40 ℃;
step twelve, fat-liquoring, which comprises the following steps:
firstly, adding the fur treated in the last step into a fatliquoring solution, wherein the using amount of the fatliquoring solution is added according to the mass ratio of water to the fur in the fatliquoring solution of 20-40; then, adjusting the pH value to 3.8-4.0 at the temperature of 50-60 ℃, treating for 120-180 min,
the fat liquor comprises the following components:
1.0-4.0 g/l of softening agent TL,
fatting agent GF 1.0-4.0 g/l,
fatting agent PD-9901.0-4.0 g/l,
fatting agent YY-7071.0-4.0 g/l,
fatting agent DPF 1.0-4.0 g/l,
filler DR-6861.0-4.0 g/l,
0.5-1.5 g/l of industrial formic acid;
step thirteen, dry finishing,
and step fourteen, obtaining a finished product.
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| CN101372717A (en) * | 2008-10-15 | 2009-02-25 | 温州大学 | Method for tanning sheep fur leather using non-chromium metal composite tanning agent |
| CN101381782A (en) * | 2008-10-15 | 2009-03-11 | 温州大学 | Method for tanning ultrathin sheepskin garment leather using non-chromium metal composite tanning agents |
| CN104313199A (en) * | 2014-10-28 | 2015-01-28 | 北京泛博化学股份有限公司 | Method of preparing sheepskin clothing face garment leather with small liquor ratio |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372717A (en) * | 2008-10-15 | 2009-02-25 | 温州大学 | Method for tanning sheep fur leather using non-chromium metal composite tanning agent |
| CN101381782A (en) * | 2008-10-15 | 2009-03-11 | 温州大学 | Method for tanning ultrathin sheepskin garment leather using non-chromium metal composite tanning agents |
| CN104313199A (en) * | 2014-10-28 | 2015-01-28 | 北京泛博化学股份有限公司 | Method of preparing sheepskin clothing face garment leather with small liquor ratio |
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Denomination of invention: Preparation of high-grade sheep clothing fur leather using chromium free polymetallic tanning agents Effective date of registration: 20231212 Granted publication date: 20210706 Pledgee: Zhejiang Tongxiang Rural Commercial Bank Co.,Ltd. Chongfu Branch Chengdong Branch Pledgor: ZHEJIANG ZHONGHUI FUR OR LEATHER TECHNOLOGY Co.,Ltd. Registration number: Y2023980070582 |