CN117646090A - Preparation method of environment-friendly anti-cracking leather - Google Patents
Preparation method of environment-friendly anti-cracking leather Download PDFInfo
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- CN117646090A CN117646090A CN202311598687.9A CN202311598687A CN117646090A CN 117646090 A CN117646090 A CN 117646090A CN 202311598687 A CN202311598687 A CN 202311598687A CN 117646090 A CN117646090 A CN 117646090A
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- leather
- cracking
- tanning
- environment
- solution
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- 239000010985 leather Substances 0.000 title claims abstract description 92
- 238000005336 cracking Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 45
- 210000003491 skin Anatomy 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 238000011282 treatment Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 16
- 102000004190 Enzymes Human genes 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 15
- 229940088598 enzyme Drugs 0.000 claims description 15
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 14
- 239000001263 FEMA 3042 Substances 0.000 claims description 14
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229920002258 tannic acid Polymers 0.000 claims description 14
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 14
- 229940033123 tannic acid Drugs 0.000 claims description 14
- 235000015523 tannic acid Nutrition 0.000 claims description 14
- 238000004049 embossing Methods 0.000 claims description 12
- 238000010409 ironing Methods 0.000 claims description 12
- 238000004043 dyeing Methods 0.000 claims description 11
- 102000008186 Collagen Human genes 0.000 claims description 10
- 108010035532 Collagen Proteins 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920001436 collagen Polymers 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 210000002615 epidermis Anatomy 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- YAXKTBLXMTYWDQ-UHFFFAOYSA-N 1,2,3-butanetriol Chemical compound CC(O)C(O)CO YAXKTBLXMTYWDQ-UHFFFAOYSA-N 0.000 claims description 4
- 108090000145 Bacillolysin Proteins 0.000 claims description 4
- 102000035092 Neutral proteases Human genes 0.000 claims description 4
- 108091005507 Neutral proteases Proteins 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 102000004139 alpha-Amylases Human genes 0.000 claims description 4
- 108090000637 alpha-Amylases Proteins 0.000 claims description 4
- 229940024171 alpha-amylase Drugs 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 235000021323 fish oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 206010033675 panniculitis Diseases 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007761 roller coating Methods 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 210000004304 subcutaneous tissue Anatomy 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- 108010059892 Cellulase Proteins 0.000 claims description 2
- 239000004367 Lipase Substances 0.000 claims description 2
- 102000004882 Lipase Human genes 0.000 claims description 2
- 108090001060 Lipase Proteins 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229940106157 cellulase Drugs 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 235000019421 lipase Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 210000004209 hair Anatomy 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
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- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 2
- 101710155891 Mucin-like protein Proteins 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000002425 soil liming agent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000006395 Globulins Human genes 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 102000016611 Proteoglycans Human genes 0.000 description 1
- 108010067787 Proteoglycans Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 anionic cations Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000003780 hair follicle Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 108020001775 protein parts Proteins 0.000 description 1
- 230000006920 protein precipitation Effects 0.000 description 1
- 210000004918 root sheath Anatomy 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 210000001519 tissue Anatomy 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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/04—Soaking
-
- 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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
- C14C1/065—Enzymatic unhairing
-
- 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
- C14C11/00—Surface finishing of leather
-
- 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
-
- 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
-
- 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
- C14C5/00—Degreasing leather
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to the technical field of leather production, provides a preparation method of environment-friendly anti-cracking leather, and solves the problems of environmental pollution and poor anti-cracking performance of finished leather caused by using high-pollution chemical reagents in the existing leather production process; the method comprises the following steps: a preparation stage; (II) tanning stage; and (III) a later finishing section to obtain the anti-cracking leather finished product.
Description
Technical Field
The invention relates to the technical field of leather production, in particular to a preparation method of environment-friendly anti-cracking leather.
Background
The leather industry is one of the oldest industrial activities and also one of the pillar industries of the worldwide light industry, which makes a great contribution to the development of the world economy. With thousands of years of development and increasing levels of industrial technology, the leather industry is becoming one of the industries with a relatively sophisticated industrial system. Leather is a natural degradable material which is changed from animal skin through a series of chemical and mechanical treatments, has the characteristics of unique mechanical property, excellent hygroscopicity and comfortableness, unique aesthetic appearance and the like, and is generally manufactured into articles such as clothes, furniture, bags and the like so as to meet various demands of human life and work.
The conversion from a piece of raw hide with hair to leather meeting the requirements requires a series of complex chemical and mechanical treatments, including multiple processes. The conventional tanning process is generally divided into three major segments: a preparation section, a tanning section and a post finishing stage. The leather change process is in the tanning stage, however, prior to tanning, a preliminary treatment of the pelt is required, i.e. a preparation stage. The preparation section is used for removing dirt, fat, hair and some useless tissues of leather in the raw leather so that the raw leather can meet the tanning requirement. The working section involves a plurality of procedures such as soaking, degreasing, unhairing, liming, deashing, softening, pickling, deacidification and the like. After tanning, the hide becomes leather, but because the physical-mechanical properties of the leather still do not meet the requirements of use, a series of subsequent finishing procedures are still needed, and the section is to change the physical-mechanical properties and appearance properties of the leather so that the leather meets the requirements of use standards.
The traditional liming treatment is mainly carried out by using sodium sulfide and lime, and is assisted by a plurality of liming aids, surfactants and other substances, so that a large amount of sludge, pollutants and harmful gases are generated due to the use of sulfide and lime, liming waste liquid is difficult to treat, and COD (chemical oxygen demand) content is increased due to the discharge of a large amount of nitrogen-containing substances, so that the living environment of human beings is seriously endangered. Therefore, people do not break the clean pollution-free ash dipping process.
The invention discloses liming equipment and liming process for natural leather treatment, wherein the liming equipment and the liming process are disclosed in the invention, firstly, raw leather and lime water which are subjected to a preparation process are put into a working cavity of a rotary drum, then excessive lime and proper amount of clear water are sent into a storage cavity of the rotary drum, the rotary drum is enabled to rotate, the raw leather is limed for 4-6 hours, then the raw leather is taken out, finally, acid is added into the working cavity of the rotary drum to precipitate protein, then liming waste liquid is discharged, and protein precipitation in the waste liquid is filtered and separated, so that the recovery of the liming waste liquid is completed. Through the zoned rotary drum of setting, cooperation one-way subassembly and one-way play water subassembly can save steps such as the pressurization filtration to liming waste liquid recovery in-process in cyclic processing process, has reduced the process step, effectively promoted technological efficiency. However, lime water is still required to be added in the liming process, the pH of the solution can be kept above 12 by using lime, but the lime not only causes a large amount of sludge to be generated, but also can not recycle the liming liquid, and the process production cannot really achieve environmental protection.
The invention discloses an ashless, alkali sulfide-free unhairing and liming treatment method for buffalo skin tanning, which has the application number of 200810163968.0 and the publication number of CN101445843B and sequentially comprises the following steps: presoaking, soaking, pretreatment, dehairing, swelling, dealkalization, softening and pickling. The invention does not use sodium sulfide, sodium hydrosulfide and lime, greatly reduces pollution in the tanning process, ensures that the wastewater discharged by the process is easier to treat, and does not generate a large amount of lime sediment and residues in the traditional process. The process of the ash skin water washing with the largest water consumption is eliminated, and the softening water washing time and the water washing amount are reduced due to less calcium scale during softening, so that the water saving is close to 20-40% of the total wastewater discharge. The liming agent has weaker hydrolysis degree to collagen fiber than the traditional process, but the physical and mechanical properties of the final leather are similar to those of the leather of the traditional process, and the liming agent cannot have good anti-cracking performance.
Disclosure of Invention
Therefore, the invention provides a preparation method of environment-friendly anti-cracking leather, aiming at the problems of environmental pollution and poor anti-cracking performance of finished leather caused by using high-pollution chemical reagents in the existing leather production process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the environment-friendly anti-cracking leather comprises the following steps:
s1, a preparation section: firstly, soaking raw leather to remove dirt carried by the raw leather, then dehairing with enzyme solution to remove wool, epidermis and other substances carried by the raw leather, then degreasing to remove fat substances, and finally pickling to adjust the pH of the pelt and loosen collagen fibers;
s2, tanning section: the tanning agent molecules penetrate into the skin and are combined with active groups of collagen molecules of the pelt to make the pelt into leather;
s3, a post finishing section: the environment-friendly anti-cracking leather is obtained through retanning, neutralization, dyeing, fatliquoring, drying, softening, ironing, dyeing, finishing and embossing treatment.
Further, the raw skin is any one of cowhide, sheep skin and pig skin.
Further, the preparation working section comprises the following specific processes:
a. soaking: immersing in the drum for 6-8 h, controlling the temperature to be 25-30 ℃ and the liquid ratio to be 2-3:1, adding 0.5-1.0 wt% of sodium bicarbonate to promote the water to be immersed into the skin rapidly, and changing the water once every 1-2h until the raw skin reaches a fresh skin state from a dry and hard state;
b. dehairing: placing the pelts into a mixed solution with the prepared enzyme solution concentration of 0.5-1.0 wt% and the salt solution concentration of 0.2-0.5 wt%, dehairing in a rotary drum, controlling the liquid ratio to be 2-3:1, and controlling the temperature to be 25-30 ℃ for 6-8 h;
c. degreasing: the method of jointly carrying out mechanical treatment and chemical treatment is adopted, firstly, a cutter is used for removing redundant fat and subcutaneous tissue on the bare skin as much as possible, and then 5-10wt% sodium carbonate solution is used for treating for 30-60 min in a revolving strand, so that clean bare skin is obtained;
d. pickling: controlling the liquid ratio to be 2-3:1, adding 5-10wt% sodium chloride and 0.5-1.0wt% diluted sulfuric acid solution, wherein the dilution ratio is 1:10-20, then placing the pelt to be pickled in acid liquor for pickling for 1-2h, and pouring out the acid liquor after pickling is finished.
Further, the enzyme solution is: alpha-amylase, neutral protease, cellulase and lipase.
Further, the salt solution is: sodium acetate, sodium sulfate, sodium molybdate, sodium silicate, sodium bicarbonate, disodium hydrogen phosphate, sodium chloride, and potassium chloride.
Further, in step S2, the specific process of the tanning stage is as follows: tanning with tannic acid solution, first placing the pickled pelts in tannic acid solution with concentration of 3-8wt%, controlling the liquid ratio to be 2:1-3:1, the temperature to be 25-38 ℃, tanning in an oscillator, controlling the oscillation frequency to be 180-200 rpm, respectively adding 8-10wt% and 10-20wt% of tannic acid into the tanning liquid in the oscillator in the 2h and 4h of tanning, and then continuing tanning for 72-96 h.
Further, the concrete process of the post-finishing working section is as follows:
a. retanning: placing leather material into tannic acid solution with concentration of 3-8wt%, controlling the liquor ratio to be 2-3:1, and the temperature to be 25-38 ℃, tanning in an oscillator, controlling the oscillation frequency to be 180-200 rpm, and discharging liquor after retanning for 1-2h to obtain retanning leather;
b. and (3) neutralization: putting the retanned leather into sodium formate and sodium bicarbonate solution with the mass ratio of 1-2:2-3, mixing, adjusting the pH value of the mixed solution to 6-7, placing the mixed solution into a drum for rotating for 1-2h at the temperature of 25-38 ℃, and discharging liquid;
c. dyeing: mixing the neutralized leather with water, adding dye for dyeing for 2-3 hours, and draining;
d. and (3) adding grease: mixing the dyed leather with water, putting the leather into a mixed solution of castor oil phosphate and sulfited fish oil in a mass ratio of 2-3:1-2, mixing for 2-3 hours at a temperature of 30-60 ℃, and discharging liquid;
e. and (3) drying: vacuum drying at 60-90 deg.c for 5-10 min in a vacuum machine;
f. and (3) softening: the soft return is carried out by using a passing type vibrating soft machine, and the speed is 10-15 m/min;
g. ironing: ironing by using a pass-through ironing machine, wherein the temperature is 100-120 ℃, the pressure is 30-40 kg, and the speed is 5-8 m/min;
h. and (3) coating: coating the anti-cracking coating on the surface of the leather billet in a spraying or roller coating mode;
i. embossing: embossing by an embossing machine at 100-120 deg.c and pressure of 80-120 kg for 5-10 s.
Further, the preparation method of the enzyme solution comprises the following steps: weighing 2-5 g of enzyme powder, adding into phosphate buffer solution with pH of 7.0-7.5, uniformly mixing, preparing into 0.5-1.0 wt%, and preserving at 4 ℃ for later use.
Further, the anti-cracking coating is prepared by the following method: adding silicone oil and allyl alcohol glycidyl ether with the molar ratio of 1:2-4 into a mixer, stirring for 15-30 min at the rotating speed of 100-120 r/min to obtain a mixture, adding a hydrosilylation reaction heterogeneous catalyst with the mass fraction of 50-60 wt%, raising the temperature to 60-90 ℃, reacting for 3-4 h to obtain a mixed solution, and uniformly mixing 1,2, 3-trihydroxybutane and the mixed solution with the mass ratio of 1:1-6 to obtain the anti-cracking coating.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the leather obtained by the preparation method of the invention has the advantages that the production process can realize green environmental protection and no pollution, and the principle is as follows: the enzyme can act on mucin and mucin-like protein at the root bottom of the raw material skin and at the junction of the root sheath and hair follicle to make the mucin and mucin-like protein be catalyzed and dissolved so as to weaken the connection of hair and epidermis, and then the hair and epidermis are separated by means of mechanical treatment so as to attain the goal of dehairing. The mechanism of action of salt-assisted enzyme treatment of naked skin is mainly that enzyme acts on protein components in naked skin fibrous interstitial, and some protein parts in viscous protein, globulin and proteoglycan are decomposed into soluble polypeptides by the catalytic action of neutral protease and enter into solution, so that fibrous interstitial is gradually removed from naked skin, and the auxiliary action of salt can promote the neutral protease to permeate into naked skin to act rapidly and has a certain removal effect on fibrous interstitial. After the fibrous matrix is removed, the bare skin collagen fibers are dispersed to a certain extent and a certain amount of active groups are exposed, so that a certain condition is provided for the later tanning process. In the preparation stage, the time for treating the pelt by adopting the enzyme system of the invention is half of that of the traditional process, and the treated pelt does not need to be subjected to the operations of deashing, softening and the likeThe pickling and tanning can be directly carried out, the tanning time is shortened, the waste of water resources is saved, and meanwhile, reagents such as sulfide, lime and the like are not adopted in the treatment process, so that S is avoided 2- And the discharge of pollutants such as sludge.
2. The leather obtained by the preparation method of the invention has good cracking resistance, and the principle is as follows: tanning is an important step of changing the quality of the pelt into leather, in the process, tannic acid is selected as a tanning agent molecule to carry out tanning, amino groups on collagen fibers and the tannic acid molecule are combined in a hydrogen bond form to form a stable structure, the adsorption capacity of the pelt to the tanning agent molecule is related to the number of active groups on the collagen fibers, the better the dispersibility of the collagen fibers is, the more the active groups on the fibers are, the better the adsorption capacity of the pelt to the tanning agent molecule is, so that leather can obtain certain chemical, thermal and microbial degradation resistance, and the durability and the service performance of leather products are improved; the auxiliary effect of the salt improves the mechanical property of crust leather, and the hydrogen phosphate ions enable the toughness of the crust leather to be stronger. The anti-cracking agent prepared by adding 1,2, 3-trihydroxybutane and siloxane on the basis of retanning is connected with anionic cations in the leather retanning agent, so that the siloxane is qualitatively arranged and effectively crosslinked with active groups on protein fibers in the leather, and the anti-cracking performance of the leather is enhanced.
Detailed Description
Example 1
The preparation method of the environment-friendly anti-cracking leather comprises the following steps:
(1) The preparation section comprises the following steps: firstly, taking a cowhide raw material skin, carrying out soaking treatment to remove dirt carried by the raw material skin, then carrying out dehairing treatment by using an alpha-amylase solution to remove materials such as wool, epidermis and the like carried by the raw material skin, then carrying out degreasing treatment to remove fatty substances, and finally, carrying out pickling to adjust the pH of the pelt and loosening collagen fibers;
(1-1) soaking: soaking in a rotary drum for 8 hours, controlling the temperature to be 30 ℃, controlling the liquid ratio to be 2:1, adding 0.5wt% of sodium bicarbonate to promote water to quickly soak into the skin, and changing water every 1 hour until the raw skin reaches a fresh skin state from a dry and hard state;
(1-2) dehairing: weighing 2g of enzyme powder, adding into phosphate buffer solution with pH of 7.0, mixing uniformly, preparing into 0.5wt%, preserving at 4 ℃ for standby, placing the pelt into prepared mixed solution of 0.5wt% alpha-amylase solution and 0.5wt% disodium hydrogen phosphate, dehairing in a rotary drum, controlling the liquid ratio to be 2:1, and controlling the temperature to be 30 ℃ for 8 hours;
(1-3) degreasing: the method of jointly carrying out mechanical treatment and chemical treatment is adopted, firstly, a cutter is used for removing redundant fat and subcutaneous tissue on the bare skin as much as possible, and then 5wt% sodium bicarbonate solution is used for treating for 30min in a revolving strand, so that clean bare skin is obtained;
(1-4) pickling: controlling the liquid ratio to be 2:1, adding 5wt% sodium chloride and 0.5wt% diluted sulfuric acid solution, wherein the dilution ratio is 1:10, then placing the pelt to be pickled in acid liquor for pickling for 2h, and pouring out the acid liquor after pickling is finished;
(2) Tanning section: tanning with tannic acid solution, firstly placing the pickled pelts in tannic acid solution with the concentration of 5wt%, controlling the liquor ratio to be 2:1, the temperature to be 30 ℃, tanning in an oscillator, controlling the oscillation frequency to be 1800rpm, respectively directly adding 10wt% and 20wt% of tannic acid into tanning liquor in the oscillator in the 2 nd and 4 th h of tanning, and then continuing tanning for 72h;
(3) A post finishing section: the environment-friendly anti-cracking leather is obtained through retanning, neutralization, dyeing, fatliquoring, drying, softening, ironing, dyeing, finishing and embossing treatment;
(3-1) retanning: placing leather materials into tannic acid solution with the concentration of 5wt%, controlling the liquor ratio to be 2:1, controlling the temperature to be 30 ℃, tanning in an oscillator, controlling the oscillation frequency to be 180rpm, and discharging liquor after retanning for 2 hours to obtain retanning leather;
(3-2) neutralization: putting the retanned leather into sodium formate and sodium bicarbonate solution with the mass ratio of 1:2, mixing, adjusting the pH value of the mixed solution to 7, placing the mixed solution into a drum for rotating for 2 hours at the temperature of 30 ℃, and draining;
(3-3) staining: mixing the neutralized leather with water, adding dye for dyeing for 2 hours, and draining;
(3-4) fatting: mixing the dyed leather with water, putting the leather into a mixed solution of castor oil phosphate and sulfited fish oil in a mass ratio of 2:1, mixing for 2 hours at the temperature of 30 ℃, and discharging liquid;
(3-5) drying: vacuum drying at 70deg.C for 8min;
(3-6) softening: performing softening by using a passing type vibration softening machine, wherein the speed is 10m/min;
(3-7) ironing: ironing by using a pass-through ironing machine, wherein the temperature is 100 ℃, the pressure is 30kg, and the speed is 5m/min;
(3-8) coating: adding silicone oil and allyl alcohol glycidyl ether with the molar ratio of 1:2 into a mixer, stirring for 30min at the rotating speed of 120r/min to obtain a mixture, adding a hydrosilylation reaction heterogeneous catalyst with the mass fraction of 60wt%, heating to 80 ℃, reacting for 4h to obtain a mixed solution, uniformly mixing 1,2, 3-trihydroxybutane and the mixed solution with the mass ratio of 1:2 to obtain an anti-cracking coating, and coating the anti-cracking coating on the surface of a leather blank in a spraying or roller coating mode;
(3-9) embossing: embossing was carried out using an embossing machine at 120℃under a pressure of 100kg for a dwell time of 5s.
Comparative example 1
Differences from example 1: the leather preparation process is not adopted, and the known process is adopted, and the leather preparation process comprises the steps of pre-soaking, pretreatment, dehairing, expansion, dealkalization, softening and pickling.
The results of the performance tests of the above example 1 product and comparative example 1 product are shown in the following table.
TABLE 1
As can be seen from the above table, the leather product produced by the method for producing environment-friendly and anti-cracking leather of the invention has significantly reduced COD in the waste liquid compared with the leather product produced by the method of comparative example 1 cr The emission concentration of BOD, suspended matters and sulfides realizes green production processThe color is environment-friendly and pollution-free. And the leather physical property data of the example 1 show that compared with the leather produced by the comparative example, the leather related performance is greatly improved in the aspects of tensile strength, elongation at break, abrasion resistance and trouser tearing, and the leather with the improved anti-cracking performance has good anti-cracking performance.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the environment-friendly anti-cracking leather is characterized by comprising the following steps of:
s1, a preparation section: firstly, soaking raw leather to remove dirt carried by the raw leather, then dehairing with enzyme solution to remove wool and epidermis substances carried by the raw leather, then degreasing to remove fat substances, and finally pickling to adjust the pH of the pelt and loosen collagen fibers;
s2, tanning section: the tanning agent molecules penetrate into the skin and are combined with active groups of collagen molecules of the pelt to make the pelt into leather;
s3, a post finishing section: the environment-friendly anti-cracking leather is obtained through retanning, neutralization, dyeing, fatliquoring, drying, softening, ironing, dyeing, finishing and embossing treatment.
2. The method for preparing the environment-friendly anti-cracking leather according to claim 1, which is characterized in that: in the step S1, the raw skin is any one of cowhide, sheep skin and pig skin.
3. The preparation method of the environment-friendly anti-cracking leather according to claim 1, wherein the preparation section comprises the following specific processes:
a. soaking: immersing in the drum for 6-8 h, controlling the temperature to be 25-30 ℃ and the liquid ratio to be 2-3:1, adding 0.5-1.0 wt% of sodium bicarbonate to promote the water to be immersed into the skin rapidly, and changing the water once every 1-2h until the raw skin reaches a fresh skin state from a dry and hard state;
b. dehairing: placing the pelts into a mixed solution with the prepared enzyme solution concentration of 0.5-1.0 wt% and the salt solution concentration of 0.2-0.5 wt%, dehairing in a rotary drum, controlling the liquid ratio to be 2-3:1, and controlling the temperature to be 25-30 ℃ for 6-8 h;
c. degreasing: the method of jointly carrying out mechanical treatment and chemical treatment is adopted, firstly, a cutter is used for removing redundant fat and subcutaneous tissue on the bare skin, and then 5-10wt% sodium carbonate solution is used for treating for 30-60 min in a rotating strand, so that clean bare skin is obtained;
d. pickling: controlling the liquid ratio to be 2-3:1, adding 5-10wt% sodium chloride and 0.5-1.0wt% diluted sulfuric acid solution, wherein the dilution ratio is 1:10-20, then placing the pelt to be pickled in acid liquor for pickling for 1-2h, and pouring out the acid liquor after pickling is finished.
4. The method for preparing the environment-friendly and anti-cracking leather according to claim 1, wherein the enzyme solution is as follows: alpha-amylase, neutral protease, cellulase and lipase.
5. The method for preparing the environment-friendly anti-cracking leather according to claim 1, wherein the salt solution is as follows: sodium acetate, sodium sulfate, sodium molybdate, sodium silicate, sodium bicarbonate, disodium hydrogen phosphate, sodium chloride, and potassium chloride.
6. The method for preparing environment-friendly anti-cracking leather according to claim 1, wherein in the step S2, the specific process of the tanning stage is as follows: tanning with tannic acid solution, first placing the pickled pelts in tannic acid solution with concentration of 3-8wt%, controlling the liquid ratio to be 2:1-3:1, the temperature to be 25-38 ℃, tanning in an oscillator, controlling the oscillation frequency to be 180-200 rpm, respectively adding 8-10wt% and 10-20wt% of tannic acid into the tanning liquid in the oscillator in the 2h and 4h of tanning, and then continuing tanning for 72-96 h.
7. The method for preparing environment-friendly anti-cracking leather according to claim 1, wherein in the step S3, the specific process of the post-finishing section is as follows:
a. retanning: placing leather material into tannic acid solution with the concentration of 3-8wt%, controlling the liquor ratio to be 2-3:1, the temperature to be 25-38 ℃, tanning in an oscillator, controlling the oscillation frequency to be 180-200 rpm, and discharging liquor after retanning for 1-2 hours to obtain retanning leather;
b. and (3) neutralization: putting the retanned leather into sodium formate and sodium bicarbonate solution with the mass ratio of 1-2:2-3, mixing, adjusting the pH value of the mixed solution to 6-7, placing the mixed solution into a drum for rotating for 1-2h at the temperature of 25-38 ℃, and discharging liquid;
c. dyeing: mixing the neutralized leather with water, adding dye for dyeing for 2-3 hours, and draining;
d. and (3) adding grease: mixing the dyed leather with water, putting the leather into a mixed solution of castor oil phosphate and sulfited fish oil in a mass ratio of 2-3:1-2, mixing for 2-3 hours at a temperature of 30-60 ℃, and discharging liquid;
e. and (3) drying: vacuum drying at 60-90 deg.c for 5-10 min in a vacuum machine;
f. and (3) softening: the vibration softening machine is used for carrying out softening, and the speed is 10-15 m/min;
g. ironing: ironing by using an ironing machine, wherein the temperature is 100-120 ℃, the pressure is 30-40 kg, and the speed is 5-8 m/min;
h. and (3) coating: coating the anti-cracking coating on the surface of the leather billet in a spraying or roller coating mode;
i. embossing: embossing by an embossing machine at 100-120 deg.c and pressure of 80-120 kg for 5-10 s.
8. The method for preparing the environment-friendly and anti-cracking leather according to claim 4, wherein the method for preparing the enzyme solution is as follows: weighing 2-5 g of enzyme powder, adding into phosphate buffer solution with pH of 7.0-7.5, uniformly mixing, preparing into 0.5-1.0 wt%, and preserving at 4 ℃ for later use.
9. The method for preparing the environment-friendly anti-cracking leather according to claim 7, wherein the anti-cracking coating is prepared by the following steps: adding silicone oil and allyl alcohol glycidyl ether with the molar ratio of 1:2-4 into a mixer, stirring for 15-30 min at the rotating speed of 100-120 r/min to obtain a mixture, adding a hydrosilylation reaction heterogeneous catalyst with the mass fraction of 50-60 wt%, raising the temperature to 60-90 ℃, reacting for 3-4 h to obtain a mixed solution, and uniformly mixing 1,2, 3-trihydroxybutane and the mixed solution with the mass ratio of 1:1-6 to obtain the anti-cracking coating.
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