CN101225450B - Chrome-free tannage producing technique for goat glove leather - Google Patents
Chrome-free tannage producing technique for goat glove leather Download PDFInfo
- Publication number
- CN101225450B CN101225450B CN2008100173537A CN200810017353A CN101225450B CN 101225450 B CN101225450 B CN 101225450B CN 2008100173537 A CN2008100173537 A CN 2008100173537A CN 200810017353 A CN200810017353 A CN 200810017353A CN 101225450 B CN101225450 B CN 101225450B
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- chrome
- tanning
- leather
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- washing
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- 239000010985 leather Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 241000283707 Capra Species 0.000 title claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 22
- 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 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- -1 aluminium chlorohydroxide Chemical group 0.000 claims description 4
- 238000004043 dyeing Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical group [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- SXZFFLUKKSLVFD-UHFFFAOYSA-N C(O)P(CO)(CO)CO.S(O)(O)(=O)=O Chemical group C(O)P(CO)(CO)CO.S(O)(O)(=O)=O SXZFFLUKKSLVFD-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012245 magnesium oxide Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000015598 salt intake Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000007844 bleaching agent Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000026731 phosphorylation Effects 0.000 description 4
- 238000006366 phosphorylation reaction Methods 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 208000028804 PERCHING syndrome Diseases 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- YIEDSISPYKQADU-UHFFFAOYSA-N n-acetyl-n-[2-methyl-4-[(2-methylphenyl)diazenyl]phenyl]acetamide Chemical compound C1=C(C)C(N(C(C)=O)C(=O)C)=CC=C1N=NC1=CC=CC=C1C YIEDSISPYKQADU-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Abstract
The invention relates to a processing technique of leather, in particular to a chrome-free tannage manufacturing technique of goat glove leather, aims at solving the problem of heavy environment pollution caused by the chrome sewage in the prior art of chrome tannage. The processing technique of leather adopts a technical proposal that the chrome-free tannage manufacturing technique of goat glove leather comprises a plurality of successively steps as followings: softening, dipping in acid, organophosphor tanning, oxidation, stacking, sammying and extension, shaving, washing, degreasing, rinse, washing, retanning and stuffing, washing, and routine following chrome tanning technique. The processing technique of leather has the advantages of eliminating the environment pollution caused by the heavy metal chrome, reducing the cost of sewage treatment, producing environment-friendly goat glove leather with soft, plumpy, highly resilient, and flowing hand feeling, smooth grain, brilliant color, qualified formaldehyde content as ecological leather, over 88 DEG C shrinkage temperature, and completely same mechanical property as routine chrome tannage leather.
Description
Technical field:
What the present invention relates to is leather processing technology, particularly a kind of chrome-free tanning production technique of goat skin gloves leather.
Background technology:
Chrome tanning is to be most widely used in the world at present and method that the tanning effect is the best, has plurality of advantages such as moisture-proof heat, good stability, finished leather are soft and full, good moldability through the leather of its tanning.Chromic tanning come out over more than 100 year, with its superior tanning performance always in occupation of dominant position.Along with the progress in epoch and the development of society, chromic tanning also will be faced with formidable challenges.Chromium reserves in the world are limited after all on the one hand, and China's chromium resource is not abundant yet, and it is the reality that is difficult to avoid that a large amount of uses can be moved towards exhaustion, and therefore studying chrome-free tanning has its certainty; The chrome tanning environmental pollution is bigger on the other hand, and along with the pay attention to day by day of people to its own existence environment and quality of life, the problem of environmental pollution of chrome tanning shows especially day by day.And along with the raising of people's quality of life, people's consumption idea is also changing, and than being tending towards pursuing natural product in the past more, advocating and produces leatherware with green material, straight chrome tanning has been difficult to satisfy the demands of consumers fully, and therefore studying chrome-free tanning has its feasibility.The generation of Green Trade Barrier, implementation of sustainable development, embodied the enhancing of people's environmental consciousnesses, also impel people to be devoted to seek to replace the pollution-free or low pollution process for tanning of chromic tanning, during producing, adopts leather and environment harmony, eco-friendly leather chemical industry material (being the green leather material) and Technology (promptly cleaning Technology), more and more receive publicity and support, and in cleaning Technology the no chromic tanning trend of leather development from now on beyond doubt.
Summary of the invention:
The object of the present invention is to provide a kind of nothing system production technique of goat glove leather, to solve the problem of high concentration chrome wastewater serious environment pollution in the existing chrome tanning tanning technology.
Purpose of the present invention is achieved through the following technical solutions:
A kind of chrome-free tanning production technique of goat skin gloves leather, include following step: softening → pickling → organic phosphine tanning → oxidation → as to take horse to leave standstill → water squeezing stretching, extension → shaving → washing → degreasing, rinsing → washing → retanning stuffing → washing, chrome tanning subsequent technique routinely carries out then, the addition of additive is a benchmark with the graywall quality in each operation
Pickling procedure: liquor ratio is 80% (normal temperature), the Industrial Salt consumption is 6%～8%, rotate 20min, the control degree Beaume is 6.0～6.5, add mass concentration then more than or equal to 85% formic acid 8%～12 ‰, divide 2-3 adding, rotate 20min at every turn, control pH is 3.4～3.6, rotates 40min again;
Described tanning operation: in pickling liquid, carry out, add the organic phosphine tanning agent, the organic phosphine tanning agent is a sulfuric acid tetra methylol phosphine, its consumption is 1.5%～2.5%, checks whether the organic phosphine tanning agent permeates fully (otch shows light yellow proof infiltration fully) with the selenium indicator behind the rotation 120min, stops then to rouse and spends the night, rotate 30min morning next day, it is 5.5～5.7 that gradation adds alkali adjusting pH, rotates 30min at every turn, rotates 60min at last; Add 1.5%～2.5% syntannin then, rotate 60min;
Described oxidation operation: the oxygenant with 0.5%～1% (liquor ratio is 150%) bleaching, rotate 60min, remove residual organic phosphine tanning agent, check that with the selenium indicator otch does not develop the color, prove that oxidation is complete;
Described retanning stuffing operation: carry out gradation with different synthetic tanning agentes and fatting agent and add.In this operation, selected several synthetic tanning agentes to carry out in conjunction with retanning, for fatting agent being permeated equably and being distributed in the leather fiber, adopted several fatting agents to carry out Fatliquoring in multi-step simultaneously, said synthetic tanning agent and fatting agent can be selected known various product for use.
Behind above-mentioned last water-washing step, also comprise stuffing again and washing step, be added with 150% 40～45 ℃ water in the stuffing operation again, 2.0% phosphate fat-liquoring agent, 1.0% synthetic fat liquor, 3.0% nonionic fatting agent are added in gradation then, rotate 60min, adding 1.0% mass concentration again, to regulate pH more than or equal to 85% formic acid be 3.3～3.4, rotates 30min.Fatting agent is permeated more equably and be distributed in and remove from office in the fiber.
Behind above-mentioned last water-washing step, also include retanning more successively, washing, neutralization, washing, dyeing, stuffing operation.To obtain high-quality colouring leather.
In the above-mentioned tanning operation, alkali can be sodium bicarbonate, sodium-acetate, magnesium oxide or yellow soda ash; In the oxidation operation,
Oxygenant can be hydrogen peroxide or Sodium peroxoborate.
In above-mentioned degreasing, the rinsing process, be added with 250%～300% 40～45 ℃ water, add 0.45%～0.5% grease-removing agent simultaneously, 0.4%～0.45% oxalic acid, 0.15%～0.2% poly phosphate rotate 60min, and regulating pH is 5.5～5.7.
In degreasing, rinsing process and retanning stuffing operation, add 0.1%～0.5% ethylenediamine tetraacetic acid (EDTA) (E.D.T.A), can improve the whiteness of white leather of finished product leather and the colour vividness of dyeing leather.
In above-mentioned retanning, the stuffing operation, can add 1.5%～2.5% zirconium tanning agent again or add 2%～4% aluminum tanning agent, described zirconium tanning agent is a zirconium sulfate, about 28%～35% (massfraction) of zirconium sesquioxide content; Aluminum tanning agent is an aluminium chlorohydroxide, about 40%～50% (massfraction) of aluminium sesquioxide content.With the high goat skin gloves leather of production shrinkage temperature.
More than unaccounted operation carry out according to common process, unaccounted leather material is commonly usedization of leather material, is industrial goods.
Compared with prior art, advantage of the present invention is: adopt organic phosphine tanning agent and supporting no chrome tanner skill to carry out the processing of goat skin gloves leather, can overcome the pollution of heavy metal chromium to environment, reduce the cost of enterprise's sewage disposal, the environment-friendly type goat glove leather of being produced is soft, plentiful, high resilience, elegant, grain are flat thin, bright-colored, the finished leather formaldehyde content meets the standard of ecological leather, shrinkage temperature (Ts) is up to more than 88 ℃, and physical and mechanical properties can reach conventional chrome-tanned requirement fully.
As follows according to the no chrome tanning goat skin gloves leather that the technology of patent of the present invention makes through the environmental-protecting performance detected result:
| The mensuration project | Formaldehyde content (mg/kg) | Content of 6-valence Cr ions (mg/kg) | Pentachlorophenol (mg/kg) | Carcinogenic aromatic amine (mg/kg) |
| The detected result technical indicator | 55.32 ＜150 | 2.06 ＜4 | Do not detect＜4 | Do not detect＜28 |
Embodiment:
A kind of chrome-free tanning production technique of goat glove leather, comprise the steps: successively to soften → pickling → organic phosphine tanning → oxidation → take horse to leave standstill → water squeezing stretching, extension → shaving → washing → degreasing, rinsing → washing → retanning stuffing → washing → stuffing → washing again → routinely chrome tanning carries out then.Subsequent technique can comprise hanging and dries dry → perching → whitening → fall soft → stretching,s extension → toggling (it is as follows that needs are covered with paint, lacquer, colour wash, etc. the skin operation: skin → spray feel is starched → pressed to back cover → spray plane) → check classification → gage to put in storage.Whole technology is basic identical with present chrome tanning production technique except master operations such as tanning and retanning, and the operation adjustment that can change aborning changes according to existing chrome tanning production technique.
Below by embodiment the present invention is elaborated, wherein only relate to improvement operation of the present invention, unaccounted operation is carried out according to common process.
Embodiment 1:
| Operation | Consumption/% | Materials | Temperature/℃ | Time/min | pH | Remarks |
| Pickling | 80 | Water | Normal temperature | |||
| 7.0 | Salt | 20 | Survey Baume 6～6.5 | |||
| 1.0 | Formic acid | 2×20+40 | 3.4～3.6 | |||
| Tanning | 2 | Organic phosphine tanning agent (Granofin FCC) | 120 | Spend the night and change 30min next day | ||
| 0.4 | Sodium bicarbonate | 5×30+60 | 5.5～5.7 | |||
| 2.0 | Syntannin (Tanicor KW) | 60 | Control liquid | |||
| Oxidation | 150 | Water | Normal temperature | |||
| 0.7 | Sodium peroxoborate | 60 | Check the oxidation situation | |||
| Washing | 200 | Water | Normal temperature | 10 | Take horse and survey Ts 〉=85 ℃ |
| Degreasing, rinsing | 300 | Water | 40 | |||
| 0.5 | Grease-removing agent (Tergolix SL-01) | Grease-removing agent consumption basis | ||||
| 0.4 | Oxalic acid | Situation is suitably adjusted | ||||
| 0.2 | Poly phosphate (Feliderm MPP) | |||||
| 0.1 | E.D.T.A. | 60 | 5.5～5.7 | Control liquid | ||
| Washing | 200 | Water | 35 | 10 | Control liquid | |
| Retanning, | 100 | Water | 35 |
| Stuffing | 0.1 | E.D.T.A. | 60 | |||
| 2.0 | Synthetic fat liquor (Derminol CST) | Fatting agent is with 60 ℃ | ||||
| 2.0 | Phosphate fat-liquoring agent (Derminol SF) | Add after the hot water emulsification | ||||
| 2.0 | Phenylethylene-maleic anhydride retanning agent (Tergotan TSP) | |||||
| 4.0 | Resin retaning agent (Tergotan RFC) | 40 | ||||
| 6.0 | Sulfone class exchange syntan (Tergotan S) | 60 | ||||
| 100 | Water (55 ℃) | 45 | 5 | |||
| 3.0 | The big right oil of sulfation (Derminol RA) | Fatting agent is with 60 ℃ | ||||
| 3.0 | Phosphate fat-liquoring agent (Derminol SF) | 60 | Add after the hot water emulsification | |||
| 1.0 | Formic acid | 10 | ||||
| 1.0 | Formic acid | 45 | 3.5～3.6 | Control liquid | ||
| Washing | 300 | Water | 45 | 10 | Control liquid | |
| Stuffing again | 150 | Water | 45 | |||
| 2.0 | Phosphate fat-liquoring agent (Derminol SF) | Fatting agent hot water | ||||
| 1.0 | Synthetic fat liquor (Derminol CST) | Add after the emulsification | ||||
| 3.0 | Nonionic fatting agent (Dermafinish LB) | 60 | ||||
| 1.0 | Formic acid | 30 | 3.3～3.4 | Control liquid | ||
| Washing | 300 | Water | 20 | 10 | Control liquid |
Annotate: English product code is the product of giving an example, and is the product of Switzerland Clariant company.
Embodiment 2:
| Operation | Consumption/% | Materials | Temperature/℃ | Time/min | pH | Remarks |
| Pickling | 80 | Water | Normal temperature | |||
| 7.0 | Salt | 20 | Survey Baume 6～6.5 | |||
| 1.0 | Formic acid |
| 0.3 | Sulfuric acid (massfraction 98%) | 2×20+ 40 | 2.5～2.8 | |||
| 3 | Zirconium tanning agent or aluminum tanning agent | 60 | ||||
| 0.5 | Sodium bicarbonate | 40 | 3.4～3.6 | |||
| Tanning | 2.5 | Organic phosphine tanning agent (Granofin FCC) | 120 | Spend the night and change 30min next day | ||
| 1.0 | Aromatic organic acid neutral salt (Feliderm DP) | |||||
| 1.0 | Cationic fat liquor (Catalix L) | 60 | ||||
| 0.3 | Sodium carbonate | 5×30+ 60 | 5.5～5.7 | |||
| 2.0 | Syntannin (Tanicor KW) | 60 | Control liquid | |||
| Oxidation | 150 | Water | Normal temperature | |||
| 0.7 | Hydrogen peroxide | 60 | Check the oxidation situation | |||
| Washing | 200 | Water | Normal temperature | 10 | Take horse and survey Ts 〉=85 ℃ |
| Degreasing/rinsing | 250 | Water | 45 | |||
| 0.45 | Grease-removing agent (Tergolix SL-01) | Grease-removing agent consumption basis | ||||
| 0.45 | Oxalic acid | Situation is suitably adjusted | ||||
| 0.15 | Poly phosphate (Feliderm MPP) | |||||
| 0.15 | E.D.T.A. | 60 | 5.5～5.7 | Control liquid | ||
| Washing | 200 | Water | 35 | 10 | Control liquid | |
| Retanning, stuffing | 100 | Water | 35 | |||
| 4.0 | Synthetic fat liquor (Derminol CST) | Fatting agent is with 60 ℃ | ||||
| 3.0 | Sulfation natural oil (Derminol RA) | Add after the hot water emulsification | ||||
| 2.0 | Styrene-maleic anhydride copolymer (Tergotan TSP) | |||||
| 4.0 | Resene retanning agent (Tergotan RFC) | 60 |
| 5.0 | Sulfone class exchange syntan (Tergotan S) | 30 | ||||
| 3.0 | Aromatic series synthetic tanning agent (Syncotan MRL) | 30 | ||||
| 1.5 | Dyestuff (Derma Brown DR) | 30 | ||||
| 5.0 | Tannin extract (Granifin AL) | 60 | ||||
| 100 | Water | 45 | 5 | |||
| 5.0 | Sulfation natural oil (Derminol RA) | Fatting agent adds after with 60 ℃ of hot water emulsifications | ||||
| 3.0 | Phosphorylation fatting agent (Derminol SF) | 60 | ||||
| 1.0 | Formic acid | 10 | ||||
| 1.0 | Formic acid | 45 | 3.5～3.6 | Control liquid | ||
| Washing | 300 | Water | 20 | 10 | Control liquid |
Annotate: English product code is the product of giving an example, and is the product of Switzerland Clariant company.
Embodiment 3 (when the goat skin gloves leather needs shrinkage temperature to be higher than 100 ℃, adopting this scheme):
| Operation | Consumption/% | Materials | Temperature/℃ | Time/min | PH | Remarks |
| This pre-treating technology is with embodiment 2. | ||||||
| Retanning, stuffing | 100 | Water | 35 | |||
| 3.0 | Phosphorylation fatting agent (Derminol SF) | 10 | ||||
| 6.0 | Tannin extract (Granofin TA) | 40 | ||||
| 1.5 | Dyestuff | 20 | ||||
| 3.0 | Styrene-maleic anhydride copolymer (Tergotan TSP) | |||||
| 2.0 | Sulphiting fatting agent (Derminol SJB) | 60 | ||||
| 1.0 | Formic acid | 30 | 3.5 | |||
| 1.0 | Levelling agent (Dermagen PC) | 40 | Control liquid | |||
| Washing | 300 | Water | 5 | Control liquid |
| Retanning again | 100 | Water | 35 | |||
| 2.0 | Cation oil (Catalix CX) | |||||
| 3.0 | Zirconium tanning agent | 60 | ||||
| 1.0 | Sodium formiate | 30 | ||||
| 0.5 | Sodium bicarbonate | 30 | 4.2 | Control liquid | ||
| Washing | 300 | Water | 5 | Control liquid | ||
| Neutralization | 100 | Water | 35 | |||
| 1.5 | Sodium formiate | 20 | ||||
| 1.0 | Bicarbonate of ammonia | 40 | 5.5 | Control liquid | ||
| Washing | 300 | Water | 5 | Control liquid | ||
| Dyeing, stuffing | 100 | Water | 45 | |||
| 1.0 | Dyestuff | 20 | ||||
| 4.0 | Phosphorylation fatting agent (Derminol SU-10) | |||||
| 3.0 | Phosphorylation fatting agent (Derminol SF) | |||||
| 4.0 | Sulphiting fatting agent (Derminol SJB) | |||||
| 3.0 | Sulfation natural oil (Derminol RA) | 60 | ||||
| 1.0 | Formic acid | 10 | ||||
| 1.0 | Formic acid | 40 | 3.3 | Control liquid | ||
| Washing | 300 | Water | 10 | Control liquid |
Claims (7)
1. the chrome-free tanning production technique of goat skin gloves leather, include following step: softening → pickling → organic phosphine tanning → oxidation → as to take horse to leave standstill → water squeezing stretching, extension → shaving → washing → degreasing, rinsing → washing → retanning stuffing → washing, chrome tanning subsequent technique routinely carries out then, the addition of additive is a benchmark with the graywall quality in each operation
Pickling procedure: liquor ratio is 80%, water temp is a normal temperature, the Industrial Salt consumption is 6%～8%, rotate 20min, the control degree Beaume is 6.0～6.5, adds mass concentration then more than or equal to 85% formic acid 8%～12 ‰, dividing 2-3 time adds, each 20min that rotates, control pH is 3.4～3.6, rotates 40min again;
Described tanning operation: in pickling liquid, carry out, add the organic phosphine tanning agent, the organic phosphine tanning agent is a sulfuric acid tetra methylol phosphine, and its consumption is 1.5%～2.5%, checks with the selenium indicator whether the organic phosphine tanning agent permeates fully behind the rotation 120min, otch shows light yellow proof infiltration fully, stop drum then and spend the night, rotate 30min morning next day, it is 5.5～5.7 that gradation adds alkali adjusting pH, each 30min that rotates rotates 60min at last; Add 1.5%～2.5% syntannin then, rotate 60min;
Described oxidation operation: liquor ratio is 150%, and the oxidant bleach with 0.5%～1% rotates 60min, removes residual organic phosphine tanning agent, checks that with the selenium indicator otch does not develop the color, and proves that oxidation is complete;
Described retanning stuffing operation: carry out gradation with different synthetic tanning agentes and fatting agent and add.
2. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 1, it is characterized in that: also comprise stuffing again and washing step behind the described last water-washing step, be added with 150% 40～45 ℃ water in the stuffing operation again, 2.0% phosphate fat-liquoring agent, 1.0% synthetic fat liquor, 3.0% nonionic fatting agent are added in gradation then, rotate 60min, adding 1.0% mass concentration again, to regulate pH more than or equal to 85% formic acid be 3.3～3.4, rotates 30min.
3. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 1 is characterized in that: also include retanning again behind the described last water-washing step successively, washing, neutralization, washing, dyeing, stuffing operation.
4. as the chrome-free tanning production technique of claim 2 or 3 described a kind of goat skin gloves leather, it is characterized in that: in the described tanning operation, alkali is sodium bicarbonate, sodium-acetate, magnesium oxide or yellow soda ash; In the oxidation operation, oxygenant is hydrogen peroxide or Sodium peroxoborate.
5. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 4, it is characterized in that: in described degreasing, the rinsing process, be added with 250%～300% 40～45 ℃ water, add 0.45%～0.5% grease-removing agent simultaneously, 0.4%～0.45% oxalic acid, 0.15%～0.2% poly phosphate, rotate 60min, regulating pH is 5.5～5.7.
6. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 5 is characterized in that: add 0.1%～0.5% ethylenediamine tetraacetic acid (EDTA) in described degreasing, rinsing process and the retanning stuffing operation, be abbreviated as E.D.T.A.
7. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 6, it is characterized in that: in described retanning, the stuffing operation, add 1.5%～2.5% zirconium tanning agent again or add 2%～4% aluminum tanning agent, described zirconium tanning agent is a zirconium sulfate, the content of zirconium sulfate is represented with the massfraction of zirconium sesquioxide, zirconium sesquioxide content 28%～35%; Aluminum tanning agent is an aluminium chlorohydroxide, and the content of aluminium chlorohydroxide is represented with the massfraction of aluminium sesquioxide, aluminium sesquioxide content 40%～50%.
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| CN102517409B (en) * | 2011-11-28 | 2013-07-24 | 郑州科信化工有限公司 | Leather retanning method |
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| CN105925735B (en) * | 2016-05-06 | 2018-11-23 | 嘉兴学院 | One kind is salt-free to exempt from pickling short route bating method without chrome |
| CN108165680B (en) * | 2018-03-05 | 2020-10-09 | 焦作隆丰皮草企业有限公司 | Comprehensive tanning agent for fur and non-dry-cleaning and chrome-free tanning process for fur |
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| CN111705171B (en) * | 2020-07-06 | 2022-04-22 | 河南中牛实业有限公司 | Production method of cow leather upper leather for dance shoes |
| CN114672598B (en) * | 2022-04-02 | 2024-01-19 | 隆丰革乐美时尚有限公司 | Chrome-free tanned sheepskin clothing leather and chrome-free tannage method thereof |
| CN116769979A (en) * | 2023-08-03 | 2023-09-19 | 江西隆华材料科技股份有限公司 | Preparation method of sheep leather |
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| CN1804045A (en) * | 2005-12-02 | 2006-07-19 | 四川大学 | Method for tanning high-temperature stable chromium-free costume soft leather |
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| CN1804045A (en) * | 2005-12-02 | 2006-07-19 | 四川大学 | Method for tanning high-temperature stable chromium-free costume soft leather |
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