CN110656209A - Method for making leather from sturgeon skin - Google Patents
Method for making leather from sturgeon skin Download PDFInfo
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- CN110656209A CN110656209A CN201910921023.9A CN201910921023A CN110656209A CN 110656209 A CN110656209 A CN 110656209A CN 201910921023 A CN201910921023 A CN 201910921023A CN 110656209 A CN110656209 A CN 110656209A
- Authority
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- Prior art keywords
- soaking
- aeration
- skin
- sturgeon
- under
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Links
- 241000881711 Acipenser sturio Species 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 102
- 239000010985 leather Substances 0.000 title claims abstract description 56
- 238000002791 soaking Methods 0.000 claims abstract description 190
- 238000005273 aeration Methods 0.000 claims abstract description 146
- 230000008569 process Effects 0.000 claims abstract description 44
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 42
- 238000004061 bleaching Methods 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 238000005554 pickling Methods 0.000 claims abstract description 35
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 238000005238 degreasing Methods 0.000 claims abstract description 15
- 238000004043 dyeing Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 238000006748 scratching Methods 0.000 claims description 51
- 230000002393 scratching effect Effects 0.000 claims description 51
- 238000005406 washing Methods 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 26
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 26
- 239000004571 lime Substances 0.000 claims description 26
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 239000013527 degreasing agent Substances 0.000 claims description 24
- 238000005237 degreasing agent Methods 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 18
- 235000013372 meat Nutrition 0.000 claims description 17
- 230000000149 penetrating effect Effects 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000011112 process operation Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims description 12
- 239000003899 bactericide agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 229940037003 alum Drugs 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 206010033675 panniculitis Diseases 0.000 claims description 7
- 210000004003 subcutaneous fat Anatomy 0.000 claims description 7
- 210000004304 subcutaneous tissue Anatomy 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 241000252335 Acipenser Species 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 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 4
- 241000876433 Acipenser dabryanus Species 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 3
- 241001125075 Acipenser baerii Species 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000007715 potassium iodide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 17
- 102000008186 Collagen Human genes 0.000 abstract description 13
- 108010035532 Collagen Proteins 0.000 abstract description 13
- 229920001436 collagen Polymers 0.000 abstract description 13
- 238000009896 oxidative bleaching Methods 0.000 abstract description 3
- 238000009895 reductive bleaching Methods 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 6
- 108090001060 Lipase Proteins 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000019421 lipase Nutrition 0.000 description 6
- 239000004519 grease Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- 210000001361 achilles tendon Anatomy 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 210000000845 cartilage Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000252344 Acipenser gueldenstaedtii Species 0.000 description 1
- 241000252355 Acipenser ruthenus Species 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 241000251464 Coelacanthiformes Species 0.000 description 1
- 102000012422 Collagen Type I Human genes 0.000 description 1
- 108010022452 Collagen Type I Proteins 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000609666 Tuber aestivum Species 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000032823 cell division Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N ***e Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/02—Fleshing, unhairing, samming, stretching-out, setting-out, shaving, splitting, or skiving skins, hides, or leather
- C14B1/04—Fleshing, unhairing, samming, stretching-out, setting-out, shaving, splitting, or skiving skins, hides, or leather using slicking, scraping, or smoothing-out cylinders or blades fixed on supports, e.g. cylinders, in a plane substantially at right angles to the working surface
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
-
- 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
- C14C1/08—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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or 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
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A method for preparing leather from sturgeon skin is characterized in that the sturgeon skin is processed through the procedures of bone plate protection → fleshing → degreasing → soaking → loose fiber → deliming softening → oxidative bleaching → reductive bleaching → pickling → deacidification → chrome tanning, and the like to obtain the wet blue leather, and the wet blue leather can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, coating, and the like according to the prior art. The hard bone plate and the grain surface can be prevented from being damaged by protecting the bone plate and the grain surface and carrying out the working procedure in the groove with the aeration function in the process of making the leather from the sturgeon skin; loosening collagen fibers through operations such as long-time uniform and mild expansion, pickling and the like in the leather making process, so that the finished leather is soft and full; bleaching by oxidation and reduction can substantially eliminate natural pigments. The method for making leather from sturgeon skin provided by the invention has strong practicability, can be used for processing different types of sturgeon skin, and can perform different operations of post-tanning wet processing and coating according to the requirements of finished products after processing the obtained blue wet leather.
Description
Technical Field
The invention belongs to the technical field of leather production and processing, and particularly relates to a processing technology for making leather from sturgeon skin.
Background
Sturgeon is a general term of fishes in Acipenserformes, originates from the mud pot age about 4.5 ~ 3.5.5 hundred million years ago today, belongs to Osteichthyes, RADIAXIABIA, Total order of cartilage and Scale, and Acipenserales, and is a kind of original cartilage and Scale fishes.
More importantly, the sturgeon has extremely high economic value. Sturgeon bone can inhibit cancer cell division, sturgeon meat has effects of caring skin, lowering blood pressure and blood lipid, nourishing brain, invigorating kidney, etc., and sturgeon liver and viscera can also be made into various foods. Sturgeon roe can be processed into caviar, and is called 'three-kind world food together with goose liver and truffle', sturgeon roe is a main species in sturgeon trade in the world and is also the most main income in sturgeon culture process in China.
In the development process of sturgeon products, the resource utilization of sturgeon skin is relatively weak. According to incomplete statistics, about 1000 tons of sturgeon skin is discarded because the sturgeon skin cannot be effectively utilized every year in China, so that precious biomass resources are wasted, and the environment is polluted. The development of a way for high-quality resource utilization of sturgeon skin becomes more and more important. At present, the sturgeon skin can be used for extracting collagen polypeptide (Liao, yellow morning, Jianghong, etc.. the response surface method optimizes the enzymolysis process [ J ] of the sturgeon skin collagen polypeptide, food technology, 2018, 4(1): 141-plus 147) and tanning (Zhangjie, the tanning process research of artificially cultured sturgeon skin [ D ] of the university of Wuhan engineering, 2012).
The sturgeon skin has special patterns, particularly five bone plates distributed on the skin, and is a special structure which is not possessed by other types of raw material skins, and the natural patterns of the sturgeon skin cannot be imitated by adopting other raw material skins. Therefore, the sturgeon skin has wide market prospect when being used for tanning. In the leather making process of the sturgeon skin, the bone plate is embedded in the skin, so that the processing technology required in the leather making process is greatly different from that of the traditional leather making process.
Disclosure of Invention
The inventor finds that the prior art has the following problems by researching the published technical data of making leather by using the sturgeon skin: plum macrostrong (plum macrostrong. sturgeon skin tanning method and sturgeon skin prepared by the method, CN 102154529A) only uses acid conditions in the process of tanning sturgeon skin, and in order to improve the softness and fullness of finished products in the conventional tanning process, liming is often needed, the common knowledge in the tanning industry is that the skin is well taken out of a ashtray, the sturgeon skin processed by the method is poor in the softness and fullness of finished leather due to the lack of the loosening effect of soda on fibers; an environment-friendly sturgeon skin tanning process, CN 103436643A, adopts pickling and then bleaching, and finally pickling and tanning are carried out again, the same procedures in the method are repeated, and waste of chemical raw materials is caused.
The inventor provides a method for making leather from sturgeon skin on the basis of carefully researching and disclosing sturgeon skin leather-making technology, sturgeon skin histology, leather-making chemistry and technology and leather-making mechanical equipment.
In the method, the leather making of the sturgeon skin is not carried out in a rotary drum commonly used for making leather, because the mutual friction between skins is severe in the rotating process of the rotary drum, and the skins have severe mechanical actions such as beating, bending and the like in the running process of the rotary drum, the interaction between a sturgeon skin bone plate and a bone plate and between the bone plate and scales is too strong, so that the bone plate is easy to wear, loosen and even fall off, and the grain surface can be damaged, therefore, the friction between the skins in the processing process is reduced as much as possible, and the severe mechanical actions such as beating, bending and the like are avoided. Carry out sturgeon skin tanning experiment in the groove of drawing that the fur coat is commonly used, if the paddle is drawn for a long time, also can cause the damage because of the friction between the skin, if further increase the liquid ratio of tanning in-process, not only can increase the waste water discharge, chemical material consumes also bigger, is unfavorable for practical application. However, the short paddle-stroke time can cause uneven distribution of the chemical materials in the bath solution, and the mechanical action of the system is too weak, so that the penetration rate of the chemical materials into the skin is reduced, the processing time or the dosage needs to be prolonged, and the method is not economical. The inventor reforms transform current scratch groove, at the trachea that scratch groove bottom installation punched, continuously aerates with compressed air in the tanning course of working to reduce the paddle and scratch the time, provide certain mechanical action again simultaneously, promote chemical material to intradermal infiltration, and make it distribute evenly in the bath lotion.
Five rows of hard bone plates on the sturgeon skin are embedded in the skin plate, the joint of the bone plate and the skin is only provided with a thin layer, once the skin connected with the thin layer is damaged or degraded in the processing process, the bone plate is easy to loosen or even fall off, and the quality of the finished leather is affected. In addition, although sturgeon skin collagen is typical type i collagen, its denaturation temperature is about 28 ℃, which is significantly lower than that of bovine achilles tendon collagen (42.81 ℃), and its resistance to enzymatic degradation is also inferior to that of bovine achilles tendon collagen (yanling, zhao yan, luliang, etc.. extraction of sturgeon skin collagen and its analysis of its physicochemical properties [ J ] food science, 2013, 34(23): 41-46). Therefore, in order to ensure that the bone plate does not fall off during the processing, the inventor firstly utilizes the characteristic that aldehydes can rapidly react with collagen, and firstly carries out the bone plate protecting process. In the process, a small amount of aldehyde substances are added to react with collagen on the surface of the leather plate to generate tanning effect, so that the enzymolysis resistance of the leather plate is improved, and the collagen at the joint of the bone plate and the leather plate is not easy to damage in the subsequent processing process of the sturgeon skin. Meanwhile, the using amount of the aldehyde substances is 0.2-0.6% of the weight of the sturgeon raw material skin, so that surface over-tanning is not caused, the grain surface appearance is not changed, and the removal of the fiber matrix and the loosening effect on the fiber in the subsequent operation are not influenced.
The hard bone plate on the sturgeon skin prevents the sturgeon skin from being fleshed by a fleshing machine or a bent knife, but the sturgeon skin is also greasy skin and must be fleshed. In the prior art, the meat is removed by using steel wire balls, so that the efficiency is low and the effect is limited. The inventor carries out fleshing through adorning the steel wire wheel on adjustable speed's buffing machine, and is not only efficient, and is effectual moreover, can not harm the skin again simultaneously. Meanwhile, the operation is carried out manually, the bone plate can be repeatedly polished in places with much grease, when the grease existing after the bone plate is removed, the polishing machine can be erected, the edge of the steel wire wheel is used for removing the meat, and the grease in the bone plate can be completely removed. After the fleshing operation, the sturgeon skin is degreased by a saponification method of a surfactant and alkali and lipase, so that the fat content in the skin is reduced.
The sodium sulfide and lime can swell the raw hide, and remove impurity proteins such as keratin and glycoprotein, thereby achieving the purpose of loosening the fiber. However, since the collagen in the skin plate has good expansibility and the hard bone plate does not expand, if the expansion is too severe, the connection between the weak bone plate and the skin plate is broken due to the large expansion difference between the two materials during the expansion process, which generates a great internal stress, so that the bone plate is loosened and falls off, and therefore, it is important to inhibit the expansion of the skin plate during the process of loosening the fibers. The inventor adopts the method of increasing the proportion of sodium hydrosulfide in sodium sulfide, adding sodium sulfide and lime in different times and increasing the dosage of liming auxiliary agent, so as to inhibit the expansion of collagen as much as possible, and simultaneously, the expansion process is mild, thereby avoiding damaging the connection between the leather plate and the bone plate. The ash removal is also carried out step by step after the ash alkali is expanded, so that the phenomenon that the connection between the leather plate and the bone plate is damaged due to the overlarge pH value difference between the surface and the inside of the leather sheet caused by using a large amount of ash removing agent is prevented.
Sturgeon skin often appears dark color such as grey black, brown and the like on the back, and the belly is white or beige, and has characteristics of itself. The sturgeon skin mainly comes from large sturgeons with roes taken, the sturgeon skin is usually long in culture period and has a lot of scars generated in the growth process, so that a lot of light-colored irregular stripes exist on a dark area on the back, and the final product is low in grade if the sturgeon skin is not bleached. After researching the common bleaching method in the leather making process, the inventor combines the process reality, selects the oxidant which can have good bleaching effect under the alkalescent condition to bleach firstly, then carries out reduction bleaching under the acidic condition, and can basically make the pelts present the uniform color from white to beige through twice bleaching. The oxidation bleaching is carried out under the alkalescent condition, the procedure of deliming and softening can be followed, then the reduction bleaching is carried out under the acidic condition, and the pickling operation can be carried out after the completion, so that the technical process is continuous, and the collagen fiber is prevented from being damaged due to the large fluctuation of the pH value or the large-range adjustment of the pH value for many times.
The inventor adds sulfuric acid and prolongs the pickling time in the pickling process, so that the aim of fully loosening fibers is fulfilled, and more importantly, hydroxyapatite in the bone plate is partially dissolved to soften the bone plate, so that the sturgeon skin can be subjected to severe mechanical processing in the retanning, dyeing and fatliquoring processes without causing the conditions of scratching, bone plate falling and the like. The pH value after pickling is very low, if tanning is directly carried out, alkali extraction at the final stage of tanning is difficult, the defects of chromium flower and the like are generated due to excessive alkali extraction times, and the plumpness of finished leather is reduced due to the low pH value at the initial stage of tanning. Thus tanning is preceded by first deacidification.
The tanning adopts chrome tanning agent as main material, and aluminum tanning agent and aldehyde tanning agent are matched at the same time. The use amount of the chrome tanning agent can be properly reduced after the aluminum tanning agent is added, so that the finished leather has the characteristics of chrome tanning and lighter blue color tone, and is suitable for processing light-colored leather. The modified glutaraldehyde is added, so that the finished leather has the characteristic of aldehyde tanning, and the grease in the sturgeon skin can be dispersed by utilizing the dispersing effect of the modified glutaraldehyde on natural grease, so that the penetration of a metal tanning agent is promoted.
On the basis of the research, the inventor provides a sturgeon skin tanning method, which is characterized in that sturgeon skin is processed through the procedures of bone plate protection → fleshing → degreasing → soaking → loose fiber → deliming softening → oxidative bleaching → reductive bleaching → pickling → deacidification → chrome tanning and the like to obtain wet blue leather, and the wet blue leather can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, coating and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows: bone protection plate: adding water with the weight of 400-500%, penetrant 0.5-1.0%, degreasing agent 0.5-1.0%, bactericide 0.2-0.5% and aldehyde substance 0.2-0.6% into sturgeon raw material skin, soaking for 18-24h under the conditions of paddling and aeration, draining and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the sturgeon skin after fleshing in water with the weight of 400-;
soaking: soaking the degreased sturgeon skin in water with the weight of 400-;
loose fibers: soaking sturgeon skin soaked in water with the weight of 400-500%, adding 0.5-1.0% of penetrating agent, 1.0-2.0% of degreasing agent, 1.0-3.0% of liming auxiliary agent and 0.2-0.4% of aldehyde substance, soaking for 1h under the condition of scratching and aeration, adding 0.8-2.0% of sodium hydrosulfide, soaking for 1-3h under the condition of scratching and aeration, adding 0.5-1.5% of sodium sulfide, 1.0-3.0% of lime and 1.0-3.0% of liming auxiliary agent, soaking for 2-4h under the condition of scratching and aeration, adding 1.0-3.0% of lime and 1.0-3.0% of liming auxiliary agent, soaking for 6-9h under the condition of scratching and aeration, adding 1.0-3.0% of lime, soaking for 4-6h under the condition of scratching and aeration, adding 1.0-3.0% of liming auxiliary agent, soaking for 4-6h under the condition of scratching and aeration, after all materials are added, intermittently performing scratching and aeration, wherein the total fiber loosening time is 96-144h, and washing after liquid drainage;
deliming and softening: soaking sturgeon skin with loose fibers in water with the weight of 400 plus materials of 500%, adding 1.0-2.5% of deliming agent, soaking for 1-3h under the conditions of paddling and aeration, washing after liquid discharge, adding water with the weight of 400 plus materials of 500% and 2.0-5.0% of deliming agent, soaking for 1-3h under the conditions of paddling and aeration, adding 0.2-0.5% of softening enzyme, soaking for 12-18h under the conditions of paddling and aeration, and washing after liquid discharge;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in water with the weight of 400-500%, adding 1.0-6.0% of oxidant, soaking for 1-5h under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 8.0-9.5 by using acid or alkali, draining liquid and washing by water;
reduction bleaching: soaking the sturgeon skin after oxidation bleaching in 60g/L sodium chloride aqueous solution with the weight of 400-500%, adding 2-4% of reducing agent, soaking for 2-6h under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 3.5-5.0 by using sulfuric acid in the process;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a 60g/L sodium chloride aqueous solution with the weight of 400-500%, adding 0.5-2.0% of organic acid, soaking for 2-6h under the conditions of paddling and aeration, adding sulfuric acid to enable the pH value of bath liquid to be 1.0-2.0, soaking for 8-10h under the conditions of paddling and aeration, intermittently paddling and aerating after all materials are added, and carrying out total pickling for 72-120 h;
acid removal: adding alkaline substances into the bath liquid after pickling, and soaking for 2-4h under paddling and aeration conditions to ensure that the pH value of the bath liquid is 2.8-3.3;
chrome tanning: adding 5-12% chrome tanning agent, 3-6% alum and 2-4% modified glutaraldehyde into the deacidified bath liquid, soaking for 36-48h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.6-4.0 under the paddling and aeration conditions for six times, and keeping the interval of 1h every time, finally heating the bath liquid to 40 ℃, and keeping the temperature for 12-24h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Wherein the sturgeon raw skin is any one of salt wet skin or 75% ethanol solution soaked for 72 h. The sturgeon skin is any one of acipenser dabryanus, acipenser ruthenus, acipenser baeri, acipenser brachypus or hybrid sturgeons. The aldehyde substance is any one of formaldehyde, glutaraldehyde or modified glutaraldehyde. The deliming agent is one or two of ammonium sulfate, ammonium chloride and ammonium-free deliming agent. The oxidant is any one of potassium permanganate, hydrogen peroxide, potassium chromate or sodium hypochlorite. The reducing agent is one or two of oxalic acid, sodium sulfite, sodium bisulfite and potassium iodide. The organic acid is any one of formic acid, acetic acid, citric acid or lactic acid. The alkaline substance used in deacidification is one or two of sodium carbonate, sodium thiosulfate, sodium sulfite and sodium bicarbonate.
The sturgeon skin tanning method provided by the invention has the following advantages:
1. the used equipment can be modified by additionally arranging a perforated air pipe at the bottom of the equipment on the basis of the existing leather (fur coat) cutting groove, so that the modification is simple, the cost is low, and the practicability is high;
2. the used chemical materials are common basic chemical materials and leather chemicals of a tannery, the sources are wide, the cost is low, the technology is mature, and meanwhile, the leather chemicals which have the same property and can realize the purpose of corresponding procedures can be selected according to the specific conditions of different factories, so that the application range is wide;
3. the process is reasonable in connection, avoids severe pH fluctuation in the processing process, reuses chemical materials for achieving the same purpose, reduces the production cost and period, reduces pollution and has strong operability.
Detailed Description
The following examples are given to illustrate the present invention in more detail, and it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that various insubstantial modifications and adaptations of the present invention will be made by those skilled in the art based on the above disclosure.
Example 1
The method comprises the following steps of soaking the skin of the Acipenser dabryanus for 72 hours in a 75% ethanol solution, processing the skin of the Acipenser dabryanus through a bone plate protection → fleshing → degreasing → soaking → loose fibers → deliming softening → oxidation bleaching → reduction bleaching → pickling → deacidification → chrome tanning and the like to obtain the wet blue leather, and performing the subsequent operations of retanning, dyeing, fatliquoring, finishing and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding 400 wt% of water, 0.5 wt% of penetrating agent, 0.5 wt% of degreasing agent, 0.2 wt% of bactericide and 0.2 wt% of glutaraldehyde into sturgeon raw material skin, soaking for 18h under the conditions of scratching and aeration, draining liquid and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the fleshed sturgeon skin in water with the weight of 400 percent and the temperature of 28 ℃, adding 1.0 percent of sodium carbonate and 1.5 percent of degreasing agent, soaking for 1 hour under the conditions of paddling and aeration, draining liquid and washing with water;
soaking: soaking degreased sturgeon skin in 400 wt% of water, adding 0.5% of penetrating agent, 1.0% of degreasing agent, 0.2% of bactericide and 30 activity units/g of lipase, soaking for 14h under paddling and aeration conditions, adjusting the pH value of bath liquid to 8.5 by using sodium carbonate, draining and washing by water;
loose fibers: soaking sturgeon skin soaked in water with the weight of 400%, adding 0.5% of penetrating agent, 1.0% of degreasing agent, 1.0% of liming auxiliary agent and 0.2% of modified glutaraldehyde, soaking for 1 hour under the scratching and aeration conditions, adding 0.8% of sodium hydrosulfide, soaking for 1 hour under the scratching and aeration conditions, adding 0.5% of sodium sulfide, 1.0% of lime and 1.0% of liming auxiliary agent, soaking for 2 hours under the scratching and aeration conditions, adding 1.0% of lime and 1.0% of liming auxiliary agent, soaking for 6 hours under the scratching and aeration conditions, adding 1.0% of lime, soaking for 4 hours under the scratching and aeration conditions, adding all materials, then intermittently scratching and aerating, totally loosening the fiber for 96 hours, draining and washing with water;
deliming and softening: soaking sturgeon skin with loose fibers in 400% of water by weight, adding 1.0% of ammonium-free deliming agent, soaking for 1h under the conditions of paddling and aeration, draining liquid, washing, adding water with the weight of 400% of the sturgeon skin and 2.0% of ammonium chloride, soaking for 1h under the conditions of paddling and aeration, adding 0.2% of softening enzyme, soaking for 12h under the conditions of paddling and aeration, draining liquid, and washing;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in 400 wt% of water, adding 1.0% of sodium hypochlorite, soaking for 1h under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 8.0 by using acid in the soaking period, draining liquid and washing by using water;
reduction bleaching: soaking the oxidized and bleached sturgeon skin in a sodium chloride aqueous solution with the weight of 400 and the concentration of 60g/L, adding 2 percent potassium iodide, soaking for 2 hours under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 3.5 by using sulfuric acid in the process;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a sodium chloride aqueous solution with the weight of 400% and the concentration of 60g/L, adding 0.5% of citric acid, soaking for 2 hours under the paddling and aeration conditions, adding sulfuric acid to enable the pH value of bath liquid to be 1.0, soaking for 8 hours under the paddling and aeration conditions, adding all materials, and then intermittently paddling and aerating for 72 hours of total pickling time;
acid removal: adding sodium carbonate and sodium bicarbonate into the bath liquid after pickling, and soaking for 2h under the paddling and aeration conditions to ensure that the pH value of the bath liquid is 2.8;
chrome tanning: adding 5% chrome tanning agent, 3% alum and 2% modified glutaraldehyde into the deacidified bath liquid, soaking for 36h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.6 under the paddling and aeration conditions for six times, and spacing for 1h every time, finally heating the bath liquid to 40 ℃, and keeping the temperature for 12h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Example 2
Processing the salt wet skin of the Acipenser gueldenstaedtii by the processes of bone plate protection → fleshing → degreasing → water soaking → loose fiber → deliming and softening → oxidation bleaching → reduction bleaching → pickling → deacidification → chrome tanning and the like to obtain the wet blue leather, wherein the wet blue leather can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, finishing and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding 500 wt% of water, 1.0 wt% of penetrating agent, 1.0 wt% of degreasing agent, 0.5% of bactericide and 0.6% of modified glutaraldehyde into sturgeon raw material skin, soaking for 24h under the conditions of scratching and aeration, draining liquid and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the fleshed sturgeon skin in water with the weight of 500% and the temperature of 32 ℃, adding 2.5% of sodium carbonate and 3.0% of degreasing agent, soaking for 3 hours under the conditions of paddling and aeration, draining liquid and washing with water;
soaking: soaking degreased sturgeon skin in 500 wt% of water, adding 1.0% of penetrant, 2.0% of degreasing agent, 0.5% of bactericide and 100 activity units/g lipase, soaking for 18h under paddling and aeration conditions, adjusting the pH value of bath liquid to 9.5 by using sodium carbonate, draining, and washing;
loose fibers: soaking sturgeon skin soaked in water with the weight of 500 percent of that of sturgeon skin, adding 1.0 percent of penetrating agent, 2.0 percent of degreasing agent, 3.0 percent of liming auxiliary agent and 0.4 percent of formaldehyde, soaking for 1 hour under the scratching and aeration conditions, adding 2.0 percent of sodium hydrosulfide, soaking for 3 hours under the scratching and aeration conditions, adding 1.5 percent of sodium sulfide, 3.0 percent of lime and 3.0 percent of liming auxiliary agent, soaking for 4 hours under the scratching and aeration conditions, adding 3.0 percent of lime and 3.0 percent of liming auxiliary agent, soaking for 9 hours under the scratching and aeration conditions, adding 3.0 percent of lime, soaking for 6 hours under the scratching and aeration conditions, scratching and aeration intermittently after all materials are added, loosening the fiber for 144 hours, and washing with water after liquid discharge;
deliming and softening: soaking sturgeon skin after loose fibers in 500% of water by weight of the sturgeon skin, adding 2.5% of ammonium sulfate, soaking for 3 hours under paddling and aeration conditions, draining liquid, washing, adding 500% of water by weight of the sturgeon skin and 5.0% of ammonium sulfate, soaking for 3 hours under paddling and aeration conditions, adding 0.5% of softening enzyme, soaking for 18 hours under paddling and aeration conditions, draining liquid, and washing;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in 500 wt% of water, adding 6.0% of hydrogen peroxide, soaking for 5h under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 9.5 by alkali during the soaking, draining liquid and washing by water;
reduction bleaching: soaking the oxidized and bleached sturgeon skin in a sodium chloride aqueous solution with the weight of 500 percent and the concentration of 60g/L, adding 4 percent of sodium bisulfite, soaking for 6 hours under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 5.0 by using sulfuric acid in the process;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a 60g/L sodium chloride aqueous solution with the weight of 500%, adding 2.0% of lactic acid, soaking for 6 hours under the paddling and aeration conditions, adding sulfuric acid to enable the pH value of bath liquid to be 2.0, soaking for 10 hours under the paddling and aeration conditions, adding all materials, and then intermittently paddling and aerating for a total pickling time of 120 hours;
acid removal: adding sodium thiosulfate into the bath liquid after the pickling, and soaking for 4h under the paddling and aeration conditions to ensure that the pH value of the bath liquid is 3.3;
chrome tanning: adding 12% chrome tanning agent, 6% alum and 4% modified glutaraldehyde into the deacidified bath liquid, soaking for 48h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 4.0 under the paddling and aeration conditions for six times, and spacing for 1h every time, finally heating the bath liquid to 40 ℃, and carrying out 24h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Example 3
The method comprises the following steps of processing sturgeon salted wet skin by the processes of bone plate protection → fleshing → degreasing → water soaking → loose fiber → deliming softening → oxidation bleaching → reduction bleaching → pickling → deacidification → chrome tanning and the like to obtain wet blue leather, and performing the subsequent operations of retanning, dyeing, fatliquoring, finishing and the like on the wet blue leather according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding 450 wt% of water, 0.8 wt% of penetrating agent, 1.0 wt% of degreasing agent, 0.4 wt% of bactericide and 0.5 wt% of formaldehyde into sturgeon raw material skin, soaking for 20h under the conditions of paddling and aeration, draining liquid and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the fleshed sturgeon skin in water with the weight of 450 and 30 ℃, adding 1.5 percent of sodium carbonate and 2.0 percent of degreasing agent, soaking for 1.5 hours under the conditions of paddling and aeration, draining liquid and washing;
soaking: soaking the degreased sturgeon skin in 400 wt% of water, adding 1.0% of penetrating agent, 1.5% of degreasing agent, 0.5% of bactericide and 50 activity units/g of lipase, soaking for 18h under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 9.2 by using sodium carbonate, draining and washing by water;
loose fibers: soaking sturgeon skin soaked in water with the weight of 500 percent of the sturgeon skin, adding 1.0 percent of penetrating agent, 1.0 percent of degreasing agent, 3.0 percent of liming auxiliary agent and 0.3 percent of glutaraldehyde, soaking for 1 hour under the scratching and aeration conditions, adding 1.0 percent of sodium hydrosulfide, soaking for 1.5 hours under the scratching and aeration conditions, adding 0.5 percent of sodium sulfide, 3.0 percent of lime and 2.0 percent of liming auxiliary agent, soaking for 4 hours under the scratching and aeration conditions, adding 2.0 percent of lime and 2.0 percent of liming auxiliary agent, soaking for 7 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 6 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 5 hours under the scratching and aeration conditions, intermittently scratching and draining after all materials are added, totally loosening the fiber for 120 hours, and washing the sturgeon water;
deliming and softening: soaking sturgeon skin after loose fibers in 500% of water by weight of the sturgeon skin, adding 1.5% of ammonium-free deliming agent, soaking for 2 hours under the paddling and aeration conditions, draining liquid, washing, adding water 400% of the weight of the sturgeon skin and 3% of ammonium sulfate, soaking for 3 hours under the paddling and aeration conditions, adding 0.3% of softening enzyme, soaking for 16 hours under the paddling and aeration conditions, draining liquid, and washing;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in 500 wt% of water, adding 2.5% of potassium chromate, soaking for 3h under paddling and aeration conditions, adjusting the pH value of bath liquid to 9.0 by alkali during the soaking, draining liquid and washing by water;
reduction bleaching: soaking the oxidized and bleached sturgeon skin in a sodium chloride aqueous solution with the weight of 400 percent and the concentration of 60g/L, adding 1 percent of oxalic acid and 2 percent of sodium sulfite, soaking for 4 hours under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 3.5 by using sulfuric acid in the period;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a 60g/L sodium chloride aqueous solution with the weight of 450% of the sturgeon skin, adding 1% acetic acid, soaking for 4 hours under the paddling and aeration conditions, adding sulfuric acid to enable the pH value of bath liquid to be 1.5, soaking for 10 hours under the paddling and aeration conditions, adding all materials, and then intermittently paddling and aerating for 96 hours of total pickling time;
acid removal: adding sodium carbonate and sodium sulfite into the bath liquid after the pickling, and soaking for 4 hours under the paddling and aeration conditions to ensure that the pH value of the bath liquid is 3.0;
chrome tanning: adding 8% chrome tanning agent, 4% alum and 2% modified glutaraldehyde into the deacidified bath liquid, soaking for 48h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.8 under the paddling and aeration conditions for six times, and spacing for 1h every time, finally heating the bath liquid to 40 ℃, and keeping the temperature for 12h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Example 4
After being soaked in 75% ethanol solution for 72 hours, the Siberian sturgeon skin is processed by the procedures of bone plate protection → fleshing → degreasing → soaking → loose fiber → deliming softening → oxidative bleaching → reductive bleaching → pickling → deacidification → chrome tanning and the like to obtain the wet blue leather, and the wet blue leather can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, finishing and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding 500 wt% of water, 1.0 wt% of penetrating agent, 1.0 wt% of degreasing agent, 0.3% of bactericide and 0.5% of formaldehyde into sturgeon raw material skin, soaking for 20h under the conditions of paddling and aeration, draining liquid and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the fleshed sturgeon skin in water with the weight of 500% and the temperature of 32 ℃, adding 2.5% of sodium carbonate and 2.0% of degreasing agent, soaking for 3 hours under the conditions of paddling and aeration, draining liquid and washing with water;
soaking: soaking degreased sturgeon skin in water with the weight of 450 percent of the weight of the sturgeon skin, adding 0.8 percent of penetrating agent, 1.5 percent of degreasing agent, 0.4 percent of bactericide and 60 activity units/g of lipase, soaking for 16 hours under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 8.8 by using sodium carbonate, draining liquid and then washing;
loose fibers: soaking sturgeon skin soaked in water with the weight of 500 percent of the sturgeon skin, adding 1.0 percent of penetrating agent, 1.5 percent of degreasing agent, 1.5 percent of liming auxiliary agent and 0.2 percent of glutaraldehyde, soaking for 1 hour under the scratching and aeration conditions, adding 1.5 percent of sodium hydrosulfide, soaking for 2 hours under the scratching and aeration conditions, adding 1.0 percent of sodium sulfide, 2.0 percent of lime and 3.0 percent of liming auxiliary agent, soaking for 2 hours under the scratching and aeration conditions, adding 3.0 percent of lime and 3.0 percent of liming auxiliary agent, soaking for 6 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 4-6 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 5 hours under the scratching and aeration conditions, intermittently scratching and draining after all materials are added, totally loosening the fiber for 100 hours, and washing the sturgeon water;
deliming and softening: soaking sturgeon skin after loose fibers in 500% of water by weight of the sturgeon skin, adding 1.5% of ammonium chloride, soaking for 1.5 hours under the paddling and aeration conditions, draining liquid, then washing, adding water by weight of 500% of sturgeon skin and 4% of ammonium sulfate, soaking for 3 hours under the paddling and aeration conditions, adding 0.5% of softening enzyme, soaking for 14 hours under the paddling and aeration conditions, draining liquid, and then washing;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in 500% of water by weight, adding 2% of potassium permanganate, soaking for 2 hours under paddling and aeration conditions, adjusting the pH value of bath liquid to 8.2 by alkali during the soaking, draining liquid and washing by water;
reduction bleaching: soaking the oxidized and bleached sturgeon skin in a sodium chloride aqueous solution with the weight of 400 percent and the concentration of 60g/L, adding 4 percent of sodium sulfite, soaking for 5 hours under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 4.0 by using sulfuric acid in the process;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a sodium chloride aqueous solution with the weight of 400% and the concentration of 60g/L, adding 1.0% formic acid, soaking for 3 hours under the paddling and aeration conditions, adding sulfuric acid to enable the pH value of bath liquid to be 1.8, soaking for 9 hours under the paddling and aeration conditions, adding all materials, and then intermittently paddling and aerating for 96 hours;
acid removal: adding sodium sulfite and sodium bicarbonate into the bath liquid after pickling, and soaking for 3h under the paddling and aeration conditions to ensure that the pH value of the bath liquid is 3.0;
chrome tanning: adding 9% chrome tanning agent, 4% alum and 3% modified glutaraldehyde into the deacidified bath liquid, soaking for 40h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.8 under the paddling and aeration conditions for six times, and spacing for 1h every time, finally heating the bath liquid to 40 ℃, and carrying out 14h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Example 5
The hybrid sturgeon salt wet skin is processed by the procedures of bone plate protection → fleshing → degreasing → water soaking → loose fiber → deliming softening → oxidation bleaching → reduction bleaching → pickling → deacidification → chrome tanning and the like to obtain the wet blue leather, and the wet blue leather can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, coating and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding 500 wt% of water, 0.5 wt% of penetrating agent, 1.0 wt% of degreasing agent, 0.5 wt% of bactericide and 0.5 wt% of modified glutaraldehyde into sturgeon raw material skin, soaking for 22h under the conditions of scratching and aeration, draining liquid and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the fleshed sturgeon skin in water with the weight of 500% and the temperature of 32 ℃, adding 1.5% of sodium carbonate and 2.5% of degreasing agent, soaking for 3 hours under the conditions of paddling and aeration, draining liquid and washing with water;
soaking: soaking degreased sturgeon skin in 500 wt% of water, adding 0.5% of penetrating agent, 1.0% of degreasing agent, 0.3% of bactericide and 50 activity units/g of lipase, soaking for 16h under paddling and aeration conditions, adjusting the pH value of bath liquid to 9.3 by using sodium carbonate, draining and washing by water;
loose fibers: soaking sturgeon skin soaked in water with the weight of 500 percent of that of sturgeon skin, adding 1.0 percent of penetrating agent, 1.0 percent of degreasing agent, 2.0 percent of liming auxiliary agent and 0.2 percent of modified glutaraldehyde, soaking for 1 hour under the scratching and aeration conditions, adding 1.0 percent of sodium hydrosulfide, soaking for 2 hours under the scratching and aeration conditions, adding 0.5 percent of sodium sulfide, 2.0 percent of lime and 2.0 percent of liming auxiliary agent, soaking for 4 hours under the scratching and aeration conditions, adding 2.0 percent of lime and 1.0 percent of liming auxiliary agent, soaking for 9 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 4 hours under the scratching and aeration conditions, adding 2.0 percent of lime, soaking for 6 hours under the scratching and aeration conditions, scratching and aeration are carried out intermittently after all materials are added, the total fiber loosening time is 120 hours, and washing with water after liquid drainage;
deliming and softening: soaking sturgeon skin after loose fibers in 500% of water by weight of the sturgeon skin, adding 1.0% of ammonium-free deliming agent, soaking for 2 hours under the paddling and aeration conditions, draining liquid, washing, adding water with the weight of 500% of the sturgeon skin and 3% of ammonium sulfate, soaking for 2 hours under the paddling and aeration conditions, adding 0.3% of softening enzyme, soaking for 17 hours under the paddling and aeration conditions, draining liquid, and washing;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in 500 wt% of water, adding 1.0 potassium permanganate, soaking for 2.5h under paddling and aeration conditions, adjusting the pH value of bath liquid to 8 by alkali during the soaking, draining liquid and washing by water;
reduction bleaching: soaking the oxidized and bleached sturgeon skin in a sodium chloride aqueous solution with the weight of 500 percent and the concentration of 60g/L, adding 1 percent of oxalic acid and 2 percent of sodium sulfite, soaking for 5 hours under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 4.5 by using sulfuric acid in the period;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a sodium chloride aqueous solution with the weight of 400% and the concentration of 60g/L, adding 1% formic acid, soaking for 3 hours under the paddling and aeration conditions, adding sulfuric acid to enable the pH value of bath liquid to be 1.5, soaking for 10 hours under the paddling and aeration conditions, adding all materials, and then intermittently paddling and aerating for a total pickling time of 120 hours;
acid removal: adding sodium carbonate and sodium thiosulfate into the bath liquid after the pickling, and soaking for 2h under the paddling and aeration conditions to ensure that the pH value of the bath liquid is 3.1;
chrome tanning: adding 6% chrome tanning agent, 3% alum and 2% modified glutaraldehyde into the deacidified bath liquid, soaking for 36h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.8 under the paddling and aeration conditions for six times, and spacing for 1h every time, finally heating the bath liquid to 40 ℃, and carrying out 18h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
Claims (9)
1. A method for preparing leather from sturgeon skin is characterized in that the sturgeon skin is processed by the procedures of bone plate protection → fleshing → degreasing → soaking → loose fiber → deliming softening → oxidation bleaching → reduction bleaching → pickling → deacidification → chrome tanning, and the like to obtain the wet blue leather which can be subjected to the subsequent operations of retanning, dyeing, fatliquoring, coating, and the like according to the prior art; the working procedures are all carried out in a paddle vat with an aeration function, the material dosage in each working procedure is based on the weight of the sturgeon raw material skin, and the concrete operation of the working procedures is as follows:
bone protection plate: adding water with the weight of 400-500%, penetrant 0.5-1.0%, degreasing agent 0.5-1.0%, bactericide 0.2-0.5% and aldehyde substance 0.2-0.6% into sturgeon raw material skin, soaking for 18-24h under the conditions of paddling and aeration, draining and washing with water;
removing meat: the sturgeon skin meat surface treated by the bone-protecting plate faces upwards, is nailed on a wood plate by a nail, and is grinded by a grinder provided with a steel wire wheel to remove the subcutaneous tissue and fat of the skin;
degreasing: soaking the sturgeon skin after fleshing in water with the weight of 400-;
soaking: soaking the degreased sturgeon skin in water with the weight of 400-;
loose fibers: soaking sturgeon skin soaked in water with the weight of 400-500%, adding 0.5-1.0% of penetrating agent, 1.0-2.0% of degreasing agent, 1.0-3.0% of liming auxiliary agent and 0.2-0.4% of aldehyde substance, soaking for 1h under the condition of scratching and aeration, adding 0.8-2.0% of sodium hydrosulfide, soaking for 1-3h under the condition of scratching and aeration, adding 0.5-1.5% of sodium sulfide, 1.0-3.0% of lime and 1.0-3.0% of liming auxiliary agent, soaking for 2-4h under the condition of scratching and aeration, adding 1.0-3.0% of lime and 1.0-3.0% of liming auxiliary agent, soaking for 6-9h under the condition of scratching and aeration, adding 1.0-3.0% of lime, soaking for 4-6h under the condition of scratching and aeration, adding 1.0-3.0% of liming auxiliary agent, soaking for 4-6h under the condition of scratching and aeration, after all materials are added, intermittently performing scratching and aeration, wherein the total fiber loosening time is 96-144h, and washing after liquid drainage;
deliming and softening: soaking sturgeon skin with loose fibers in water with the weight of 400 plus materials of 500%, adding 1.0-2.5% of deliming agent, soaking for 1-3h under the conditions of paddling and aeration, washing after liquid discharge, adding water with the weight of 400 plus materials of 500% and 2.0-5.0% of deliming agent, soaking for 1-3h under the conditions of paddling and aeration, adding 0.2-0.5% of softening enzyme, soaking for 12-18h under the conditions of paddling and aeration, and washing after liquid discharge;
oxidizing and bleaching: soaking the delimed and softened sturgeon skin in water with the weight of 400-500%, adding 1.0-6.0% of oxidant, soaking for 1-5h under the conditions of paddling and aeration, adjusting the pH value of bath liquid to 8.0-9.5 by using acid or alkali, draining liquid and washing by water;
reduction bleaching: soaking the sturgeon skin after oxidation bleaching in 60g/L sodium chloride aqueous solution with the weight of 400-500%, adding 2-4% of reducing agent, soaking for 2-6h under the conditions of paddling and aeration, and adjusting the pH value of bath liquid to 3.5-5.0 by using sulfuric acid in the process;
pickling: soaking the sturgeon skin subjected to reduction bleaching in a 60g/L sodium chloride aqueous solution with the weight of 400-500%, adding 0.5-2.0% of organic acid, soaking for 2-6h under the conditions of paddling and aeration, adding sulfuric acid to enable the pH value of bath liquid to be 1.0-2.0, soaking for 8-10h under the conditions of paddling and aeration, intermittently paddling and aerating after all materials are added, and carrying out total pickling for 72-120 h;
acid removal: adding alkaline substances into the bath liquid after pickling, and soaking for 2-4h under paddling and aeration conditions to ensure that the pH value of the bath liquid is 2.8-3.3;
chrome tanning: adding 5-12% chrome tanning agent, 3-6% alum and 2-4% modified glutaraldehyde into the deacidified bath liquid, soaking for 36-48h under the paddling and aeration conditions, then utilizing sodium bicarbonate to adjust the pH value of the bath liquid to 3.6-4.0 under the paddling and aeration conditions for six times, and keeping the interval of 1h every time, finally heating the bath liquid to 40 ℃, and keeping the temperature for 12-24h under the paddling and aeration conditions;
the blue wet leather can be obtained by tanning through the above process operations, and the temperature is normal temperature when other processes are carried out except the described process operations.
2. The sturgeon skin tanning method according to claim 1, characterized in that sturgeon raw skin is any one of salt wet skin or 75% ethanol solution soaked for 72 h.
3. A method of making leather from sturgeon skin according to claim 1 or 2, characterized in that the sturgeon skin is any one of acipenser dabryanus, acipenser ruthensis, acipenser baeri, acipenser brevifilis or hybrid sturgeon.
4. The sturgeon skin tanning method according to claim 1, characterized in that the aldehyde substance is any one of formaldehyde, glutaraldehyde or modified glutaraldehyde.
5. The sturgeon skin tanning method as claimed in claim 1, wherein the deliming agent is one or both of ammonium sulfate, ammonium chloride and an ammonium-free deliming agent.
6. The sturgeon skin tanning method according to claim 1, characterized in that the oxidant is any one of potassium permanganate, hydrogen peroxide, potassium chromate or sodium hypochlorite.
7. The sturgeon skin tanning method as claimed in claim 1, wherein the reducing agent is one or two of oxalic acid, sodium sulfite, sodium bisulfite and potassium iodide.
8. The sturgeon skin tanning method according to claim 1, characterized in that the organic acid is any one of formic acid, acetic acid, citric acid or lactic acid.
9. The method for tanning sturgeon skin according to claim 1, characterized in that the alkaline substance used in the deacidification is one or two of sodium carbonate, sodium thiosulfate, sodium sulfite and sodium bicarbonate.
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| CN115232891A (en) * | 2022-07-28 | 2022-10-25 | 四川大学 | Leather-making ammonium-free deliming agent with grain surface protection function and deliming method |
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