CN103243182A - Tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution - Google Patents
Tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 27
- 239000011651 chromium Substances 0.000 title claims abstract description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 235000008733 Citrus aurantifolia Nutrition 0.000 title claims abstract description 17
- 235000011941 Tilia x europaea Nutrition 0.000 title claims abstract description 17
- 239000004571 lime Substances 0.000 title claims abstract description 17
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract 4
- 230000008569 process Effects 0.000 claims abstract description 38
- 230000035617 depilation Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000007654 immersion Methods 0.000 claims description 31
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000000149 penetrating effect Effects 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 108091005502 Aspartic proteases Proteins 0.000 claims description 12
- 102000035101 Aspartic proteases Human genes 0.000 claims description 12
- 102000035092 Neutral proteases Human genes 0.000 claims description 12
- 108091005507 Neutral proteases Proteins 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 241000370738 Chlorion Species 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 108010006035 Metalloproteases Proteins 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 108090000145 Bacillolysin Proteins 0.000 claims description 4
- 108010019160 Pancreatin Proteins 0.000 claims description 4
- 229940055695 pancreatin Drugs 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 102000035195 Peptidases Human genes 0.000 claims description 2
- 108091005804 Peptidases Proteins 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 210000002784 stomach Anatomy 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 21
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 210000004209 hair Anatomy 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- -1 chromium-zirconium-aluminium Chemical compound 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000004919 hair shaft Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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Abstract
The invention discloses a tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution. The tanning method is characterized in that the pollution of lime, sulfide, chloride ion and heavy metal chromium is not generated in the whole pre-tanning preparation and tanning process, so that main pollutants for tanning are completely eliminated. The processes include a soaking pre-treatment process, a composite enzyme depilation process and a chromium-free tanning process which are combined in an optimized manner and cooperated to develop a novel clean tanning method, so that the prepared finished leather satisfies the national standards, and a lime, sulfide, chloride ion and heavy metal chromium pollution problem which troubles the tanning industry all the time is radically solved, and therefore, the environment is protected and the waste is turned into things of value. Moreover, the tanning method further can be used for greatly lowering the material cost and increasing the economic benefits.
Description
Technical field
The present invention relates to a kind of method for leather-making that lime, sulfide, chlorion and heavy metal chromium pollute that do not have, belong to the leather-making technology field.
Background technology
Tanning industry is with a long history, also is the characteristic conventional industries that China has comprehensive advantage, is bringing into play important effect at aspects such as foreign exchange earnings.But tanning industry has also produced pollution to environment to a certain extent when bringing economic interests and social benefit.Therefore, pollutent from source reduction process hides process, carrying out in an all-round way cleans Technology, adopts novel low dirt, pollution-free technology extremely urgent.
As everyone knows, preparing workshop section before tanning is the main source of tanning industry pollutent.Have data to show, prepare BOD that workshop section produces before tanning and be 88% of BOD that whole process of production produces, COD is 73%, and suspended solid is 83%, and neutral salt is 85%.Preparing to pollute in the workshop section the heaviest, the most unmanageable before tanning is the depilation operation.Polluting material such as a large amount of lime, sulfide have been used in the tradition depilation operation, BOD, the COD and the suspended substance that produce as liming depilation operation account for 48%, 52% and the 56%(Konrad C for preparing workshop section respectively, Bichler B, Lorber K, et al. Input/Output Analysis at a Chilean Tannery. Journal of The Society of Leather Technologists and Chemists, 2000,84:223-226.).
In addition, since chromic tanning was bathed in Dennis invention one in 1883, because the chrome tanned leather good comprehensive performances, chrome tanning agent became the main tanning agent of leather (light leather) tanning, almost can not be substituted.Along with the continuous progress of development of times and society, chromic tanning also is faced with formidable challenges.On the one hand, chromium reserves in the world is limited and be Nonrenewable resources, and China is poor chromium country, and it is the reality that is difficult to avoid that a large amount of uses can be moved towards exhaustion.On the other hand, the sewage in the leather production, mud, contain also intractable of chromium solid waste.
At a pollution difficult problem of preparing workshop section before tanning, existing many technology of cleaning emerge, and bathe grey alkaline process less as modification, utilize sulfide concentration more high, the principle more strong to the hair effect reaching under the prerequisite of better hair removal effect, save the consumption of sulfide, reduced grey alkali pollution; The recycle of the multiple grey waste liquid of depilation liming also is to reduce pollution by reducing grey alkali consumption for another example; Also can reduce pollution such as methods such as guarantor's hair epilations in addition, protect the hair epilation by controlling reductive agent and alkali to the action condition of hair, make its effect hair root rather than hair shaft, thereby stay complete hair.Can effectively reduce the pollutions such as organism in the waste water like this, reduce BOD and the COD of waste water, reduce the consumption of sulfide and (but defend China, Wang Kunyu. ecological process hides philosophy and technique [M]. Beijing: China Environmental Science Press, 2009:96-105.) in order to alleviate pollution of chromium, people turn to sight to no chrome tanning, high-absorption chrome tanning or few chromium in conjunction with tanning.At present few chromium in conjunction with tanning in, chromium and other melts combine tannings occupy critical role, wherein have chromium-aluminium in conjunction with tanning, chromium-rare earth in conjunction with tanning, chromium-zinc in conjunction with tan, chromium-zirconium-aluminium combination is tanned etc.Though these few chrome tanning systems have reduced pollution of chromium, or the performance of finished leather descends to some extent, or has brought new pollution, so all there is not really to realize industrial applications.
In sum, still there is following shortcoming in the existing technology that cleans:
(1) prior art is not broken the process hides common process mostly, just cuts down the quantity discharged of pollutent on the basis of common process, does not have thorough removal of pollutants.
(2) existingly clean technology and too rely on the novel green leather chemicals, utilize the very high green leather chemical of price to reduce the pollution of process hides process, cost is higher, and leather-making enterprises is difficult to bear.
Summary of the invention
The objective of the invention is provides a kind of no lime at the deficiencies in the prior art; sulfide; the method for leather-making that chlorion and heavy metal chromium pollute; be characterized in by immersion pretreatment technology plate; prozyme dehairing process plate; Chrome-free tanning process plate; under the optimum combination and synergy of these three technology plates; developed a kind of novel method for leather-making that cleans; not only can meet national standard at the finished leather of guaranteeing to make; fundamentally solved the lime that always perplexs leather industry; sulfide; the pollution problem of chlorion and heavy metal chromium; protected environment; turn waste into wealth; can also reduce material cost significantly, increase economic benefit.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except specifying.
The method of the process hides of no lime, sulfide, chlorion and heavy metal free pollution of chromium may further comprise the steps:
1), immersion pretreatment technology plate may further comprise the steps,
By weight, 100 parts of raw material skins with after the group batch place rotary drum, add water 100 ~ 250 parts under the normal temperature, 0.1 ~ 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 ~ 0.3 part rotates 10 ~ 40min, rotates 10min afterwards, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, after this rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, control liquid; Add water 100 ~ 250 parts again, under the normal temperature, add 0.1 ~ 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 ~ 0.3 part, 0.1 ~ 0.5 part of prozyme Y rotates 30 ~ 120min, stops 20min, regulates pH=9.5 ~ 11.5 with alkali, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 5min afterwards, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, stop drum and spend the night, control liquid next day;
2), prozyme dehairing process plate may further comprise the steps,
By weight: with the pretreated raw material skin of above-mentioned immersion, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion, 30 ~ 40 ℃ of temperature add water 30 ~ 150 parts, and 0.3 ~ 1.6 part of prozyme T rotates 30 ~ 150min, control liquid; Add water 50 ~ 200 parts again, 0.05 ~ 0.3 part of penetrating agent JFC, 0.05 ~ 0.5 part in sodium hydroxide, 1 ~ 5 part in content 30% hydrogen peroxide rotates 20 ~ 100min, after depilation is clean, continues to change 30min;
3), Chrome-free tanning process plate mainly may further comprise the steps,
By weight: the raw material skin with after the above-mentioned depilation, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion; Under the normal temperature, add water 10 ~ 100 parts, cationic fat liquor 0.5% ~ 5%, rotate 30min, add the many metals of DMT-II and cooperate 4 ~ 20 parts of tanning agents, 1 ~ 10 part of prozyme R, rotate 30 ~ 180min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, regulate pH=3.5 ~ 4.5, add water 20 ~ 200 parts, temperature is 38 ~ 45 ℃, changes 30 ~ 180min, stops drum and spends the night.
The preparation of prozyme Y, by weight: 40 ~ 60 parts of Sumizyme MPs, 10 ~ 30 parts of industrial pancreatin, 1 ~ 5 part of anhydrous sodium sulphate, 1 ~ 5 part of ammonium salt and additive B are mixed for 20 ~ 40 parts, obtain prozyme Y.
The preparation of prozyme T, by weight: 20 ~ 40 parts of neutral proteases, 10 ~ 20 parts of Sumizyme MPs, 1 ~ 10 part of aspartic protease, 1 ~ 5 part of anhydrous sodium sulphate, 1 ~ 5 part of ammonium salt, 5 ~ 20 parts of additive A and additive B are mixed for 30 ~ 50 parts, obtain prozyme T.
The preparation of prozyme R, by weight: 10 ~ 30 parts of 20 ~ 40 parts of aspartic protease A, aspartic protease B, 1 ~ 10 part of ammonium salt, 1 ~ 5 part of anhydrous sodium sulphate, 20 ~ 40 parts of additive A and additive B are mixed for 20 ~ 60 parts, obtain prozyme R.
Sumizyme MP is at least a in 209 Sumizyme MPs, 289 Sumizyme MPs and 2709 Sumizyme MPs of unit of activity 3 ~ 100,000 units; Aspartic protease is that unit of activity is at least a in 537 aspartic proteases, 3350 aspartic proteases, stomach acidity proteolytic enzyme and the papoid of 5 ~ 100,000 units; Neutral protease is that unit of activity is that AS1.398 neutral protease, 166 neutral proteases, 3942 neutral proteases, 172 neutral proteases and the unit of activity of 3 ~ 50,000 units is at least a in the pancreatin of 1:10 ~ 25 times.
Additive therefor A is any in kaolin, diatomite, the wilkinite; Additive B is any in flour, fine rice bran, the thin straw powder; Described ammonium salt is selected from any in ammonium sulfate, the ammonium chloride.
Performance test
By the prepared finished leather of above method, its performance meets the technical requirements of following national standard:
1, clothing leather meets State Standard of the People's Republic of China's " GB/T 1872-1993 clothes leather ", and trivalent chromium and sexavalent chrome all can't check.
2, upper leather meets State Standard of the People's Republic of China's " GB/T 1873-2010 vamp leather ", and trivalent chromium and sexavalent chrome all can't check.
3, upholstery leather meets State Standard of the People's Republic of China's " GB/T 16799-2008 furniture leather ", and trivalent chromium and sexavalent chrome all can't check.
The present invention has following advantage:
(1) the present invention is used for preceding the preparation and tanning of tanning of ox-hide, sheepskin, the multiple process hides raw material of pigskin skin, do not use lime, sulfide, industrial table salt and heavy metal chromium in whole process hides process these are poisonous, harmful leather chemicalses, have thoroughly eliminated the principal pollutant of leather industry from the source.
(2) use technology of the present invention and carry out process hides processing, the principal pollutant in the waste water reduce significantly than common process, have greatly reduced cost of sewage disposal.
(3) the used leather chemicals of the present invention is cheap and easy to get, and is good with existing leather-making technology system consistency, need not to increase any mechanical means, is easy to apply.
Embodiment:
By the following examples the present invention is carried out concrete description; be necessary that again this is pointed out that present embodiment only is used for further specifying that the present invention carries out; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
(1) immersion pretreatment technology plate may further comprise the steps,
By weight, 100 parts of raw material skins with after the group batch place rotary drum, add water 100 parts under the normal temperature, 0.1 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 part is rotated 10min, rotates 10min afterwards, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, after this rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, control liquid; Add water 100 parts again, under the normal temperature, add 0.1 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 part, 0.1 part of prozyme Y rotates 30min, stops 20min, regulates pH=9.5 with alkali, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 5min afterwards, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, stop drum and spend the night, control liquid next day;
(2) prozyme dehairing process plate may further comprise the steps,
By weight: with the pretreated raw material skin of above-mentioned immersion, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion, 30 ℃ of temperature add water 30 parts, and 0.3 part of prozyme T rotates 30min, control liquid; Add water 50 parts again, 0.05 part of penetrating agent JFC, 0.05 part in sodium hydroxide, 1 part in content 30% hydrogen peroxide rotates 20min, after depilation is clean, continues to change 30min;
(3) Chrome-free tanning process plate mainly may further comprise the steps,
By weight: the raw material skin with after the above-mentioned depilation, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion; Under the normal temperature, add water 10 parts, cationic fat liquor 0.5%, rotate 30min, add the many metals of DMT-II and cooperate 4 parts of tanning agents, 1 part of prozyme R, rotate 30min, add 0.1 part in sodium bicarbonate, rotate 20 min, add 0.1 part in sodium bicarbonate, rotate 20 min, add 0.1 part in sodium bicarbonate, rotate 20 min, add 0.1 part in sodium bicarbonate, rotate 20 min, add 0.1 part in sodium bicarbonate, rotate 20 min, add 0.1 part in sodium bicarbonate, rotate 20 min, regulate pH=3.5, add water 20 parts, temperature is 38 ℃, changes 30min, stops drum and spends the night.
Embodiment 2
(1) immersion pretreatment technology plate may further comprise the steps,
By weight, 100 parts of raw material skins with after the group batch place rotary drum, add water 150 parts under the normal temperature, 0.3 part of penetrating agent JFC, immersion auxiliary agent SA-C0.1 part is rotated 20min, rotates 10min afterwards, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, after this rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, control liquid; Add water 150 parts again, under the normal temperature, add 0.3 part of penetrating agent JFC, immersion auxiliary agent SA-C0.1 part, 0.3 part of prozyme Y rotates 60min, stops 20min, regulates pH=10 with alkali, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 5min afterwards, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, stop drum and spend the night, control liquid next day;
(2) prozyme dehairing process plate may further comprise the steps,
By weight: with the pretreated raw material skin of above-mentioned immersion, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion, 35 ℃ of temperature add water 100 parts, and 1 part of prozyme T rotates 80min, control liquid; Add water 100 parts again, 0.1 part of penetrating agent JFC, 0.3 part in sodium hydroxide, 2 parts in content 30% hydrogen peroxide rotates 60min, after depilation is clean, continues to change 30min;
(3) Chrome-free tanning process plate mainly may further comprise the steps,
By weight: the raw material skin with after the above-mentioned depilation, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion; Under the normal temperature, add water 60 parts, cationic fat liquor 2%, rotate 30min, add the many metals of DMT-II and cooperate 10 parts of tanning agents, 5 parts of prozyme R, rotate 100min, add 0.3 part in sodium bicarbonate, rotate 20 min, add 0.3 part in sodium bicarbonate, rotate 20 min, add 0.3 part in sodium bicarbonate, rotate 20 min, add 0.3 part in sodium bicarbonate, rotate 20 min, add 0.3 part in sodium bicarbonate, rotate 20 min, add 0.3 part in sodium bicarbonate, rotate 20 min, regulate pH=4, add water 100 parts, temperature is 40 ℃, changes 90min, stops drum and spends the night.
Embodiment 3
(1) immersion pretreatment technology plate may further comprise the steps,
By weight, 100 parts of raw material skins with after the group batch place rotary drum, add water 250 parts under the normal temperature, 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.3 part is rotated 40min, rotates 10min afterwards, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, after this rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, control liquid; Add water 250 parts again, under the normal temperature, add 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.3 part, 0.5 part of prozyme Y rotates 120min, stops 20min, regulates pH=11.5 with alkali, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 5min afterwards, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, stop drum and spend the night, control liquid next day;
(2) prozyme dehairing process plate may further comprise the steps,
By weight: with the pretreated raw material skin of above-mentioned immersion, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion, 40 ℃ of temperature add water 150 parts, and prozyme T1.6 part is rotated 150min, control liquid; Add water 200 parts again, 0.3 part of penetrating agent JFC, 0.5 part in sodium hydroxide, 5 parts in content 30% hydrogen peroxide rotates 100min, after depilation is clean, continues to change 30min;
(3) Chrome-free tanning process plate mainly may further comprise the steps,
By weight: the raw material skin with after the above-mentioned depilation, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion; Under the normal temperature, add water 100 parts, cationic fat liquor 5%, rotate 30min, add the many metals of DMT-II and cooperate 20 parts of tanning agents, 10 parts of prozyme R, rotate 180min, add 0.5 part in sodium bicarbonate, rotate 20 min, add 0.5 part in sodium bicarbonate, rotate 20 min, add 0.5 part in sodium bicarbonate, rotate 20 min, add 0.5 part in sodium bicarbonate, rotate 20 min, add 0.5 part in sodium bicarbonate, rotate 20 min, add 0.5 part in sodium bicarbonate, rotate 20 min, regulate pH=4.5, add water 200 parts, temperature is 45 ℃, changes 180min, stops drum and spends the night.
Annotate: it is that Chengdu one hundred happy golden biotechnology has company to produce that the DMT-II cooperates tanning agent, and all the other industrial chemicals are bought by market.
Claims (6)
1. the method for not having the process hides of lime, sulfide, chlorion and heavy metal free pollution of chromium is characterized in that this method may further comprise the steps:
1), immersion pretreatment technology plate may further comprise the steps,
By weight, 100 parts of raw material skins with after the group batch place rotary drum, add water 100 ~ 250 parts under the normal temperature, 0.1 ~ 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 ~ 0.3 part rotates 10 ~ 40min, rotates 10min afterwards, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, rotate 10min, stop 20min, after this rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, control liquid; Add water 100 ~ 250 parts again, under the normal temperature, add 0.1 ~ 0.5 part of penetrating agent JFC, immersion auxiliary agent SA-C0.05 ~ 0.3 part, 0.1 ~ 0.5 part of prozyme Y rotates 30 ~ 120min, stops 20min, regulates pH=9.5 ~ 11.5 with alkali, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 20min, stop 20min, rotate 5min afterwards, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, rotate 5min, stop 55min, stop drum and spend the night, control liquid next day;
2), prozyme dehairing process plate may further comprise the steps,
By weight: with the pretreated raw material skin of above-mentioned immersion, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion, 30 ~ 40 ℃ of temperature add water 30 ~ 150 parts, and 0.3 ~ 1.6 part of prozyme T rotates 30 ~ 150min, control liquid; Add water 50 ~ 200 parts again, 0.05 ~ 0.3 part of penetrating agent JFC, 0.05 ~ 0.5 part in sodium hydroxide, 1 ~ 5 part in content 30% hydrogen peroxide rotates 20 ~ 100min, after depilation is clean, continues to change 30min;
3), Chrome-free tanning process plate may further comprise the steps,
By weight: the raw material skin with after the above-mentioned depilation, place rotary drum, heavily be 100 parts in weight before this raw material skin immersion; Under the normal temperature, add water 10 ~ 100 parts, cationic fat liquor 0.5% ~ 5%, rotate 30min, add the many metals of DMT-II and cooperate 4 ~ 20 parts of tanning agents, 1 ~ 10 part of prozyme R, rotate 30 ~ 180min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, add 0.1 ~ 0.5 part in sodium bicarbonate, rotate 20 min, regulate pH=3.5 ~ 4.5, add water 20 ~ 200 parts, temperature is 38 ~ 45 ℃, changes 30 ~ 180min, stops drum and spends the night.
2. according to the method for the process hides of the described no lime of claim 1, sulfide, chlorion and heavy metal free pollution of chromium, it is characterized in that the preparation of prozyme Y, by weight: 40 ~ 60 parts of Sumizyme MPs, 10 ~ 30 parts of industrial pancreatin, 1 ~ 5 part of anhydrous sodium sulphate, 1 ~ 5 part of ammonium salt and additive B are mixed for 20 ~ 40 parts, obtain prozyme Y.
3. according to the method for the process hides of the described no lime of claim 1, sulfide, chlorion and heavy metal free pollution of chromium, it is characterized in that the preparation of prozyme T, by weight: 20 ~ 40 parts of neutral proteases, 10 ~ 20 parts of Sumizyme MPs, 1 ~ 10 part of aspartic protease, 1 ~ 5 part of anhydrous sodium sulphate, 1 ~ 5 part of ammonium salt, 5 ~ 20 parts of additive A and additive B are mixed for 30 ~ 50 parts, obtain prozyme T.
4. according to the method for the process hides of the described no lime of claim 1, sulfide, chlorion and heavy metal free pollution of chromium, it is characterized in that the preparation of prozyme R, by weight: 10 ~ 30 parts of 20 ~ 40 parts of aspartic protease A, aspartic protease B, 1 ~ 10 part of ammonium salt, 1 ~ 5 part of anhydrous sodium sulphate, 20 ~ 40 parts of additive A and additive B are mixed for 20 ~ 60 parts, obtain prozyme R.
5. according to the method for the process hides of the described no lime of claim 1, sulfide, chlorion and heavy metal free pollution of chromium, it is characterized in that Sumizyme MP is at least a in 209 Sumizyme MPs, 289 Sumizyme MPs and 2709 Sumizyme MPs of unit of activity 3 ~ 100,000 units; Aspartic protease is that unit of activity is at least a in 537 aspartic proteases, 3350 aspartic proteases, stomach acidity proteolytic enzyme and the papoid of 5 ~ 100,000 units; Neutral protease is that unit of activity is that AS1.398 neutral protease, 166 neutral proteases, 3942 neutral proteases, 172 neutral proteases and the unit of activity of 3 ~ 50,000 units is at least a in the pancreatin of 1:10 ~ 25 times.
6. according to the method for the process hides of the described no lime of claim 1, sulfide, chlorion and heavy metal free pollution of chromium, it is characterized in that additive therefor A is any in kaolin, diatomite, the wilkinite, additive B is flour, fine rice bran, thin straw powder etc., and described ammonium salt is selected from any in ammonium sulfate, the ammonium chloride.
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| CN103555866A (en) * | 2013-11-08 | 2014-02-05 | 浙江明新皮业有限公司 | Ecological automobile leather manufacturing method by adopting novel enzyme unhairing |
| CN105441602A (en) * | 2015-12-23 | 2016-03-30 | 天津科技大学 | Method for tanning by jointly using compound protease soaked with water, titanium salt and zinc salt |
| CN105441600A (en) * | 2015-11-28 | 2016-03-30 | 成都德善能科技有限公司 | Tanning method for free-chrome tanning agent in leather production |
| CN105624339A (en) * | 2015-12-23 | 2016-06-01 | 天津科技大学 | Method for shortening leather making soaking time |
| CN113278745A (en) * | 2021-05-20 | 2021-08-20 | 河北中皮东明科技有限公司 | Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103555866A (en) * | 2013-11-08 | 2014-02-05 | 浙江明新皮业有限公司 | Ecological automobile leather manufacturing method by adopting novel enzyme unhairing |
| CN103555866B (en) * | 2013-11-08 | 2016-04-13 | 浙江明新皮业有限公司 | A kind of eco-car leather manufacture method adopting novel enzyme unhairing |
| CN105441600A (en) * | 2015-11-28 | 2016-03-30 | 成都德善能科技有限公司 | Tanning method for free-chrome tanning agent in leather production |
| CN105441600B (en) * | 2015-11-28 | 2017-10-27 | 成都德善能科技有限公司 | Chrome-free tanning agent process for tanning in a kind of leather production |
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| CN105624339A (en) * | 2015-12-23 | 2016-06-01 | 天津科技大学 | Method for shortening leather making soaking time |
| CN105441602B (en) * | 2015-12-23 | 2017-12-12 | 天津科技大学 | Titanium salt and the method for zinc salt combination tanning are used after compound protease immersion |
| CN105624339B (en) * | 2015-12-23 | 2018-05-18 | 天津科技大学 | A kind of method for shortening process hides soaking time |
| CN113278745A (en) * | 2021-05-20 | 2021-08-20 | 河北中皮东明科技有限公司 | Solid dispersion medium for anhydrous and low-water leather processing, preparation method and leather preparation process |
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| CN103243182B (en) | 2014-11-26 |
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