CN106518955A - Method for using cowhair recycled by hair saving and unhairing in leather process to prepare protein filling used in leather - Google Patents
Method for using cowhair recycled by hair saving and unhairing in leather process to prepare protein filling used in leather Download PDFInfo
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- CN106518955A CN106518955A CN201610983143.8A CN201610983143A CN106518955A CN 106518955 A CN106518955 A CN 106518955A CN 201610983143 A CN201610983143 A CN 201610983143A CN 106518955 A CN106518955 A CN 106518955A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/12—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by hydrolysis, i.e. solvolysis in general
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- 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
- C14C3/08—Chemical tanning by organic agents
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Abstract
The invention discloses a method for using cowhair recycled by hair saving and unhairing in leather process to prepare protein filling used in leather. The method is characterized by comprising the steps of using the cowhair recycled by hair saving and unhairing in leather process as a raw material, adopting an alkaline process to conduct synthetic hydrolysis on cowhair, and filtering and collecting filtrate liquor; using little amount of strong base to conduct hydrolysis again on filter residue at a high temperature and high pressure, and filtering and collecting filtrate liquor; mixing the filtrate liquor collected in the two steps above, and using inorganic acid to adjust pH to obtain a liquid protein filling, or drying the mixed liquor to obtain a solid protein filling; conducting high-temperature roasting on the filter residue to obtain powder which is reused in alkaline hydrolysis of the cowhair. According to the method for using cowhair recycled by hair saving and unhairing in leather process to prepare protein filling used in leather, rapid filtration after hydrolysis of the cowhair is achieved, the obtained liquid or solid protein filling is light in color, the hydrolysis rate of the cowhair is high, and no solid waste is generated. Therefore, the method for industrialized production of the protein filling is easy to operate, and economical and practical.
Description
Technical field
The invention belongs to it is former that the method for preparing protolysate, more particularly to one kind process hides protect hair depilation to reclaim ox hair
The method that material prepares process hides protein filling.
Background technology
In order to reduce the pollution for ruining that mao epilation is caused to waste water, leather-making enterprises are just widelyd popularize to apply enables ox hair completeer
The whole hair saving process for coming off.Thus obtained recovery ox hair enormous amount and keratin is rich in, can in addition resource after recovery
Change and utilize.In leather industry, ox hair can be reclaimed it is hydrolyzed to the suitable protolysate of molecular weight distribution and fill out preparing albumen
Material, for process hides retanning filling work procedure, is obtained the leather with good hand and sanitation performance.This is not only recycling cattle
The effective way of hair, and meet the demand for development of recycling economy.At present, the method for hydrolyzing ox hair has acid-hydrolysis method, basic hydrolysiss
Method, enzyme hydrolysis method, hydrogen peroxide Hydrolyze method, alkali-enzyme synergetic hydrolysis method etc..It is constitutionally stable in alkali hydrolysis method energy rapid damage ox hair
Cystine linkage, interrupts peptide bond and sat linkage, hair is dissolved completely, while which is simple to operate, equipment requirements are low, is the extensive water of industrialization
The prefered method of solution ox hair.
In the prior art, Chinese patent CN101260140 is " a kind of to prepare process hides protein filling by raw material of animal wool
Method " disclose a kind of first with mineral acid and reducing agent dipping pretreatment, after the ox hair hydrolysis side that hydrolyzed with alkali compoundss
Method.The problem that the method is present is gained protein filling color depth, for having a strong impact on the color and luster of leather after retanning filling work procedure
And sense organ, strongly limit its application in process hides.The reason for producing this problem is to contain a large amount of pigments in alkaline hydrolyzate
And do not hydrolyze the impurity such as ox hair, but as its viscosity is big, in starchiness, it is impossible to efficiently separated, directly can only concentrate dry
Use after dry.Chinese patent CN104523549A " a kind of method that utilization ox hair prepares uvioresistant wetting agent " discloses one kind
First use mineral acid and alkali compoundss dipping pretreatment, after the ox hair method for hydrolysis that hydrolyzed with alkali compoundss, the aqueous alkali for obtaining
Solution liquid only has Jing high speed centrifugations separate protein liquid with solid waste, and supernatant is equally rich in pigment, and color is deeper.
Document（Pu Jianmin, Mao Pei, Shen Xiaojun, etc. protect the research that ox hair basic hydrolysiss technique is reclaimed in hair depilation. leather science and work
Journey, 2014,24 (3): 52-58.）Report one kind and first use NaHSO3Pretreatment, after with NaOH hydrolyze ox hair hydrolysis side
Method, its problem for existing is that, during cold filtration, in sticky hydrolyzed solution, the soft yielding solid impurity of matter can form knot
The fine and close filter cake easily compressed by structure, suspended particulates therein can block filtration channel, cause to be difficult to filter, while pigment is remained in
In hydrolyzed solution, make hydrolysate color still deeper.Although additionally, ox hair all have passed through pretreatment and aqueous alkali in above-mentioned these methods
Solution two-step reaction, but its percent hydrolysis is below 90%, even if can be separated after basic hydrolysiss, can still produce more solid and give up
Gurry.
The content of the invention
The technical problem to be solved is, for shortcoming present in prior art or deficiency, there is provided Yi Zhongyong
Process hides is protected hair depilation and reclaims the method that ox hair is that raw material prepares process hides protein filling, being capable of quick mistake after being characterized in basic hydrolysiss
Filter and efficient decolorizing, the liquid for obtaining or solid-state protein filler color are light, ox hair percent hydrolysiss are high, and do not produce solid waste.
A kind of method for preparing process hides protein filling with process hides guarantor's hair depilation recovery ox hair that the present invention is provided, the method
Processing step and condition it is as follows, be calculated as by weight：
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 6-20 part highly basic is added, 4-10 parts are alkaline oxygenated
Thing, 0.5-2 part sodium aluminosilicate, 500-1000 part water at temperature 70-90 DEG C react 3-10h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5-2 part highly basic, 50-100 part water, in pressure 0.2-
1-5h is reacted at 0.8MPa, temperature 130-190 DEG C, filter and collect filtrate；
（3）By step（2）Filtering residue at temperature 500-800 DEG C roasting 1-4h, the powder for obtaining is back to step（1）Middle replacement
Basic anhydride and sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 5.5-7.5 using mineral acid, obtains liquid process hides egg
White filler, or solid-state process hides protein filling is obtained after liquid process hides protein filling is dried.
The alkali compoundss are NaOH, Ca (OH)2With at least one in KOH.
Described basic anhydride are MgO, CaO and Al2O3In at least one.
The mineral acid is at least one in hydrochloric acid, sulphuric acid, nitric acid and phosphoric acid.
The present invention can realize that alkaline hydrolyzate is filtered and the principle of decolouring is, the filter process after ox hair basic hydrolysiss
In, the basic anhydride or sodium aluminosilicate of addition are hard and in irregular shape because of quality, help to be formed loose, multi-pore channel, can not
The filter cake of compression, increases flow channel, reduces flow resistance, promotes ox hair hydrolysed mix solid-liquid sharp separation；Meanwhile, it is selected
Surface is in strong electropositive at reaction conditions for the basic anhydride selected or sodium aluminosilicate, can adsorb electronegative particle diameter less
Pigment and particle, the colourity of hydrolyzed solution can be reduced to a certain extent.Further study show that by present inventor,
Add a certain amount of sodium aluminosilicate while adding basic anhydride, under both synergism, ox hair hydrolysed mix is not
Only can sharp separation, it is often more important that can efficient decolorizing, significantly reduce the colourity of ox hair hydrolyzed solution, the liquid that finally gives or
Solid-state protein filler color is light.Subsequently, basic anhydride and sodium aluminosilicate enter filtering residue, it is fired after can be back to the first step
In basic hydrolysiss.
In addition, the inventors have found that, ox hair passes through the strong work of the grey material such as alkali and sulfide in depilation liming operation
With its scale layer is destroyed and even peels off.In ox hair hydrolytic process, it is directly added into highly basic and can have directly acted on cortex
Layer., compared with not preprocessed ox hair, its basic hydrolysiss rate is essentially identical, and the face of hydrolysate for the ox hair of distinct methods pretreatment
Color, property all similar.Therefore, ox hair need not carry out pretreatment before basic hydrolysiss.
The present invention compared with prior art, has the advantages that：
（1）The present invention protects hair depilation using highly basic, basic anhydride and the process hides of sodium aluminosilicate synergetic hydrolysis and reclaims ox hair, and existing
Ox hair basic hydrolysiss technology compare, can realize that ox hair hydrolyzed solution is separated with the fast filtering of solid slag, but can efficient absorption remove
Pigment in ox hair hydrolyzed solution, significantly reduces the colourity of hydrolyzed solution, it is ensured that protein filling has excellent in process hides retanning filling
Good application effect.
（2）The present invention makes ox hair percent hydrolysiss reach more than 95%, with existing ox hair basic hydrolysiss technology by hydrolyzing twice
Compare, significantly improve the utilization rate to keratin resource in ox hair, while further through rationally setting hydrolysising condition, Effective Regulation
The range of molecular weight distributions of ox hair hydrolysate, makes the protein filling have excellent retanning filling effect.
（3）The present invention is back to gained powder in basic hydrolysiss and replaces basic anhydride and silicon by roasting residue filtering residue
Sodium aluminate, equally with significant drainage and the effect decolourized.Compared with existing ox hair basic hydrolysiss technology, whole method is not produced
Raw solid waste, realizes resource circulation utilization.
Specific embodiment
The present invention is specifically described below by example, it is necessary to it is pointed out here that be the present embodiment be served only for this
Invention is further illustrated, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in the field can basis
The content of the invention described above makes some nonessential modifications and adaptations.
Embodiment 1
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 16 parts of NaOH, 4 parts of MgO, 1.5 parts of sial are added
Sour sodium, 800 parts of water at 90 DEG C of temperature react 10h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 2 parts of KOH, 100 parts of water, in pressure 0.2MPa, 130 DEG C of temperature
Lower reaction 5h, filters and collects filtrate；
（3）By step（2）Filtering residue at 500 DEG C of temperature roasting 4h, the powder for obtaining is back to step（1）Middle replacement MgO and
Sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 6 using hydrochloric acid, obtains liquid process hides protein filling, or
Solid-state process hides protein filling is obtained after liquid process hides protein filling is dried.
In this step, determine step（1）With（2）The colourity value of chromatism of the mixing filtrate of collection（The results are shown in Table 1）.
Comparative example 1：
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 16 parts of NaOH are added, 800 parts of water, in temperature 90
10h is reacted at DEG C, is centrifuged and is collected supernatant；
（2）By step（1）Precipitate be placed in reactor, add 2 parts of KOH, 100 parts of water, in pressure 0.2MPa, temperature 130
5h is reacted at DEG C, is centrifuged and is collected supernatant；
（3）By step（1）With（2）The supernatant mixing of collection.
In this step, determine step（1）With（2）The colourity value of chromatism of the mixing supernatant of collection（The results are shown in Table 1）.
Comparative example 2：
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 16 parts of NaOH of addition, 4 parts of MgO, 800 parts of water,
10h is reacted at 90 DEG C of temperature, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 2 parts of KOH, 100 parts of water, in pressure 0.2MPa, 130 DEG C of temperature
Lower reaction 5h, filters and collects filtrate；
（3）By step（1）With（2）The filtrate mixing of collection.
In this step, determine step（1）With（2）The colourity value of chromatism of the mixing filtrate of collection（The results are shown in Table 1）.
Comparative example 3：
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 16 parts of NaOH of addition, 1.5 parts of sodium aluminosilicate, 800
Part water, at 90 DEG C of temperature reacts 10h, filters and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 2 parts of KOH, 100 parts of water, in pressure 0.2MPa, 130 DEG C of temperature
Lower reaction 5h, filters and collects filtrate；
（3）By step（1）With（2）The filtrate mixing of collection.
In this step, determine step（1）With（2）The colourity value of chromatism of the mixing filtrate of collection（The results are shown in Table 1）.
Colourity aberration values determination method：
Mixing filtrate/the supernatant of 4 mL embodiments 1, comparative example 1, comparative example 2 and comparative example 3 is taken respectively, is diluted to 20 mL.
Above-mentioned 4 groups of L, a, b value is determined with spectrophotometric color measurement instrument, with comparative example 1 as a control group（Because its color it is most deep）, Δ is calculated respectively
L, Δ a, Δ b and Δ E（, refer to total color difference）.Δ E is bigger, illustrates hydrolyzed solution compared with matched group
Color is more shallow, and decolorizing effect is better.
1 colourity value of chromatism measurement result of table
。
As known from Table 1, the total color difference Δ E of 1 filtrate of embodiment is noticeably greater than comparative example 1, hence it is evident that better than comparative example 2 and contrast
Example 3.Thus illustrate, in the present invention, basic anhydride and sodium aluminosilicate have excellent collaboration decolorization, its hydrolyzed solution face
Color is most shallow.Therefore, the present invention protects hair depilation using highly basic, basic anhydride and the process hides of sodium aluminosilicate synergetic hydrolysis and reclaims cattle
Hair, energy efficient absorption remove the pigment in ox hair hydrolyzed solution, significantly reduce the colourity of hydrolyzed solution.
Embodiment 2
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 6 parts of KOH of addition, 8 parts of CaO, 1 part of sodium aluminosilicate,
1000 parts of water, react 8h under temperature 70 C, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5 part of NaOH, 0.5 part of Ca (OH)2, 0.5 part of KOH, 50 parts
Water, at pressure 0.8MPa, 190 DEG C of temperature reacts 2h, filters and collect filtrate；
（3）By step（2）Filtering residue at 800 DEG C of temperature roasting 1h, the powder for obtaining is back to step（1）Middle replacement CaO and
Sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 7.5 using sulphuric acid, obtains liquid process hides protein filling,
Or it is dried to obtain process hides solid-state protein filler.
Embodiment 3
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 20 parts of Ca (OH) are added2, 2 parts of CaO, 2 parts
Al2O3, 2 parts of MgO, 1 part of sodium aluminosilicate, 700 parts of water at 87 DEG C of temperature react 6h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5 part of NaOH, 80 parts of water, in pressure 0.6MPa, temperature 170
3h is reacted at DEG C, is filtered and is collected filtrate；
（3）By step（2）Filtering residue at 700 DEG C of temperature roasting 3h, the powder for obtaining is back to step（1）Middle replacement CaO,
Al2O3, MgO and sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 6 using nitric acid, obtains liquid process hides protein filling, or
It is dried to obtain solid-state process hides protein filling.
Embodiment 4
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 8 parts of Ca (OH) are added2, 8 parts of NaOH, 4 parts of MgO,
6 parts of CaO, 0.5 part of sodium aluminosilicate, 500 parts of water at 90 DEG C of temperature react 3h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5 part of KOH, 0.5 part of NaOH, 80 parts of water, in pressure
0.5MPa, reacts 3h at 150 DEG C of temperature, filters and collect filtrate；
（3）By step（2）Filtering residue at 800 DEG C of temperature roasting 2h, the powder for obtaining is back to step（1）Middle replacement MgO,
CaO and sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of middle collection, adjusts pH to 5.5 using nitric acid and phosphoric acid, obtains liquid process hides use
Protein filling, or it is dried to obtain solid-state process hides protein filling.
Embodiment 5
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 6 parts of Ca (OH) are added2, 10 parts of KOH, 3 parts of MgO,
3 parts of Al2O3, 1 part of sodium aluminosilicate, 600 parts of water at 80 DEG C of temperature react 10h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5 part of NaOH, 1.5 parts of Ca (OH)2, 70 parts of water, in pressure
0.7MPa, reacts 3h at 150 DEG C of temperature, filters and collect filtrate；
（3）By step（2）Filtering residue at 800 DEG C of temperature roasting 1h, the powder for obtaining is back to step（1）Middle replacement MgO,
Al2O3And sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 7 using nitric acid and hydrochloric acid, obtains liquid process hides albumen
Filler, or it is dried to obtain solid-state process hides protein filling.
Embodiment 6
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, addition 6 parts of NaOH, 6 parts of KOH, 3 parts of CaO, 3 parts
Al2O3, 1.5 parts of sodium aluminosilicate, 600 parts of water at 85 DEG C of temperature react 6 h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 0.5 part of KOH, 1.5 parts of Ca (OH)2, 100 parts of water, in pressure
0.6MPa, reacts 2h at 170 DEG C of temperature, filters and collect filtrate；
（3）By step（2）Filtering residue at 600 DEG C of temperature roasting 4h, the powder for obtaining is back to step（1）Middle replacement CaO,
Al2O 3And sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 7 using hydrochloric acid and sulphuric acid, obtains liquid process hides albumen
Filler, or it is dried to obtain solid-state process hides protein filling.
Embodiment 7
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 6 parts of NaOH, 3 parts of KOH, 3 parts of Ca (OH) are added2,
10 parts of Al2O3, 2 parts of sodium aluminosilicate, 1000 parts of water at 90 DEG C of temperature react 8h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 1 part of NaOH, 95 parts of water, in 0.4 MPa of pressure, 170 DEG C of temperature
Lower reaction 3h, filters and collects filtrate；
（3）By step（2）Filtering residue at 700 DEG C of temperature roasting 3h, the powder for obtaining is back to step（1）Middle replacement Al2O3
And sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 6 using hydrochloric acid and phosphoric acid, obtains liquid process hides albumen
Filler, or it is dried to obtain solid-state process hides protein filling.
Embodiment 8
（1）100 parts of process hides are protected hair depilation recovery ox hair to be placed in reactor, 16 parts of NaOH, 5.5 parts of 1 steps of embodiment are added
（3）The powder for obtaining, 800 parts of water at 90 DEG C of temperature react 10h, filter and collect filtrate；
（2）By step（1）Filtering residue be placed in reactor, add 2 parts of KOH, 100 parts of water, in pressure 0.2MPa, 130 DEG C of temperature
Lower reaction 5h, filters and collects filtrate；
（3）By step（2）Filtering residue at 800 DEG C of temperature roasting 2h, the powder for obtaining is back to step（1）Middle replacement embodiment
1 step（3）The powder for obtaining；
（4）By step（1）With（2）The filtrate mixing of collection, adjusts pH to 6 using hydrochloric acid, obtains liquid process hides protein filling, or
Solid-state process hides protein filling is obtained after liquid process hides protein filling is dried.
To embodiment 2-8 gains（Step（1）With（2）The mixing filtrate of collection）Have also been made color the same manner as in Example 1
Result the no significant difference of degree value of chromatism measure, its measurement result and embodiment 1, therefore deposited stating no longer is done herein.
Claims (4)
1. a kind of process hides is protected hair depilation and reclaims the method that ox hair prepares process hides protein filling, it is characterised in that the method is included
Following processing step：
（1）By weight, hair depilation recovery ox hair is protected by 100 parts to be placed in reactor, add 6-20 part highly basic, 4-10 part alkali
Property oxide, 0.5-2 part sodium aluminosilicate, 500-1000 part water react 3-10h at temperature 70-90 DEG C, filter and collect filter
Liquid；
（2）By weight, by step（1）Filtering residue be placed in reactor, add 0.5-2 part highly basic, 50-100 part water, pressure
Strong 0.2-0.8MPa, reacts 1-5h at temperature 130-190 DEG C, filters and collect filtrate；
（3）By step（2）Filtering residue at temperature 500-800 DEG C roasting 1-4h, the powder for obtaining is back to step（1）Middle replacement
Basic anhydride and sodium aluminosilicate；
（4）By step（1）With（2）The filtrate mixing of middle collection, adjusts pH to 5.5-7.5 using mineral acid, obtains liquid process hides use
Protein filling, or solid-state process hides protein filling is obtained after liquid process hides protein filling is dried.
2. a kind of process hides according to claim 1 is protected hair depilation and reclaims the method that ox hair prepares process hides protein filling,
It is characterized in that the highly basic is NaOH, Ca (OH)2With at least one in KOH.
3. a kind of process hides according to claim 1 is protected hair depilation and reclaims the method that ox hair prepares process hides protein filling,
It is characterized in that described basic anhydride are MgO, CaO and Al2O3In at least one.
4. a kind of process hides according to claim 1 is protected hair depilation and reclaims the method that ox hair prepares process hides protein filling,
It is characterized in that the mineral acid is at least one in hydrochloric acid, sulphuric acid, nitric acid and phosphoric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610983143.8A CN106518955B (en) | 2016-11-09 | 2016-11-09 | A method of hair depilation recycling ox hair, which is protected, with process hides prepares process hides protein filling |
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| CN201610983143.8A CN106518955B (en) | 2016-11-09 | 2016-11-09 | A method of hair depilation recycling ox hair, which is protected, with process hides prepares process hides protein filling |
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|---|---|---|---|---|
| CN108342524A (en) * | 2018-03-05 | 2018-07-31 | 嘉兴学院 | A kind of resource utilization method of discarded animal wool and the vinyl-based Retanning Materials based on keratin hydrolysate and application |
| CN108342524B (en) * | 2018-03-05 | 2020-06-12 | 嘉兴学院 | Resource utilization method of waste animal hair, vinyl retanning material based on keratin hydrolysate and application |
| CN111793726A (en) * | 2020-07-23 | 2020-10-20 | 嘉兴学院 | Method for preparing leather retanning agent by taking waste animal hair as raw material |
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