CN109593898B - Biomass-based reactive amphoteric retanning agent and preparation method thereof - Google Patents
Biomass-based reactive amphoteric retanning agent and preparation method thereof Download PDFInfo
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- CN109593898B CN109593898B CN201910048456.8A CN201910048456A CN109593898B CN 109593898 B CN109593898 B CN 109593898B CN 201910048456 A CN201910048456 A CN 201910048456A CN 109593898 B CN109593898 B CN 109593898B
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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 relates to the field of leather science, in particular to a preparation method of an amphoteric retanning agent based on a biomass-based reaction type, which is characterized in that waste leather collagen is used as a raw material, a collagen hydrolysate is prepared by industrial compound enzyme, then bio-enzyme is adopted to carry out catalytic oxidation on tannin extract, and the catalytic oxidation tannin extract is used for carrying out cross-linking modification on hydrolyzed collagen to prepare the amphoteric reaction type environment-friendly organic retanning agent of collagen.
Description
Technical Field
The invention relates to the field of leather science, in particular to a reactive amphoteric retanning agent based on a biomass base and a preparation method thereof.
Background
China is a big leather-making country, the estimated annual amount of chrome tanning waste is more than 30 million tons, and the current piling method or burning method adopted by factories can cause serious pollution to the environment. The chrome leather scrap waste contains a large amount of collagen, and if the collagen in the chrome leather scrap waste is further processed by modification to prepare the collagen retanning agent, the chrome leather scrap is changed into valuable, the requirements of green chemistry and sustainable development are met, and certain guiding significance is provided for development and application of an environment-friendly retanning agent and optimization of a cleaning processing technology.
At present, the collagen retanning agent is prepared by modifying collagen by glutaraldehyde, resin and the like. The glutaraldehyde modified organic retanning agent is easy to generate excessive crosslinking with skin collagen in the tanning process, so that the grain surface is too compact, glutaraldehyde is toxic, and the glutaraldehyde modified organic retanning agent can only be used for retanning dark-colored leather, so that the application of the glutaraldehyde modified organic retanning agent is limited. The resin modified retanning agent is used for tanning leather, because the resin can absorb water, the water absorption is fast, the water absorption capacity is large, most of the absorbed water is combined water, the water is not easy to remove after short-time drying, and formaldehyde can be generated in the process of ageing the leather, so that leather fibers are dried and cracked, and the using amount is small.
In summary, in view of the problems of the above-mentioned collagen-based retanning agents, the present invention relates to a biomass-based retanning agent prepared by cross-linking hydrolyzed collagen with a catalytic oxidation tannin extract. The tannin extract is a plant extract containing tannin, is mainly used for tanning leather, has the advantages of no toxicity, little pollution, biodegradability and the like, does not contain heavy metal ions and formaldehyde, and meets the environmental protection requirement of clean production and the production concept of green and safe products.
Disclosure of Invention
The invention relates to a preparation method of a biomass-based reactive amphoteric retanning agent, and aims to provide a green and low-cost preparation method of a collagen retanning agent based on a biomass base.
In order to achieve the purpose, the invention adopts the technical scheme that:
a biomass-based reactive amphoteric retanning agent, obtainable by a process comprising the steps of:
(1) preparation of collagen hydrolysate: accurately weighing 10-20 g of collagen into a 150-500 mL three-neck flask, then adding 50-250 mL of water, putting the three-neck flask into a constant-temperature water bath kettle, and adjusting the temperature to 37 ℃; accurately weighing industrial complex enzyme with the weight of 5-15% of the collagen, adding the industrial complex enzyme into a three-neck flask, setting the rotating speed of a stirrer to be about 10-30 r/min, and reacting for 2-6 h; after the reaction is finished, placing the three-neck flask on an electric heating furnace for heating and boiling, immediately cooling, and finally freeze-drying for later use;
(2) preparation of bio-enzyme catalytic oxidation tannin extract: weighing 3-6 g of tannin extract in a reaction kettle, adding 0.09-0.18 g of biological enzyme in the reaction kettle, stirring and dissolving, fully mixing, adjusting the temperature of a reaction water bath to be 30-50 ℃, adjusting the pH to be 5.0-6.0, and reacting for 20-30 h;
(3) preparation of a biomass-based reactive amphoteric retanning agent: pouring 7.5-15 g of collagen hydrolysate prepared in the step (1) into a reaction kettle, pouring 3-6 g of catalytic oxidation tannin extract prepared in the step (2) into the reaction kettle, reacting for 20-30 h at the temperature of 30-50 ℃ and with the pH adjusted to 5.0-6.0, and freeze-drying for later use after the reaction is completed.
The further improvement of the invention is that the collagen hydrolysate in the step (1) is obtained by hydrolyzing collagen extracted from waste leather by using industrial complex enzyme, and the number average molecular mass Mn of the collagen hydrolysate is 1000-3000.
The invention is further improved in that the reaction temperature in the step (1) is 30-50 ℃, and the stirring reaction time is 2-6 h.
The invention is further improved in that the cross-linking agent in the step (2) is tannin extract which is catalyzed and oxidized by biological enzyme.
The invention is further improved in that the dosage of the biological enzyme in the step (2) is 2-5% of the dosage of tannin extract.
The further improvement of the invention is that the dosage of the oxidation tannin extract in the step (3) is 10-50% of the weight of the collagen hydrolysate, the temperature of the reaction water bath is 30-50 ℃, the pH is adjusted to 5.0-6.0, and the reaction time is 24 hours.
According to the invention, the tannin extract is subjected to biological enzyme catalytic oxidation, so that partial hydroxyl of the tannin extract is converted into a quinoid structure, covalent crosslinking can be formed with collagen side chain amino, meanwhile, the oxidation process can also cause tannin extract molecule degradation, and the intradermal penetration capability of the tannin extract is enhanced. After catalytic oxidation treatment, active groups are introduced into the tannin extract, so that the tannin extract has high reactivity and remarkably enhanced tanning property, and then the tannin extract is crosslinked and modified with collagen hydrolysate prepared by industrial complex enzyme to prepare a reactive amphoteric retanning agent with full biomass components, which is used for retanning leather, can improve the pI of the leather tanned by the organic tanning agent, fundamentally improve the absorption and combination capacity of the leather tanned by the organic tanning agent on the traditional wet finishing material, ensure that the finished leather quality is close to that of chrome tanned leather, and is suitable for all leather products.
Compared with the prior art, the technology has the following advantages:
(1) the method takes the waste skin collagen as the raw material, has rich sources and low price, and the prepared retanning agent provides a way for recycling the waste skin collagen;
(2) according to the invention, the collagen is hydrolyzed into the collagen or the collagen polypeptide with smaller molecular weight through the industrial complex enzyme, the structure of the collagen polypeptide is very similar to that of a collagen side chain of leather, and the collagen or the collagen polypeptide can be well fused into a collagen fiber system and has good filling performance;
(3) the retanning agent is prepared by using hydrolyzed collagen as a raw material, and the hydrolyzed collagen fully exposes amino and carboxyl of a side chain of the hydrolyzed collagen, so that the hydrolyzed collagen has the amphoteric characteristic and the permeability of the hydrolyzed collagen in crust leather is obviously improved;
(4) according to the invention, the catalytic oxidized tannin extract is used for modifying collagen, the tannin extract after being catalyzed and oxidized by biological enzyme has high reactivity, the tanning property is obviously enhanced, the mechanical property and the chemical stability of finished leather can be well improved, and the prepared collagen retanning agent is a full-biomass component and can be completely biodegraded.
Detailed Description
While the present invention will be described in conjunction with the embodiments set forth below, it is to be understood that the present invention is not limited to the precise embodiments described herein, and that various modifications and changes may be effected therein by one skilled in the art without departing from the scope of the invention as defined by the appended claims.
Example 1
(1) Preparation of collagen hydrolysate: accurately weighing 10g of collagen in a 150 mL three-neck flask, then adding 50 mL of water, putting the three-neck flask into a constant-temperature water bath kettle, and adjusting the temperature to 37 ℃; accurately weighing industrial complex enzyme with the weight of 5% of the collagen, adding the industrial complex enzyme into a three-neck flask, setting the rotating speed of a stirrer to be about 10 r/min, and reacting for 2 hours; after the reaction is finished, placing the three-neck flask on an electric heating furnace for heating and boiling, immediately cooling, and finally freeze-drying for later use;
(2) preparation of bio-enzyme catalytic oxidation tannin extract: weighing 3 g of tannin extract in a reaction kettle, adding 0.09 g of biological enzyme in the reaction kettle, stirring and dissolving, fully mixing, adjusting the temperature of a reaction water bath to be 30 ℃, adjusting the pH to be 5.0, and reacting for 20 hours;
(3) preparation of a biomass-based reactive amphoteric retanning agent: pouring 7.5g of collagen hydrolysate prepared in the step (1) into a reaction kettle, pouring 3 g of catalytic oxidation tannin extract prepared in the step (2) into the reaction kettle, adjusting the pH value to 5.0 at the temperature of reaction water bath of 30 ℃, reacting for 20 hours, and after the reaction is finished, freezing and drying for later use.
Example 2
(1) Preparation of collagen hydrolysate: accurately weighing 15g of collagen in a 250 mL three-neck flask, then adding 100 mL of water, putting the three-neck flask into a constant-temperature water bath kettle, and adjusting the temperature to 37 ℃; accurately weighing industrial complex enzyme with the weight of 10% of the collagen, adding the industrial complex enzyme into a three-neck flask, setting the rotating speed of a stirrer to be about 20 r/min, and reacting for 4 hours; after the reaction is finished, placing the three-neck flask on an electric heating furnace for heating and boiling, immediately cooling, and finally freeze-drying for later use;
(2) preparation of bio-enzyme catalytic oxidation tannin extract: weighing 4.5 g of tannin extract in a reaction kettle, adding 0.135 g of biological enzyme in the reaction kettle, stirring and dissolving, fully mixing, adjusting the temperature of reaction water bath to 37 ℃, adjusting the pH to 5.5, and reacting for 24 hours;
(3) preparation of a biomass-based reactive amphoteric retanning agent: pouring 10g of collagen hydrolysate prepared in the step (1) into a reaction kettle, pouring 4.5 g of catalytic oxidation tannin extract prepared in the step (2) into the reaction kettle, adjusting the pH value to 5.5 at the temperature of reaction water bath of 40 ℃, reacting for 24 hours, and after the reaction is finished, freezing and drying for later use.
Example 3
(1) Preparation of collagen hydrolysate: accurately weighing 20 g of collagen in a 500 mL three-neck flask, then adding 250 mL of water, putting the three-neck flask into a constant-temperature water bath kettle, and adjusting the temperature to 37 ℃; accurately weighing industrial complex enzyme accounting for 15% of the weight of the collagen, adding the industrial complex enzyme into a three-neck flask, setting the rotating speed of a stirrer to be about 30 r/min, and reacting for 6 hours; after the reaction is finished, placing the three-neck flask on an electric heating furnace for heating and boiling, immediately cooling, and finally freeze-drying for later use;
(2) preparation of bio-enzyme catalytic oxidation tannin extract: weighing 6 g of tannin extract in a reaction kettle, adding 0.18 g of biological enzyme in the reaction kettle, stirring and dissolving, fully mixing, adjusting the pH to 6.0 at the temperature of reaction water bath of 50 ℃, and reacting for 30 hours;
(3) preparation of a biomass-based reactive amphoteric retanning agent: pouring 15g of collagen hydrolysate prepared in the step (1) into a reaction kettle, pouring 6 g of catalytic oxidation tannin extract prepared in the step (2) into the reaction kettle, adjusting the pH value to 6.0 at the temperature of reaction water bath of 50 ℃, reacting for 30 hours, and after the reaction is finished, freezing and drying for later use.
Example 4
The synthetic collagen retanning filler is applied to a sheepskin tanning experiment, the dosage of the oxidized tannin extract and the dosage of the hydrolyzed collagen during crosslinking are optimized, the dosage of the oxidized tannin extract is respectively set to be 10%, 20%, 30%, 40% and 50% of the weight of the hydrolyzed collagen protein, the synthetic retanning filler is applied to the same tanning process, and the tanning performance of the tanned leather is analyzed.
The shrinkage temperature of the tanned leathers was measured and the results are shown in Table 1. The retanning agent of the oxidized tannin extract modified collagen with different dosages has different increases on the shrinkage temperature, wherein the shrinkage temperature of the synthesized retanning filler is increased most obviously under the condition that the dosage of the oxidized tannin extract is 30 percent, the increase is about 6 ℃, and the difference with the 6.3 ℃ increase of the retanning agent prepared by the glutaraldehyde modified collagen is not large. The retanning filler prepared by the method can improve the shrinkage temperature of leather and has certain tanning property.
TABLE 1 shrinkage temperature test results
The physical and mechanical properties of the finished leather, such as tensile strength, elongation at break, etc., were examined and analyzed, and the results are shown in the following table.
TABLE 2 tensile Strength test results
It can be found from table 2 that the tensile strength of leather is improved to a certain extent after the retanning filler of oxidized tannin extract modified collagen is added, and the tensile strength of leather of the collagen retanning agent after the tannin extract modification is similar to that of the collagen retanning agent after the glutaraldehyde modification, which shows that the retanning filler prepared by the method can enable fibers to be woven more tightly, and can improve certain mechanical properties of leather.
TABLE 3 elongation at break test results
It can be found from table 3 that the elongation at break of the leather after retanning filling is improved, which indicates that the filler makes the leather fiber more compact, the elongation at break of the oxidized tannin extract modified collagen is similar, and the elongation at break of the glutaraldehyde modified collagen is slightly lower.
Claims (6)
1. A preparation method based on biomass-based reactive amphoteric retanning agent is characterized in that a quinoid structure in catalytic oxidation tannin extract and amino groups in collagen hydrolysate are subjected to crosslinking modification to obtain the biomass-based reactive amphoteric retanning agent, and comprises the following steps:
dissolving collagen hydrolysate and catalytic oxidation tannin extract in water for reaction at the temperature of 30-50 ℃ and the reaction pH = 5.0-6.0, and fully reacting to obtain a biomass-based reactive amphoteric retanning agent;
the catalytic oxidation tannin extract is obtained by performing biological enzyme catalytic oxidation on tannin extract;
the collagen hydrolysate is one or more of collagen and collagen polypeptide with the number-average relative molecular mass Mn = 1000-3000; the mass ratio of the collagen hydrolysate to the catalytic oxidation tannin extract is (6-15) to (3-6);
the collagen hydrolysate is obtained by catalytic hydrolysis of collagen by industrial complex enzyme.
2. The method for preparing amphoteric retanning agent based on biomass-based reaction type as claimed in claim 1, wherein after the reaction of collagen hydrolysate with catalytic oxidation tannin extract is completed, the reaction solution is freeze-dried, separated and purified.
3. The preparation method of the amphoteric retanning agent based on the biomass-based reactive type according to claim 1, characterized by comprising the following steps:
1) preparation of collagen hydrolysate: accurately weighing 10-20 g of collagen, adding 50-250 mL of water, heating in a water bath, and adjusting the temperature to 37 ℃; adding industrial complex enzyme which accounts for 5-15% of the weight of the collagen, reacting for 2-6 hours at the rotating speed of 10-30 r/min, boiling the reaction liquid after the reaction is finished, immediately cooling, and freeze-drying for later use;
2) preparation of bio-enzyme catalytic oxidation tannin extract: weighing 3-6 g of tannin extract to dissolve, adding 0.09-0.18 g of biological enzyme to stir and dissolve, adjusting the temperature of a reaction water bath to be 30-50 ℃, adjusting the pH to be 5.0-6.0, and reacting for 20-30 h;
3) preparation of amphoteric retanning agent based on biomass-based reaction: dissolving 6-15 g of the collagen hydrolysate prepared in the step 1) in a proper amount of water, adding 3-6 g of the catalytic oxidation tannin extract prepared in the step 2), heating in a water bath, adjusting the reaction temperature to be 30-50 ℃, adjusting the pH to be 5.0-6.0, reacting for 20-30 h, and after the reaction is finished, freeze-drying to obtain the powdery biomass-based reactive amphoteric retanning agent.
4. The preparation method of the amphoteric retanning agent based on the biomass-based reactive type according to claim 3, wherein the active ingredients of the industrial complex enzyme in the step 1) comprise industrial pancreatin, papain and 172 neutral enzyme; the mass ratio of the industrial pancreatin to the papain to the 172 neutral enzyme is (1-5): 0.5-2): 1-3.
5. The method for preparing amphoteric retanning agent based on biomass-based reaction type according to claim 3, characterized in that the biological enzyme catalyzing oxidation of tannin extract in step 2) is one or more of tyrosinase, laccase and catechol oxidase.
6. A biomass-based reactive amphoteric retanning agent prepared by the method of any one of claims 1-5.
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| CN114774594A (en) * | 2022-05-05 | 2022-07-22 | 陕西科技大学 | Collagen-hyperbranched amphoteric polymer retanning agent and preparation method thereof |
| CN115011742A (en) * | 2022-06-29 | 2022-09-06 | 陕西科技大学 | Epoxy modified collagen polypeptide-based organic chromium-free tanning agent, preparation method and application |
| CN117418047A (en) * | 2023-10-19 | 2024-01-19 | 齐鲁工业大学(山东省科学院) | High-absorption chrome tanning auxiliary agent containing dithiocarbamate structure, and preparation method and application thereof |
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