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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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 25
- 102000008186 Collagen Human genes 0.000 claims abstract description 73
- 108010035532 Collagen Proteins 0.000 claims abstract description 73
- 229920001436 collagen Polymers 0.000 claims abstract description 72
- 235000018553 tannin Nutrition 0.000 claims abstract description 46
- 229920001864 tannin Polymers 0.000 claims abstract description 46
- 239000001648 tannin Substances 0.000 claims abstract description 46
- 239000000284 extract Substances 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 108090000790 Enzymes Proteins 0.000 claims description 29
- 102000004190 Enzymes Human genes 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229920001184 polypeptide Polymers 0.000 claims description 4
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 4
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 4
- 229940088598 enzyme Drugs 0.000 claims 10
- 150000001875 compounds Chemical class 0.000 claims 3
- 108010019160 Pancreatin Proteins 0.000 claims 2
- 108090000526 Papain Proteins 0.000 claims 2
- 239000004365 Protease Substances 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 2
- 229940055695 pancreatin Drugs 0.000 claims 2
- 229940055729 papain Drugs 0.000 claims 2
- 235000019834 papain Nutrition 0.000 claims 2
- 108010031396 Catechol oxidase Proteins 0.000 claims 1
- 102000030523 Catechol oxidase Human genes 0.000 claims 1
- 102000003425 Tyrosinase Human genes 0.000 claims 1
- 108060008724 Tyrosinase Proteins 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000004922 lacquer Substances 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 12
- 239000000413 hydrolysate Substances 0.000 description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
本发明涉及皮革科学领域，具体为一种基于生物质基反应型两性复鞣剂的制备方法，其特征在于以废弃皮胶原蛋白为原料，通过工业复合酶制备胶原水解物，然后采用生物酶对栲胶进行催化氧化，再用催化氧化栲胶对水解胶原蛋白进行交联改性，制备出一种两性反应型的环保型胶原蛋白有机复鞣剂，该复鞣剂为全生物质组分，可生物降解，用于皮革的复鞣，可以提高有机鞣剂鞣革的pI，适用于所有皮革加工过程的复鞣工序。The invention relates to the field of leather science, in particular to a method for preparing a biomass-based reactive amphoteric retanning agent. The tannin extract is subjected to catalytic oxidation, and then the hydrolyzed collagen is cross-linked and modified with the catalytic oxidation tannin extract to prepare an amphoteric-reactive type of environmentally friendly collagen organic retanning agent, which is a whole biomass component, Biodegradable, used for retanning of leather, can improve the pI of organic tanning agent tanned leather, suitable for retanning process of all leather processing.
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)
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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 containing dithiocarbamate structure and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960428A (en) * | 1988-01-29 | 1990-10-02 | Rohm Gmbh | Method for liming skins and hides |
| CN1450175A (en) * | 2003-05-06 | 2003-10-22 | 四川大学 | Plant polyphenol-protein composite leather filler and preparation process thereof |
| CN105838829A (en) * | 2016-05-03 | 2016-08-10 | 安徽银河皮革有限公司 | Environment-friendly leather retanning agent based on protein hydrolysate |
| CN108285937A (en) * | 2018-04-16 | 2018-07-17 | 陕西科技大学 | A method of based on biological enzyme oxidation vegetable extract and its for leather tanning |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960428A (en) * | 1988-01-29 | 1990-10-02 | Rohm Gmbh | Method for liming skins and hides |
| CN1450175A (en) * | 2003-05-06 | 2003-10-22 | 四川大学 | Plant polyphenol-protein composite leather filler and preparation process thereof |
| CN105838829A (en) * | 2016-05-03 | 2016-08-10 | 安徽银河皮革有限公司 | Environment-friendly leather retanning agent based on protein hydrolysate |
| CN108285937A (en) * | 2018-04-16 | 2018-07-17 | 陕西科技大学 | A method of based on biological enzyme oxidation vegetable extract and its for leather tanning |
Non-Patent Citations (2)
| Title |
|---|
| THE PHYLOGENY AND CHEMICAL DIVERSITY OF;J. HERBERT WAITE;《Comp.Biochem.Physiol.》;19900115;第97卷(第1期);正文第2页第2段，图1 * |
| 复合酶制备牛皮胶原多肽;戴丹琴等;《精细化工》;20130531;第30卷(第5期);第562页第1.2节 * |
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