CN116103451A - Multi-working-procedure effective synergistic beach sheepskin harmless tanning method - Google Patents
Multi-working-procedure effective synergistic beach sheepskin harmless tanning method Download PDFInfo
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- 230000002195 synergetic effect Effects 0.000 title claims abstract description 7
- 239000010985 leather Substances 0.000 claims abstract description 28
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 25
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 25
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 25
- 238000005554 pickling Methods 0.000 claims abstract description 24
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
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Images
Classifications
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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
- C14C3/28—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
-
- 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
- C14C3/22—Chemical tanning by organic agents using polymerisation products
-
- 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
- C14C7/00—Pasting processes (chemical part)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- 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)
Abstract
The invention provides a multi-station effective synergistic beachsheep skin harmless tanning method, which comprises the following steps: (1) pickling with polyphosphate instead of sodium chloride; (2) Using epoxy copolymer to seal and modify the side chain amino of collagen; (3) Tanning the Tan sheep skin by adopting a bath-free tanning method to obtain tanned leather. The polyphosphate adopted by the invention is sodium hexametaphosphate, and the dosage is 20-40 g/L. The invention realizes excellent tanning effect by cooperating with the functions of polyphosphate, epoxy compound and glutaraldehyde, avoids the use of sodium chloride and heavy metal chromium salt from the source, ensures good penetration and uniform crosslinking of glutaraldehyde, and avoids the problem of yellowing of the leather plate caused by too fast action of glutaraldehyde and leather collagen. The tanning method provided by the invention can effectively reduce the chloride ion content of the fur processing wastewater, obviously reduce the free formaldehyde content in fur products, and realize the efficient, green and high-quality production of the Chan sheep skin.
Description
Technical Field
The invention belongs to the technical field of tanning, and particularly relates to a multi-station effective synergistic beach sheepskin harmless tanning method.
Background
The formaldehyde tanned Tan sheep skin is the most widely used Tan sheep skin tanning technology at present because of the advantages of low tanning cost, mao Sebai, soft skin plate and the like. However, in the technology of tanning the Tan sheep skin by formaldehyde, besides the product quality problem caused by improper control of the processing process and the harm to the health of operators due to volatilization of formaldehyde in the processing process, a great amount of free formaldehyde remains in the product, which is up to 600mg/kg, and the technology has potential harm to the health of consumers. Thus, glutaraldehyde, which reacts rapidly with leather collagen, has high binding capacity and excellent crosslinking performance, has been attracting attention as a substitute for formaldehyde.
However, glutaraldehyde tanned leather is poor in fullness, and as glutaraldehyde is extremely easy to polymerize by itself, the fur and fur are easily turned yellow, and the appearance requirement of fur is difficult to meet. In order to meet the requirement of dyeing the Channa skin and developing new color varieties in recent years, the Channa skin tanned by formaldehyde is usually subjected to chromium retanning. However, the chromium retanning process generates a large amount of chromium-containing wastewater and the product has the potential for hexavalent chromium overstock. In addition, the beach sheepskin processing process also has the problems of large water consumption, low mechanization degree, high labor intensity, heavy pollution load of waste water and the like, and meanwhile, the water consumption is large, so that the absorption and utilization rate of the added chemicals is low, and the waste water has pollutants such as grease, formaldehyde, heavy metal chromium and the like with higher concentration, so that the problems need to be overcome.
In addition, a large amount of neutral salt (sodium chloride) is generally used for preventing leather from acid swelling, resulting in chloride ion content in leather-making wastewater of 10000mg/L or more, thereby resulting in wasteThe difficulty of water biochemical treatment is high, and the operation cost is high, so that the sewage treatment of most fur production enterprises is difficult to reach the standard, and the local water resource is greatly damaged. Cl in tanning wastewater - The problems that the water is difficult to treat, is discharged into the outside to corrode the building and the drainage pipeline, irrigates the land to lead to the yield reduction of crops, pollutes drinking water to endanger the health and the like exist, thereby realizing Cl - Zero emissions has been an important criterion for clean production of pelts.
The fur tanning technology without chromium and formaldehyde is a necessary trend of industrial development, and meanwhile, the clean processing process is developed to reduce the emission of pollutants and wastewater, which is a necessary requirement of sustainable development of fur tanning industry.
Therefore, how to provide a new tanning process to achieve chromium-free, formaldehyde-free tanning of pelts and to reduce the emission of pollutants and waste water is a challenge to be overcome.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a beachmice skin harmless tanning method with effective cooperation of multiple steps. The technical aim of the invention is to provide a chromium-free formaldehyde-free tanning technology for Channa skin on one hand, and a harmless method for reducing pollutant and wastewater discharge on the other hand.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a multi-working-procedure effective synergistic beachsheep skin harmless tanning method comprises the following steps:
(1) Pickling with polyphosphate instead of sodium chloride;
(2) Using epoxy copolymer to seal and modify the side chain amino of collagen;
(3) Tanning the Tan sheep skin by adopting a bath-free tanning method to obtain tanned leather.
Further, in the step (1), the polyphosphate is sodium hexametaphosphate.
Further, the amount of the polyphosphate used in the step (1) is 20 to 40g/L.
Further, the blocking modification method in the step (2) specifically comprises the following steps:
adding polyphosphate into water, adding the soaked fur, adjusting pH to 7 with sodium bicarbonate, and adding 10g/L epoxy copolymer for tanning.
Further, when the epoxy copolymer is added for tanning, the tanning liquid is soaked for 3 hours, then the catalyst is added, sodium carbonate is used for extracting alkali, the pH value is adjusted to 9, the temperature is raised to 45 ℃ overnight, and the tanning is finished after 48 hours.
Further, the epoxy copolymer is glycerol triglycidyl ether.
Further, the specific steps of the bath-free tanning method are as follows: the leather sample obtained by pre-tanning the modified epoxy copolymer is controlled to have the moisture content of 40-56%, the dosage of glutaraldehyde crosslinking agent is 10-25%, the tanning time is 24 hours, the pH value of the tanning liquid is 9, and the dilution multiple is 1:1.
the beneficial effects of the invention are as follows:
the invention firstly utilizes advanced materials such as high-efficiency low-toxicity bactericides, neutral protease and the like to reduce or completely cancel the use of sodium chloride in the pretreatment process before tanning. And secondly, the polyphosphate pickling auxiliary agent is used for pickling instead of sodium chloride, so that the polyphosphate can generate certain crosslinking effect and prevent acid swelling, further the use of sodium chloride is reduced from the source, and the biochemical treatment and recycling of wastewater are facilitated. And then, the epoxy copolymer is used for carrying out blocking modification on the amino groups of the side chains of the collagen, so that the bonding rate of aldehyde groups and collagen fibers is slowed down, the bonding uniformity in the skin is improved, and the leather forming performance is improved. Through the synergistic effect of polyphosphate, epoxy compound and glutaraldehyde, the excellent tanning effect is realized, the use of sodium chloride and heavy metal chromium salt is avoided from the source, good penetration and uniform crosslinking of glutaraldehyde are ensured, and the problem of yellowing of the leather plate caused by too fast action of glutaraldehyde and leather collagen is avoided.
In conclusion, the tanning method can effectively reduce the chloride ion content of the fur processing wastewater, remarkably reduce the free formaldehyde content in fur products, and realize the efficient, green and high-quality production of the Chan sheep skin.
On the basis of the method, a passing type bath-free tanning method based on a micro-jet technology is adopted (see patent CN 201911361028.7), the prepared glutaraldehyde tanning agent is injected into the pretreated beachsheep skin plate through micro-jet, so that the rapid penetration and combination are realized, the glutaraldehyde is prevented from contacting wool fibers, the aim of avoiding yellowing of the wool is achieved, and the zero emission of waste liquid in the tanning process is realized.
Drawings
FIG. 1 is a flow chart of a tanning process employed in the present invention;
FIG. 2 is a schematic diagram of rabbit fur segmentation;
FIG. 3 shows otter rabbit skin Ts (E: EDGE, T: TGIC, G: GPE) tanned with different epoxy tanning agents;
FIG. 4 shows otter rabbit skin Ts at different tanning temperatures (45℃and room temperature for A and B respectively);
FIG. 5 is a DSC curve of rex rabbit fur before and after cross-linking modification;
FIG. 6 is a DSC curve of a wool fiber before and after cross-linking modification;
FIG. 7 is an X-ray diffraction pattern of rex rabbit hair fibers before and after tanning;
fig. 8 shows rex rabbit skin Ts with different moisture contents;
FIG. 9 shows otter rabbit skin Ts with different GA dosages;
fig. 10 shows otter rabbit skin Ts at different tanning times;
FIG. 11 is a comparison of skin whiteness after bath-free tanning;
fig. 12 is a comparison of Mao Baidu after no bath tanning;
FIG. 13 is a graph showing physical properties of a fur of rex rabbits;
fig. 14 is an SEM micrograph of beaver rabbit skin collagen fibers after bath-free tanning.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be specifically described with reference to the following examples, which are provided for explaining and illustrating the present invention only and are not intended to limit the present invention. Some non-essential modifications and adaptations of the invention according to the foregoing summary will still fall within the scope of the invention.
The tanning process flow used in the following examples is shown in fig. 1.
Example 1
Chlorine-free pickling process:
in this experiment, sodium hexametaphosphate (SPP) was used for pickling in order to avoid the use of sodium chloride from the source. Sodium hexametaphosphate has a molecular formula of (NaPO) 3 ) 6 The pickling can avoid introducing Cl into the leather-making wastewater - The molecular weight of the modified starch is 611.17g/mol, and the modified starch is generally white powder or colorless block, and can be used in the food field, such as improving the water retention of food and preserving food.
Primary materials:
sodium hexametaphosphate (NaPO) 3 ) 6 Sulfuric acid, formic acid, lactic acid.
(II) main experimental method and steps:
the effect of the amount of sodium hexametaphosphate and the acid type on the acid swelling inhibition ability was investigated. Experiments show that 20g/L of sodium hexametaphosphate can achieve the effect of inhibiting the acid swelling, the thickness change of the pickled leather blank is only 2-3%, and when different types of acid (sulfuric acid, formic acid and lactic acid) are used for pickling, the sodium hexametaphosphate can also prevent the leather from acid swelling, so that the sodium hexametaphosphate has the acid swelling inhibition capability.
Table 1 salt-free pickling process
(1) Acid swelling inhibition performance of sodium hexametaphosphate (SPP):
the conventional pickling was performed using 30g/L of SPP pickling and without using neutral salt, and the procedure was referred to in Table 1 above, and the degree of swelling of the acid skin was measured after the pickling was completed to determine whether SPP could suppress acid swelling.
(2) Influence of the acid species on the acid swelling inhibition ability of sodium hexametaphosphate:
acids used in conventional pickling include formic acid and sulfuric acid, and organic acids are generally used in high yield and soft, but organic acids have high cost, so that two factors of cost and quality of the finished product need to be considered when selecting the acids. In order to explore the relation between SPP pickling and the types of acidic solutions, sulfuric acid, formic acid and lactic acid are used for pickling respectively, the dosage of SPP is 30g/L, after pickling, an MH-YDI thickness tester is used for testing the swelling degree of the acid skin, and the acid swelling inhibition capability of SPP and different acidic liquids during pickling is studied.
(3) SPP pickling usage optimization
When NaCl is used for pickling, the concentration can be effectively inhibited from swelling bare skin only when a certain value is needed, so that the influence of the SPP consumption on the pickling effect is explored. SPP amounts were 10g/L, 15g/L, 20g/L, 30g/L, respectively, and the thickness changes of the skin blanks before and after pickling were separately tested.
(III) experimental results:
the test results of the above experiments are shown in tables 2 to 4 below.
TABLE 2 degree of swelling of sodium hexametaphosphate pickling peels (A: SPP, B: blank group)
TABLE 3 degree of skin swelling after acid leaching
TABLE 4 degree of skin swelling after pickling at different SPP levels
Example 2
Adopting epoxy compound to seal and modify side chain amino group of collagen:
primary materials:
glycerol triglycidyl ether (GPE), triglycidyl isocyanurate (TGIC), ethylene Glycol Diglycidyl Ether (EGDE).
(II) main experimental method and steps:
the effect of the type of epoxy compound and the tanning temperature on its crosslinking modifying ability was investigated.
(1) The crosslinking modification process comprises the following steps:
the method for cutting the beaver rabbit skin into small pieces comprises symmetrically cutting adjacent parts of the skin, wherein the cutting method is shown in figure 2, adding neutral salt into water, adding the skin, adjusting pH to 7 with sodium bicarbonate, and adding 10g/L epoxy compound tanning agent. After the tanning liquid is soaked for 3 hours, a catalyst is added, sodium carbonate is used for extracting alkali, the pH value is regulated to about 9, and the temperature is raised to 45 ℃ overnight. After tanning for 24 hours, changing the temperature according to the experimental requirements, after 12 hours, recovering the room temperature, and after the total time is 48 hours, the tanning is finished. Shrinkage temperatures were measured at 24h, 36h, 48h of tanning, respectively.
(2) To investigate the relationship between the kind of epoxy tanning agent and the shrinkage temperature, three suitable epoxy compounds were selected for comparative experiments, the experimental protocols are shown in table 5. The tanning process of table 5 was followed with 3 sets of pelts. The three epoxide tanning agents were Ethylene Glycol Diglycidyl Ether (EGDE), triglycidyl isocyanurate (TGIC) and glycerol triglycidyl ether (GPE), respectively, and were each prepared with 8mL/L of triethylamine (Et) 3 N) as catalyst. The epoxy compound having the best tanning property is selected by comparing the shrinkage temperatures.
TABLE 5GPE crosslinking modification (pretanning) Process
(3) The shrinkage temperature of crust leather is an important index for evaluating the crosslinking modification effect. After tanning is completed, the shrinkage temperature of the crust leather sample is measured by adopting an HY-852 leather shrinkage thermometer according to the QB/T1271-2012 national standard method. Mao Ti is divided before sampling, the size of the cut specimen (50.+ -. 2) mm× (7.0.+ -. 0.2) mm, and each sample is measured four times, and then the arithmetic average is taken.
(III) experimental results:
the shrinkage temperature (Ts) of the otter rabbit skin tanned by different epoxy tanning agents is shown in figure 3, the temperature conditions of the otter rabbit skin tanned by different epoxy tanning agents are shown in figure 4, the DSC curves of the otter rabbit skin before and after crosslinking modification are shown in figure 5, and the DSC curves of the wool fibers before and after crosslinking modification are shown in figure 6.
(1) The following conclusions were drawn by single factor experiments: GPE can be selected when the EC tanning agent is used for tanning beaver rabbit skin. When GPE is used for tanning beaver rabbit skin, the dosage is 10g/L, the tanning time is 36h, 8ml/L of Et3N is added after three hours of tanning, the pH=9 after alkali extraction, and the Ts can reach 77 ℃.
(2) After the rex rabbit skin is tanned by the GPE final process, DSC is adopted to analyze the fiber heat stability change of the skin and the fur before and after the tannage. The results show that the heat denaturation temperature after tanning is increased and the heat stability of the wool fibers is also increased, indicating that GPE cross-links both the skin and the wool fibers.
(3) XRD analysis results show that the crystallinity of the wool fiber is lower after tanning than before tanning, and the crystallinity is reduced so that the wool fiber is easier to color, and the mechanical strength is reduced. Infrared analysis experiments show that wool fibers do cross-link with GPE. Because of the partial cross-linking, the cross-linked amino acid can not react with glutaraldehyde to generate chromophore, so the tanned hair is kept white.
(4) The physical and mechanical properties of the tanned leather board are analyzed by the experiment, and the result shows that the mechanical strength and the tearing strength of the GPE tanned rex rabbit fur meet the requirements, the fullness is good, but the softness is slightly poor, the fur is tightly connected with the fur, and the fur is smooth. SEM is adopted to observe the dispersion condition of the leather fibers before and after tanning and the damage degree of the scale layers of the wool fibers, and the scale layers of the wool fibers before and after tanning are orderly arranged and are in a closed state, which is also the reason that the wool quilt can keep smooth after tanning.
Example 3
Non-bath glutaraldehyde tanning technology
The bath-free tanning process is used for tanning the fur without preparing excessive water for tanning the fur, thereby achieving the purpose of saving water resources, avoiding swelling of the fur by adding neutral salt, and reducing the using amount of the neutral salt. All tanning agents are only present on the skin embryo during bath-free tanning, and are not required to be dissolved in water to cause waste or be stained with hair to cause hair to be polluted to turn yellow. In order to study the feasibility of the method for tanning the beaver rabbit skin, the technological parameters are optimized on the basis of feasibility, and the tanning performance, such as fiber dispersion degree, hair whiteness, thermal stability and the like, is evaluated by detecting the correlation of finished products, so that the beaver rabbit skin bath-free tanning technology based on Glutaraldehyde (GA) is realized.
The effect of the moisture content of the leather board on the absorption of the tanning agent by the leather board is obvious when the leather board is tanned without bath. The moisture that the leather board contains reduces, will make the leather board fibre bonding possibility increase, and the moisture that the leather board contains increases, will lead to the leather board to the absorption performance of tanning agent to reduce, and both cases can influence the entering of follow-up process chemistry thing, influence the quality of finished leather. To examine the effect of skin moisture content on retanning performance, 16 GPE pre-tanned skin samples were prepared, divided into 4 groups, each group moisture content being controlled as follows: 40.77%, 46.01%, 50.56%, 56% of GA was used in each of 4 samples of 10%, 15%, 20%, 25%, respectively. Remaining parameters were identical (see table 6): tanning time is 24 hours, pH value of tanning liquid is 9, dilution multiple is 1:1.
TABLE 6 experimental investigation of GPE-GA tanning Process
The X-ray diffraction curve graph of the beaver rabbit fur fiber before and after tanning is shown in fig. 7, the shrinkage temperature (Ts) of beaver rabbit fur with different moisture content is shown in fig. 8, the beaver rabbit fur Ts with different GA dosage is shown in fig. 9, the beaver rabbit fur Ts with different tanning time is shown in fig. 10, the whiteness contrast of the beaver rabbit fur after no bath tanning is shown in fig. 11, the whiteness contrast of the beaver rabbit fur after no bath tanning is shown in fig. 12, the physical property of the beaver rabbit fur is shown in fig. 13, and the SEM micrograph of the beaver rabbit fur fiber after no bath tanning is shown in fig. 14.
Experimental results show that the reaction speed of GA and protein is high, and under proper conditions, ts can reach more than 80 ℃ within 1 h. When GA is used for bath-free tanning, ts reaches 86.5 ℃ after 1h, and after 2h, the Ts reaches 87 ℃ at most. In order to explore the relationship between GPE-GA tanning time and tanning performance, ts were measured after 1h,4h,7h,10h, respectively, after bath-free tanning, and other process conditions were: the moisture content was 52%, the GA usage was 15%, the dilution factor was 1:1, tanning liquor ph=4. The Ts reaches 86.5 ℃ within 1h, and the change of the Ts is not large when the time is increased again, so that the Ts is considered to be unchanged. The time increases for another 3 hours, ts starts to decrease, only 86 ℃, and when the time increases to 10 hours again, ts continues to decrease to 85 ℃. After subsequent measurement, ts is maintained above 85 ℃, so that the tanning time of GPE-GA can be longer than 10 hours for stabilization.
Claims (7)
1. The harmless tanning method for the beachmice skin with the effective and synergistic multiple steps is characterized by comprising the following steps of:
(1) Pickling with polyphosphate instead of sodium chloride;
(2) Using epoxy copolymer to seal and modify the side chain amino of collagen;
(3) Tanning the Tan sheep skin by adopting a bath-free tanning method to obtain tanned leather.
2. A tanning process according to claim 1, wherein in step (1) the polyphosphate is sodium hexametaphosphate.
3. A tanning process according to claim 1 or 2, wherein the polyphosphate in step (1) is used in an amount of from 20 to 40g/L.
4. Tanning process according to claim 1 or 2, characterized in that the block modification process of step (2) is in particular:
adding polyphosphate into water, adding the soaked fur, adjusting pH to 7 with sodium bicarbonate, and adding 10g/L epoxy copolymer for tanning.
5. A tanning process according to claim 4, wherein, when the epoxide copolymer is added for tanning, the tanning liquor is soaked for 3 hours, then a catalyst is added, sodium carbonate is used for extracting alkali, the pH value is adjusted to 9, the temperature is raised to 45 ℃ overnight, and the tanning is finished after 48 hours.
6. A tanning process according to claim 1 or 2, wherein the epoxy copolymer is glycerol triglycidyl ether.
7. Tanning process according to claim 1 or 2, characterized in that the specific steps of the bath-free tanning process are: the leather sample obtained by pre-tanning the modified epoxy copolymer is controlled to have the moisture content of 40-56%, the dosage of glutaraldehyde crosslinking agent is 10-25%, the tanning time is 24 hours, the pH value of the tanning liquid is 9, and the dilution multiple is 1:1.
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