A method for preparing a nitrogen-, sulfur-heteroatom-rich collagen fiber-based material

Abstract

The application discloses a preparation method of nitrogen and sulfur heteroatom-rich collagen fiber-based material, and comprises the following steps: treating tanning waste according to the steps of crushing, washing, drying and the like, then performing space and structure activation treatment on the tanning waste by using alkali liquor, washing the tanning waste to neutral by using deionized water, and drying the tanning waste to obtain alkali-activated collagen fiber; transferring the alkali-activated collagen fiber to an aldehyde solution, adding a certain amount of amino thiazole substance, and performing cross-linking and solidification reaction by heating and stirring, and then performing filtration, washing and drying on the reaction product to obtain the preparation method of the nitrogen and sulfur heteroatom-rich collagen fiber-based material. The thiazole ring functional group is solidified and grafted on the interface of the alkali-activated collagen fiber, the content of active sites for selectively capturing iodine vapor is increased, the adsorption amount of iodine vapor is increased, the captured iodine is not easy to volatilize, meanwhile, the polymer material structure is stable, and therefore, the polymer material can be used as an ideal candidate material for efficiently and selectively capturing radioactive iodine vapor in the gas-borne effluent in the spent fuel reprocessing process.

Description

Technical Field

[0001] This invention belongs to the environmental protection field of using biomass waste resources for the adsorption of radioactive iodine vapor in the environment, specifically a method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms. Background Technology

[0002] Leather waste mainly refers to the scraps and waste generated during the production of clothing, footwear, and other products. The vast majority of these scraps are difficult to reuse, resulting not only in a waste of raw material resources but also causing serious environmental impacts as the waste accumulates. Burning leather waste produces large amounts of toxic gases such as sulfur dioxide and nitrogen oxides, posing significant health risks. Therefore, how to achieve the recycling of leather waste resources has always been a key concern for scientists. Collagen fibers extracted from leather waste are white, short-fiber solids that are hydrophilic, insoluble in water, and disperse after swelling. Collagen fibers are structural proteins, and the amino acids that make up collagen are rich in active groups, such as primary amino, hydroxyl, and carboxyl groups. Furthermore, type I collagen, the main component of collagen fibers, has a characteristic triple helix structure and is chemically stable. These characteristics and structures indicate that collagen fibers are a rich, modifiable, and biodegradable resource, capable of adsorbing various molecules such as dyes and heavy metals through physical and chemical interactions. At the same time, it is inexpensive, non-toxic, harmless, and biodegradable, making it a novel biomass material.

[0003] To meet the growing energy demand and address greenhouse gas emissions, nuclear energy has been identified as a viable alternative to fossil fuels due to its advantages such as safety, cleanliness, economy, and efficiency. Currently, over 400 nuclear reactors are located worldwide, supplying more than 10% of the electricity. With the development of nuclear energy, the safety of nuclear power plants and the disposal of nuclear waste have remained at the forefront of research. Radioactive isotope iodine, as one of the fission products of uranium, is a major product of nuclear waste. Major isotopes include... 131 I (half-life of 8 days) and 129 I (half-life is 1.57 × 10⁻⁶) 7 Radioactive isotopes, generally existing as the diatomic element iodine (I₂) and organic iodides, with I₂ exhibiting high volatility and mobility. When the natural environment is contaminated by radioactive isotopes, it has a significant impact, such as damaging the ecological environment and endangering human health. Iodine volatilizing into the air can directly enter the human body, causing internal irradiation, or adhere to the skin, causing prolonged direct damage. Furthermore, radioactive iodine entering the body through the air can accumulate in the thyroid gland, causing prolonged concentrated irradiation and leading to damage to the immune system.

[0004] Currently, radioactive iodine capture mainly includes two strategies: wet scrubbing and solid adsorption. Wet scrubbing further includes acidic and alkaline scrubbing. Because wet scrubbing produces large amounts of liquid residue, generates new pollutants, and poses a risk of secondary environmental pollution, only alkaline scrubbing is currently used in reprocessing plants. Compared to wet scrubbing, solid adsorption has rapidly developed due to its advantages such as fast and stable adsorption rates and ease of operation. Solid adsorption is widely used for radioactive iodine capture due to its environmental friendliness, low cost, and ease of operation. However, solid adsorption is susceptible to the influence of the material itself and external factors, such as pore size, the number of adsorption sites, and the environment. Various solid adsorbent materials have been used to capture volatile radioactive iodine, including activated carbon, silver-containing mordenite zeolite, chalcogenide aerogels, microporous polymers, and metal-organic frameworks (MOFs). Among these, activated carbon and silver-containing mordenite zeolite have been widely used in industrial applications to capture iodine from waste gas streams. On the one hand, activated carbon has several drawbacks, including low adsorption capacity, low auto-ignition temperature, and difficulty in regeneration. Furthermore, iodine adsorbed on activated carbon exists primarily in the form of iodine molecules, making it easily desorbed and migrated. On the other hand, limited usable surface area, high manufacturing costs, low recyclability, and adverse environmental impacts on silver hinder the further application of silver-containing mordenite zeolite. Therefore, it is essential to develop an adsorbent that is simple to prepare, low-cost, environmentally friendly, and highly efficient at capturing iodine. Summary of the Invention

[0005] To address the aforementioned technical deficiencies, this invention provides a method for preparing a nitrogen- and sulfur-rich collagen fiber-based material that is low-cost, simple in preparation, does not cause secondary pollution to the environment, is stable, has a high iodine vapor adsorption capacity, is naturally biodegradable, and is non-toxic and harmless. This invention leverages the characteristics of collagen fibers. After alkaline treatment of the biomass raw material, more hydroxyl and amino groups are exposed within the collagen fibers, enhancing their affinity for iodine vapor. Simultaneously, the cross-linking effect of glutaraldehyde immobilizes aminothiazole on the collagen fibers, introducing a large number of nitrogen and sulfur atoms. The lone pairs of electrons on these nitrogen and sulfur atoms have an extremely high binding capacity for iodine vapor, thereby enhancing the adsorption capacity for iodine.

[0006] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0007] To achieve these objectives and other advantages according to the present invention, a method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms is provided, comprising the following steps:

[0008] Step 1: After processing the leather tanning waste through crushing, washing, and drying, a precursor is obtained;

[0009] Step 2: The precursor is spatially and structurally activated with alkaline solution, then washed with deionized water until neutral and dried to obtain alkali-activated collagen fibers.

[0010] Step 3: Transfer the alkali-activated collagen fibers to an aldehyde solution of a certain concentration, then add a certain amount of aminothiazole substances to the mixed solution, heat and stir to carry out cross-linking and curing reaction, and after filtration, washing and drying of the reaction product, a collagen fiber-based material rich in nitrogen and sulfur heteroatoms is obtained.

[0011] Preferably, in step one, the pulverizing time is 0.5 to 10 minutes and the drying temperature is 70 to 80°C.

[0012] Preferably, in step two, the alkaline solution is one or a mixture of two of NaOH and KOH solutions; the pH value of the precursor solution activated by the alkaline solution is maintained at 9-14.

[0013] Preferably, in step three, the concentration of the aldehyde solution is 1 wt% to 30 wt%; the aldehyde solution is one or a mixture of formaldehyde and glutaraldehyde.

[0014] Preferably, in step three, the aminothiazole substance is a thiazole derivative, including but not limited to one or a combination of aminothiazole, chlorothiazole, and bromothiazole.

[0015] Preferably, in step three, the mass percentage of collagen fibers in the mixture of aminothiazole substances and collagen fibers is 25% to 75%; the mass-to-volume ratio of collagen fibers to aldehyde solution is 1g:100 to 500ml.

[0016] Preferably, in step three, the heating temperature for the crosslinking curing reaction is set to 30–70°C, and the stirring time is 1–24 h.

[0017] Preferably, in step three, the drying temperature is 50–100°C and the drying time is 12–24 hours.

[0018] The present invention has at least the following beneficial effects:

[0019] (1) The collagen fibers after alkali modification and activation release a large number of active groups that are conducive to iodine-induced adsorption and thiazole ring solidification grafting. They are chemically stable, selectively adsorb iodine vapor, and have a high adsorption capacity. Iodine is not easily volatilized after adsorption, which is conducive to the stable storage and treatment of radioactive gaseous iodine.

[0020] (2) The raw materials used in this invention are waste materials generated from leather processing, which are recycled and avoid environmental pollution problems, and the sources are wide.

[0021] (3) The aminothiazoles selected in this invention have stable structures, are not easily decomposed, have low toxicity, are easy to store and use, and are inexpensive.

[0022] (4) The preparation process of this invention is safe, simple to operate, green and environmentally friendly, and waste liquid is recycled and reused, avoiding secondary pollution to the environment during the preparation process.

[0023] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0024] Figure 1 .a is a SEM image of the nitrogen-rich, sulfur-rich heteroatom-based collagen fiber material prepared in Example 3 of this invention;

[0025] Figure 1 .b is a physical image of the collagen fibers (CF) prepared in Comparative Example 1;

[0026] Figure 1 .c is a photograph of the alkali-activated collagen fibers (ACF) prepared in Comparative Example 2;

[0027] Figure 1 .d is a physical image of the nitrogen-rich, sulfur-rich heteroatom-based collagen fiber material (AT@ACF) prepared in Example 1 of this invention;

[0028] Figure 1 .e is a physical image of the nitrogen-rich, sulfur-containing heteroatom-rich collagen fiber-based material (AT@ACF) prepared in Example 2 of this invention;

[0029] Figure 1 .f is a physical image of the nitrogen-rich, sulfur-rich heteroatom-based collagen fiber material (AT@ACF) prepared in Example 3 of this invention;

[0030] Figure 1 .g is a physical image of the nitrogen-rich, sulfur-rich collagen fiber-based material prepared in Example 1 of this invention after adsorbing iodine vapor (AT@ACF-I);

[0031] Figure 1 .h is a physical image of the nitrogen-rich, sulfur heteroatom-rich collagen fiber-based material prepared in Example 2 of this invention after adsorbing iodine vapor (AT@ACF-I);

[0032] Figure 1 .i is a physical image of the nitrogen-rich, sulfur-containing heteroatoms-rich collagen fiber-based material prepared in Example 3 of this invention after adsorbing iodine vapor (AT@ACF-I);

[0033] Figure 2The graphs show the adsorption results of iodine vapor on the unmodified leather waste collagen fibers of Comparative Example 1, the alkali-activated collagen fibers prepared in Comparative Example 2, and the nitrogen- and sulfur heteroatom-rich collagen fiber-based materials of Examples 1-3.

[0034] Figure 3 The images show the FT-IR results of the unmodified leather waste collagen fibers of Comparative Example 1, the alkali-activated collagen fibers prepared in Comparative Example 2, the nitrogen- and sulfur heteroatom-rich collagen fiber-based material of Example 1, and the nitrogen- and sulfur heteroatom-rich collagen fiber-based material after adsorbing iodine vapor in Example 1.

[0035] Figure 4 The thermogravimetric analysis (TGA) results are shown for the unmodified leather waste collagen fiber of Comparative Example 1, the alkali-activated collagen fiber prepared in Comparative Example 2, the nitrogen- and sulfur heteroatom-rich collagen fiber-based material of Example 1, and the nitrogen- and sulfur heteroatom-rich collagen fiber-based material after adsorbing iodine vapor in Example 1.

[0036] Figure 5 The images show the XRD results of the unmodified leather waste collagen fibers of Comparative Example 1, the alkali-activated collagen fibers prepared in Comparative Example 2, the nitrogen- and sulfur heteroatom-rich collagen fiber-based material of Example 1, and the nitrogen- and sulfur heteroatom-rich collagen fiber-based material after adsorbing iodine vapor in Example 1.

[0037] Figure 6 EDS results of the nitrogen-rich, sulfur-heteroatom-rich collagen fiber-based material prepared in Example 3 of this invention after iodine adsorption;

[0038] Figure 7 The graph shows the adsorption of iodine vapor at different intervals by the nitrogen-rich, sulfur-rich collagen fiber-based material prepared in Example 3 of this invention.

[0039] Figure 8 The image shows the UV-Vis result of the adsorption of iodine on the nitrogen-rich, sulfur-containing heteroatoms-based collagen fiber material prepared in Example 3 of this invention after adsorption in ethanol. Detailed Implementation

[0040] The present invention will be further described in detail below with reference to several embodiments so that those skilled in the art can implement it based on the description.

[0041] Example 1:

[0042] A method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms includes the following steps:

[0043] Step 1: Crush the leather waste in a pulverizer for 2 minutes, ultrasonically clean it in deionized water for 3 hours, filter it, and dry it in a vacuum drying oven at 75°C for 12 hours to obtain the precursor.

[0044] Step 2: Add the dried precursor to deionized water, add sodium hydroxide to adjust the pH of the solution to 12; sonicate in a 60℃ water bath for 6 hours, wash repeatedly with deionized water until neutral, filter, and dry in a 75℃ vacuum oven to obtain alkali-activated collagen fibers.

[0045] Step 3: Add 1g of alkali-activated collagen fiber to 100ml of 4wt% glutaraldehyde solution, and add 0.5g of 2-aminothiazole to the solution; heat to 50℃ and stir for 6h in a constant temperature magnetic stirrer, wash, filter, and dry in a vacuum oven at 75℃ to obtain a collagen fiber-based material rich in nitrogen and sulfur heteroatoms.

[0046] Example 2:

[0047] A method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms includes the following steps:

[0048] Step 1: Crush the leather waste in a pulverizer for 2 minutes, ultrasonically clean it in deionized water for 3 hours, filter it, and dry it in a vacuum drying oven at 75°C for 12 hours to obtain the precursor.

[0049] Step 2: Add the dried precursor to deionized water, add sodium hydroxide to adjust the pH of the solution to 13; sonicate in a 60℃ water bath for 6 hours, wash repeatedly with deionized water until neutral, filter, and dry in a 75℃ vacuum oven to obtain alkali-activated collagen fibers.

[0050] Step 3: Add 1g of alkali-activated collagen fiber to 100ml of 3wt% glutaraldehyde solution, and add 1g of 2-aminothiazole to the solution; heat to 50℃ and stir for 6h in a constant temperature magnetic stirrer, wash, filter, and dry in a vacuum oven at 75℃ to obtain a collagen fiber-based material rich in nitrogen and sulfur heteroatoms.

[0051] Example 3:

[0052] A method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms includes the following steps:

[0053] Step 1: Crush the leather waste in a pulverizer for 2 minutes, ultrasonically clean it in deionized water for 3 hours, filter it, and dry it in a vacuum drying oven at 75°C for 12 hours to obtain the precursor.

[0054] Step 2: Add the dried precursor to deionized water, add sodium hydroxide to adjust the pH of the solution to 13; sonicate in a 60℃ water bath for 6 hours, wash repeatedly with deionized water until neutral, filter, and dry in a 75℃ vacuum oven to obtain alkali-activated collagen fibers.

[0055] Step 3: Add 1g of alkali-activated collagen fiber to 100ml of 3wt% glutaraldehyde solution, and add 2g of 2-aminothiazole to the solution; heat to 50℃ and stir for 6h in a constant temperature magnetic stirrer, wash, filter, and dry in a vacuum oven at 75℃ to obtain a collagen fiber-based material rich in nitrogen and sulfur heteroatoms.

[0056] Comparative Example 1:

[0057] A method for preparing collagen fibers includes the following steps:

[0058] Tannery waste hides were crushed in a pulverizer for 2 minutes, ultrasonically cleaned in deionized water for 3 hours, filtered, and dried in a vacuum drying oven at 75°C for 12 hours to obtain unmodified collagen fibers.

[0059] Comparative Example 2:

[0060] Step 1: Crush the leather waste in a pulverizer for 2 minutes, ultrasonically clean it in deionized water for 3 hours, filter it, and dry it in a vacuum drying oven at 75°C for 12 hours to obtain unmodified collagen fibers.

[0061] Step 2: Add the dried collagen fibers to deionized water, add sodium hydroxide to adjust the pH of the solution to 12; sonicate in a 60℃ water bath for 6 hours, wash repeatedly with deionized water until neutral, filter, and dry in a 75℃ vacuum oven to obtain alkali-activated collagen fibers.

[0062] Iodine vapor adsorption experiments were conducted on the nitrogen-rich, sulfur-rich leather waste collagen fiber base materials of Examples 1-3, the unmodified collagen fiber prepared in Comparative Example 1, and the alkali-activated collagen fiber prepared in Comparative Example 2. The method was as follows: non-radioactive iodine was used instead of radioactive iodine. First, excess iodine was placed at the bottom of a 500 mL gas collecting bottle. 50 mg of modified collagen fiber (Examples 1-4) was placed in a small crucible, which was placed at the bottom of the gas collecting bottle. The bottle cap was tightened, and the gas collecting bottle was placed in a 75°C oven. After adsorption for a maximum of 24 hours at different time intervals, the bottle was removed from the oven, cooled to room temperature, and the content of iodine vapor adsorbed by the modified collagen fiber was determined by gravimetric method. The calculation formula is as follows: Q=(m2-m1) / m1×100wt%, where Q (wt%) is the amount of iodine adsorbed, m1 (mg) and m2 (mg) are the weights of the modified collagen fiber material before and after iodine adsorption, respectively. Each adsorbent material is subjected to three parallel adsorption experiments, and the average value is taken.

[0063] The present invention will now be described in further detail with reference to the accompanying drawings:

[0064] Appendix Figure 1Image .a is a SEM image of the preparation method of the nitrogen-rich, sulfur heteroatom-rich collagen fiber-based material prepared in Example 3 of the present invention. It can be seen from the image that after the alkali-activated collagen fiber (ACF) is grafted with aminothiazole, a nanometer-thick film can be clearly observed on the surface.

[0065] Appendix Figure 1 .b~ Figure 1 The figures in .f are physical images of the preparation methods of unmodified collagen fibers (CF) in Comparative Example 1, alkali-activated collagen fibers (ACF) in Comparative Example 2, and nitrogen-rich, sulfur-containing heteroatom-based collagen fiber materials (AT@ACF) prepared in Examples 1-3, respectively. The results show that the alkali-activated collagen fibers (ACF) are darker and looser than collagen fibers (CF). At the same time, the collagen fibers (AT@ACF) grafted with aminothiazole become darker in color as the ratio of aminothiazole to ACF increases.

[0066] Appendix Figure 1 .g~ Figure 1 Image .i shows the actual images of the nitrogen-rich, sulfur-containing heteroatoms-rich collagen fiber-based materials (AT@ACF) prepared in Examples 1-3 of this invention after adsorbing iodine vapor. The color of AT@ACF with different proportions after adsorbing iodine vapor is black, indicating that the prepared materials can effectively adsorb iodine vapor.

[0067] Figure 2 The figures show the adsorption results of iodine vapor on unmodified leather waste collagen fiber (CF) of Comparative Example 1, alkali-activated collagen fiber (ACF) prepared in Comparative Example 2, and nitrogen- and sulfur-rich heteroatom-rich collagen fiber-based materials (AT@ACF) of Examples 1-3. The results show that the adsorption capacity of unmodified collagen fiber (CF) is only 609.3 mg / g, which increases to 915.4 mg / g after alkali activation. The adsorption capacity of modified collagen fiber (AT@ACF) for iodine is significantly increased, and the highest adsorption capacity of 2318.6 mg / g is reached when the mass ratio of 2-aminothiazole to collagen fiber in the mixed solution is 2:1.

[0068] Figure 3 The images show the FT-IR spectra of unmodified collagen fibers (CF) in Comparative Example 1, alkali-activated collagen fibers (ACF) in Comparative Example 2, the preparation method of nitrogen- and sulfur-rich heteroatom-based collagen fiber material in Example 1 (AT@ACF), and the bismuth-based collagen fiber material after adsorption of iodine vapor in Example 1 (AT@ACF-I). The results show that the infrared spectra of CF, ACF, AT@ACF, and AT@ACF-I are typical of protein structures. A broad peak is observed at 3339.48 cm⁻¹. -1 The left and right angles are mainly attributed to the tensile vibration of –OH, with a peak value of 1638.30 cm. -1 This should be attributed to the characteristic absorption peak of C=O tensile vibration. Peak value: 1543.78 cm⁻¹-1 and 1384.66cm -1 The peaks are characteristic absorption peaks of N–H bending vibration and C–N stretching vibration. The peaks are enhanced after grafting with aminothiazole, and shift to 1522.52 cm⁻¹ after iodine adsorption. -1 and 1401.54cm -1 After grafting with aminothiazole, AT@ACF reached 1119.49 cm. -1 The peak value at [location] is the characteristic absorption peak of the C–S–C tensile vibration; after iodine adsorption, the peak value shifts to 1115.71 cm⁻¹. -1 In addition, 620.01cm -1 The peaks at these values ​​represent the out-of-plane bending vibrations of the N–H groups of amines and the O–H groups of alcohols, respectively. The FT-IR results indicate that aminothiazole was successfully grafted onto ACF.

[0069] Figure 4 The thermogravimetric analysis (TGA) results are shown for Comparative Example 1 (unmodified collagen fiber (CF), Comparative Example 2 (alkali-activated collagen fiber (ACF), Example 1 (nitrogen- and sulfur-rich heteroatom-rich collagen fiber material (AT@ACF)), and Example 1 (AT@ACF) after iodine vapor adsorption (AT@ACF-I). The results show that the TGA curves of CF, ACF, and AT@ACF are basically the same, indicating that the thermal stability of alkali-activated collagen fiber (ACF) and modified collagen fiber (AT@ACF) is similar to that of CF, exhibiting good thermal stability. However, the thermal stability of (AT@ACF-I) after iodine capture is poor, mainly due to the volatilization of physically adsorbed iodine and the chemically adsorbed iodine I3. - Analysis.

[0070] Figure 5 The XRD results of the following materials after adsorbing iodine vapor are shown: Comparative Example 1: Unmodified collagen fiber (CF); Comparative Example 2: Alkali-activated collagen fiber (ACF); Example 1: Nitrogen-rich, sulfur-heteroatom-rich collagen fiber-based material (AT@ACF); and Example 1 (AT@ACF-I). The results show that CF, ACF, and AT@ACF have amorphous structures, and no obvious iodine crystal peaks were observed after AT@ACF adsorbed iodine, indicating that the adsorption of iodine vapor by AT@ACF is mainly chemical adsorption.

[0071] Figure 6 The image shows the EDS results after iodine adsorption in the preparation method of the nitrogen-rich, sulfur heteroatom-rich collagen fiber matrix material prepared in Example 3 of this invention. The results show that after the grafted aminothiazole ACF (AT@ACF) captures iodine, a strong peak of iodine appears, and the proportion of iodine is about 53.89%, proving that AT@ACF effectively captures iodine.

[0072] Figure 7 The figure shows the adsorption results of iodine vapor at different time intervals in the preparation method of the collagen fiber matrix material rich in nitrogen and sulfur heteroatoms prepared in Example 3 of the present invention. The results show that in the first 16 hours, the adsorption amount of iodine by AT@ACF continuously increases with the increase of adsorption time, and the adsorption amount reaches saturation of about 2118.9 mg / g after about 16 hours.

[0073] Figure 8 The image shows the UV-Vis results of the adsorption of iodine in ethanol after the preparation of the nitrogen-rich, sulfur-heteroatom-rich collagen fiber-based material prepared in Example 3 of this invention. The results show that when AT@ACF after iodine adsorption is placed in an excess of ethanol solution, the concentration of iodine in the solution gradually increases over time, reaching the maximum adsorption amount at about 72 hours.

[0074] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A method for preparing a collagen fiber-based material rich in nitrogen and sulfur heteroatoms, characterized in that, Includes the following steps: Step 1: After processing the leather tanning waste through crushing, washing, and drying, a precursor is obtained; Step 2: The precursor is spatially and structurally activated with alkaline solution, then washed with deionized water until neutral and dried to obtain alkali-activated collagen fibers. Step 3: Transfer the alkali-activated collagen fibers to an aldehyde solution of a certain concentration, then add a certain amount of thiazole derivative to the mixed solution, heat and stir to carry out cross-linking and curing reaction, and after filtration, washing and drying of the reaction product, a collagen fiber-based material rich in nitrogen and sulfur heteroatoms is obtained. In step three, the thiazole derivatives include one or more of 2-aminothiazole, chlorothiazole, and bromothiazole. In step three, the mass percentage of collagen fibers in the mixture of thiazole derivatives and collagen fibers is 25% to 75%; the mass-volume ratio of collagen fibers to aldehyde solution is 1g:100 to 500ml. In step three, the heating temperature of the cross-linking curing reaction is set to 30~70℃, and the stirring time is 1~24 h; In step three, the drying temperature is 50~100℃ and the time is 12~24 h. In step three, the concentration of the aldehyde solution is 1wt% to 30wt%; the aldehyde solution is one or a mixture of formaldehyde and glutaraldehyde.

2. The method for preparing the nitrogen- and sulfur-rich collagen fiber-based material as described in claim 1, characterized in that, In step one, the pulverizing time is 0.5~10 min and the drying temperature is 70~80℃.

3. The method for preparing the nitrogen- and sulfur-rich collagen fiber-based material as described in claim 1, characterized in that, In step two, the alkaline solution is one or a mixture of two of NaOH and KOH solutions; the pH value of the solution for activating the precursor with alkaline solution is maintained at 9-14.

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