Method for converting waste particles into efficient adsorbents based on amyloid-like protein-mediated surface engineering

Abstract

This invention discloses a method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering. The method uses a disulfide bond reducing agent to induce an amyloid transformation in the protein, forming an amyloid protein film that is then used to engineer the surface of the waste particles, thus transforming the waste particles into a highly efficient adsorbent – ​​effectively "turning waste into treasure." This invention offers advantages such as low cost, high versatility, high efficiency, simple operation, environmental friendliness, no secondary pollution, and good biocompatibility. The adsorbent prepared by this method can achieve highly efficient and selective adsorption of precious metal ions (gold, silver, platinum, palladium, ruthenium, rhodium, osmium, iridium), and can be reused multiple times, making it easy to promote industrial applications.

Description

Technical Field

[0001] This invention belongs to the field of waste utilization technology, specifically involving a low-cost, green, environmentally friendly, simple and efficient method that transforms waste particles (such as fly ash and slag) into high-value adsorbents through surface engineering, thus realizing the transformation of waste into treasure. Background Technology

[0002] Industrial solid waste causes enormous damage to the environment, and finding simple, green methods to achieve its high-value utilization remains a major challenge. Industrial production typically generates waste particulate matter, such as fly ash from thermal power plants. Large quantities of this waste not only pollute soil, water, and air but also endanger human health. Therefore, achieving the recycling and value-added utilization of waste particulate matter is of great significance for reducing environmental pollution and developing a circular economy.

[0003] Adsorption materials have been widely used in purification, separation, catalysis, and pollution control in many industrial sectors. In summary, on the one hand, a large amount of solid waste is not utilized, and on the other hand, the adsorbent market is enormous. Therefore, converting solid waste into high-performance adsorbents has broad market prospects. Summary of the Invention

[0004] The purpose of this invention is to transform waste particles into highly efficient adsorbents through surface engineering mediated by amyloid proteins, and to promote the application of these adsorbents.

[0005] To achieve the above objectives, the present invention provides a method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering: the waste particles are surface-modified using an amyloid protein film formed after a phase transition induced by a disulfide bond reducing agent, thereby obtaining a protein-modified particle adsorbent; wherein the waste particles are any one of fly ash, slag, waste plastic particles, waste rubber particles, and waste textile particles.

[0006] The specific method for converting waste particles into a highly efficient adsorbent based on amyloid protein-mediated surface engineering is as follows: waste particles are mixed evenly with a 1-50 mg / mL protein aqueous solution and a 10-100 mM tris(2-carboxyethyl)phosphine hydrochloride aqueous solution with pH 4-6, and reacted at room temperature for 1-24 h. After the reaction is completed, the particles are centrifuged, washed, and freeze-dried to obtain the protein-modified particulate adsorbent. The ratio of the amount of waste particles to the protein aqueous solution and the tris(2-carboxyethyl)phosphine hydrochloride aqueous solution is 0.1-10 g: 25 mL: 25 mL.

[0007] Furthermore, the preferred method for converting waste particles into a highly efficient adsorbent based on surface engineering mediated by amyloid protein is as follows: the waste particles are mixed evenly with a 5-15 mg / mL protein aqueous solution and a 40-60 mM tris(2-carboxyethyl)phosphine hydrochloride aqueous solution with pH 4-5, and reacted at room temperature for 1-24 h. After the reaction is completed, the particles are centrifuged, washed, and freeze-dried to obtain the protein-modified particulate adsorbent; wherein the ratio of the waste particles to the protein aqueous solution and the tris(2-carboxyethyl)phosphine hydrochloride aqueous solution is 1-2 g: 25 mL: 25 mL.

[0008] The aforementioned protein is any one of bovine serum albumin, lysozyme, insulin, α-lactalbumin, β-lactoglobulin, human serum albumin, fibrinogen, β-amyloid, Aβ peptide, prion, α-synuclein, cystatin C, huntingtin protein, and immunoglobulin light chain, with the preferred protein being any one of bovine serum albumin, lysozyme, β-lactoglobulin, and fibrinogen.

[0009] The disulfide bond reducing agent mentioned above is any one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, glutathione, dimercaptosuccinic acid, 2-mercaptoethanol, sodium sulfite, and dithiothreitol, preferably any one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, and glutathione.

[0010] This invention utilizes amyloid protein-mediated surface engineering to convert waste particles into highly efficient adsorbents, which can then be used to adsorb precious metal ions from water. The water can be any one of industrial wastewater, ore leaching solution, or electronic waste leaching solution, and the precious metal ions can be any one or more of gold, silver, platinum, palladium, ruthenium, rhodium, osmium, and iridium.

[0011] The beneficial effects of this invention are as follows:

[0012] This invention utilizes phase transition protein nanofilms to modify the surface of waste particles, successfully transforming waste particles, especially fly ash, into valuable high-performance adsorbents, thus realizing "turning waste into treasure." This method is simple to operate, low in cost, and economical. The resulting adsorbent exhibits excellent adsorption performance for precious metal ions and can rapidly and selectively extract precious metals from low-grade ore leachates or electronic waste leachates, demonstrating very promising prospects for widespread application. Attached Figure Description

[0013] Figure 1 This is a scanning electron microscope image of PTB@FA ​​after PTB surface engineering in Example 1.

[0014] Figure 2 This is a comparison chart of the adsorption capacity of gold ions by FA and PTB@FA.

[0015] Figure 3 This study investigates the effects of different temperatures and concentrations of gold ion solutions on the amount of gold ions adsorbed by PTB@FA.

[0016] Figure 4 This is a comparison chart of the adsorption capacity of noble metal ions by FA and PTB@FA.

[0017] Figure 5 It is the selective adsorption of gold ions in low-grade ore leachate by PTB@FA.

[0018] Figure 6 It is the selective adsorption of precious metal ions in PTB@FA ​​electronic waste. Detailed Implementation

[0019] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0020] Example 1

[0021] Weigh 1g of fly ash (FA) into a 50mL centrifuge tube, then add 25mL of 10mg / mL bovine serum albumin (BSA) aqueous solution and 25mL of 50mM tris(2-carboxyethyl)phosphonic acid hydrochloride (TCEP) aqueous solution at pH 4.5. Mix well using a mixer and react at room temperature for 2 hours. After the reaction is complete, centrifuge, wash, and freeze-dry to obtain the adsorbent PTB@FA ​​(e.g., Figure 1 ).

[0022] Example 2

[0023] In this embodiment, the fly ash in Example 1 was replaced with an equal mass of slag, and the other steps were the same as in Example 1, to obtain the adsorbent PTB@Slag.

[0024] Example 3

[0025] In this embodiment, the fly ash in Example 1 was replaced with waste plastic pellets (WPP) of equal mass, and the other steps were the same as in Example 1, to obtain the adsorbent PTB@WPP.

[0026] Example 4

[0027] In this embodiment, an equal volume of 10 mg / mL lysozyme (Ly) aqueous solution was used to replace the bovine serum albumin aqueous solution in Example 1, and the other steps were the same as in Example 1, to obtain the adsorbent PTB@FA.

[0028] Example 5

[0029] In this embodiment, an equal volume of 10 mg / mL fibrinogen (Fib) aqueous solution was used to replace the bovine serum albumin aqueous solution in Example 1. The other steps were the same as in Example 1, and the adsorbent PTF@FA was obtained.

[0030] Example 6

[0031] In this embodiment, an equal volume of 10 mg / mL insulin (Ins) aqueous solution was used to replace the bovine serum albumin aqueous solution in Example 1, and the other steps were the same as in Example 1, to obtain the adsorbent PTB@FA.

[0032] To demonstrate the beneficial effects of the present invention, the adsorption performance of the adsorbent PTB@FA ​​prepared in Example 1 on adsorbing metal ions was tested. The specific experiments and results are as follows:

[0033] 1. Effect of adsorption time on the adsorption performance of adsorbent PTB@FA

[0034] At 298 K, the adsorption capacity was positively correlated with the initial gold ion concentration and adsorption time. With an initial gold ion concentration of 200–400 ppm, the adsorption equilibrium time was 5–8 days. Specifically, at 298 K, with an adsorption time of 7 days and an initial gold ion concentration of 400 ppm, PTB@FA ​​achieved an adsorption capacity of 58.7 mg / g for gold ions, while the control group FA only achieved 18.9 mg / g, a difference of 3.1 times (see [link to relevant documentation]). Figure 2 ).

[0035] 2. Effects of gold ion concentration and temperature on the adsorption performance of PTB@FA ​​adsorbent

[0036] The effect of adsorption temperature on adsorption behavior further reflects a positive correlation between the adsorption capacity of gold ions and temperature. As the temperature changes from 298 K to 333 K, the adsorption capacity of gold ions by PTB@FA ​​increases from 58 mg / g to 247 mg / g (see...). Figure 3 ).

[0037] 3. Adsorption of noble metal ions by adsorbent PTB@FA ​​at different temperatures

[0038] At different temperatures, PTB@FA ​​exhibits higher adsorption capacity for noble metals than FA. Specifically, at 298 K, the adsorption capacities of FA for Rh, Os, Ru, Ag, Pd, Pt, and Ir are 0.1 mg / g, 1.2 mg / g, 0.22 mg / g, 1.1 mg / g, 1.8 mg / g, 2.1 mg / g, and 0.3 mg / g, respectively, while the adsorption capacities of PTB@FA ​​for Rh, Os, Ru, Ag, Pd, Pt, and Ir are 2.5 mg / g, 3.8 mg / g, 2.0 mg / g, 7.8 mg / g, 5.7 mg / g, 8.9 mg / g, and 5.9 mg / g, respectively. Compared to FA, PTB@FA ​​showed a significant increase in the adsorption capacity for noble metals, with increases of 25 times, 3.2 times, 9.1 times, 7.1 times, 3.2 times, 4.2 times, and 19.7 times for Rh, Os, Ru, Ag, Pd, Pt, and Ir, respectively (see [reference needed]). Figure 4 ).

[0039] 4. Selective adsorption of gold ions in low-grade ore leachate by adsorbent PTB@FA

[0040] Low-grade gold ore was soaked in aqua regia for 24 hours to obtain a leachate containing various metal ions. After filtration through a 0.22 μm filter membrane, the leachate was diluted with water. PTB@FA ​​was then immersed in the diluted leachate for adsorption. The adsorption of gold ions in the low-grade ore was not significantly interfered with by other common competing metal cations. Compared with gold ions, other common metal ions (such as Mg, Zn, Mn, As, Co, Bi, Cr, and Cd) showed no significant adsorption. The adsorption rate of gold ions by PTB@FA ​​reached 80.14% (the gold ion concentration in the ore before adsorption was 1.41 ppm, and after adsorption it was 0.28 ppm) (see...). Figure 5 ).

[0041] 5. Selective adsorption of precious metal ions in electronic waste by adsorbent PTB@FA

[0042] Electronic waste was soaked in aqua regia for 24 hours to obtain a leachate containing various metal ions. After filtration through a 0.22 μm filter membrane, the leachate was diluted with water. PTB@FA ​​was then immersed in the diluted leachate for adsorption. The concentrations of other competing metal ions (such as Ni, Mn, Cu, As, Zn, Co, and Bi) did not change significantly before and after PTB@FA ​​adsorption. PTB@FA ​​exhibited good selectivity for noble metal ions (such as Au 81.7%, Pd 88.7%, Ir 69.1%, Pt 80.7%, and Ru 65.4%) in the leachate (see [link to article]). Figure 6 ).

Claims

1. A method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering, characterized in that: This method uses a disulfide bond reducing agent to induce a phase transition in proteins, forming an amyloid protein film that modifies the surface of waste particles to obtain a protein-modified particulate adsorbent; wherein the waste particles are any one of fly ash, slag, waste plastic particles, waste rubber particles, and waste textile particles. The specific method is as follows: waste particles are mixed evenly with 1-50 mg / mL protein aqueous solution and 10-100 mM reducing agent aqueous solution with pH=4-6, and reacted at room temperature for 1-24 h. After the reaction is completed, the particles are centrifuged, washed, and freeze-dried to obtain protein-modified particulate adsorbent; wherein, the ratio of the amount of waste particles to protein aqueous solution and tris(2-carboxyethyl)phosphine hydrochloride aqueous solution is 0.1-10 g: 25 mL: 25 mL. The protein-modified particulate adsorbent is used to adsorb precious metals, wherein the precious metals are any one or more of gold, silver, platinum, palladium, ruthenium, rhodium, osmium, and iridium.

2. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to claim 1, characterized in that: Waste particles were mixed evenly with a protein aqueous solution of 1–50 mg / mL and a tris(2-carboxyethyl)phosphine hydrochloride aqueous solution of 10–100 mM pH=4–6, and reacted at room temperature for 1–24 h. After the reaction was completed, the mixture was centrifuged, washed, and freeze-dried to obtain the protein-modified particulate adsorbent. The ratio of the waste particles to the protein aqueous solution and the tris(2-carboxyethyl)phosphine hydrochloride aqueous solution was 0.1–10 g: 25 mL: 25 mL.

3. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to claim 1, characterized in that: Waste particles were mixed evenly with a 5–15 mg / mL protein aqueous solution and a 40–60 mM tris(2-carboxyethyl)phosphine hydrochloride aqueous solution at pH 4–5, and reacted at room temperature for 1–24 h. After the reaction was completed, the mixture was centrifuged, washed, and freeze-dried to obtain the protein-modified particulate adsorbent. The ratio of the waste particles to the protein aqueous solution and the tris(2-carboxyethyl)phosphine hydrochloride aqueous solution was 1–2 g: 25 mL: 25 mL.

4. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to any one of claims 1 to 3, characterized in that: The protein is any one of bovine serum albumin, lysozyme, insulin, α-lactalbumin, β-lactoglobulin, human serum albumin, fibrinogen, β-amyloid, Aβ peptide, prion, α-synuclein, cystatin C, huntingtin, and immunoglobulin light chain.

5. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to any one of claims 1 to 3, characterized in that: The protein is any one of bovine serum albumin, lysozyme, β-lactoglobulin, and fibrinogen.

6. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to any one of claims 1 to 3, characterized in that: The disulfide bond reducing agent is any one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, glutathione, dimercaptosuccinic acid, 2-mercaptoethanol, sodium sulfite, and dithiothreitol.

7. The method for converting waste particles into highly efficient adsorbents based on amyloid protein-mediated surface engineering according to any one of claims 1 to 3, characterized in that: The disulfide bond reducing agent is any one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, and glutathione.

8. The application of the protein-modified particulate adsorbent according to claim 1 in the adsorption of precious metal ions in water, wherein the water is any one of industrial wastewater, ore leaching solution, and electronic waste leaching solution.

9. The application of the protein-modified particulate adsorbent according to claim 8 in the adsorption of noble metal ions in water, characterized in that: The precious metal is any one or more of gold, silver, platinum, palladium, ruthenium, rhodium, osmium, and iridium.

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