Long-acting high-activity antioxidant inhibitor and preparation method thereof

Abstract

The preparation method comprises the steps that an antioxidant is prepared, and the antioxidant is formed by modifying anthocyanidin through the auxiliary color effect and comprises amino acid modified anthocyanidin, organic acid modified anthocyanidin, succinic anhydride modified anthocyanidin or metal ion modified anthocyanidin; the prepared antioxidant is added into distilled water, stirring is conducted to enable the antioxidant to be completely dissolved, the long-acting high-activity antioxidant type inhibitor is obtained, and the concentration of the antioxidant ranges from 1 wt% to 7 wt%. The long-acting high-activity antioxidant inhibitor prepared through the preparation method has high antioxidant activity and good high-temperature stability, and spontaneous combustion of coal can be effectively inhibited.

Description

Technical Field

[0001] The invention belongs to the technical field of coal spontaneous combustion inhibitors, and relates to a long-acting, high-activity antioxidant inhibitor and a preparation method thereof. Background Art

[0002] Coal resources have long been the main energy source and important industrial raw material in my country. Coal spontaneous combustion is one of the main safety hazards in coal mining, which seriously threatens the safe production of coal mines and the life and health of underground workers. Effectively suppressing coal spontaneous combustion disasters is crucial to ensuring safe and efficient mining of coal mines and stable development of the industrial economy.

[0003] Coal spontaneous combustion inhibitors are a common measure to prevent coal spontaneous combustion disasters. Existing inhibitors can be divided into physical inhibitors and chemical inhibitors according to the mechanism of preventing coal spontaneous combustion. Physical inhibitors are generally used in large doses, and the inhibitory effect weakens or even fails as the water evaporates. Chemical inhibitors have problems such as environmental pollution and high costs in practical applications. Anthocyanins, as renewable green resources and natural products with antioxidant functions, are applied as antioxidants in the field of coal spontaneous combustion prevention and control technology. They can react with active functional groups in the coal structure to terminate the coal-oxygen chain reaction, thereby achieving the purpose of inhibiting coal spontaneous combustion in a green and environmentally friendly way. However, the coal spontaneous combustion inhibitor prepared using existing conventional anthocyanins has poor thermal stability and is easily affected by environmental factors such as temperature, which weakens the original antioxidant properties and has a poor inhibitory effect on coal spontaneous combustion, making it difficult to apply in actual production. Summary of the invention

[0004] One object of the present invention is to provide a long-lasting and highly active antioxidant inhibitor, which solves the problem that the existing antioxidant inhibitor has poor thermal stability, a short inhibition life for coal spontaneous combustion, and is difficult to apply in actual production.

[0005] Another object of the present invention is to provide a method for preparing a long-lasting and highly active antioxidant inhibitor. The first technical solution adopted by the present invention is a method for preparing a long-acting and highly active antioxidant inhibitor, comprising the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation effect, including anthocyanin modified with amino acids, anthocyanin modified with organic acids, anthocyanin modified with succinic anhydride, or anthocyanin modified with metal ions; Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 to 7 wt%.

[0006] The amino acid modified anthocyanidin comprises mixing anthocyanidin and L-proline in a round-bottom flask at a molar ratio of 1:750, adding deionized water to dissolve, adjusting the pH of the mixed solution to 2-3 with a hydrochloric acid solution, placing the round-bottom flask in a water bath for continuous stirring and heating reaction, cooling to room temperature after the reaction is completed, and finally drying to obtain an antioxidant.

[0007] Place the round-bottom flask in a water bath and continuously stir and heat to react at a temperature of 85 to 95°C for 6 to 8 hours.

[0008] Organic acid modified anthocyanins include dissolving malic acid, pyridine and anthocyanins in 50% ethanol solution, wherein the concentration of malic acid is 8.7-8.8 g / L, the concentration of anthocyanins is 2-3 g / L, the volume ratio of pyridine to ethanol solution is 1:3, stirring the reaction in a 50°C water bath environment for 5h-7h, then removing pyridine and ethanol under negative pressure using a rotary evaporator, and finally vacuum drying to obtain an antioxidant.

[0009] The method comprises the following steps: dissolving anthocyanin powder in a 30% methanol solution to form a mixed solution, wherein the anthocyanin concentration in the mixed solution is 16-17 g / L, adding a hydrochloric acid solution to adjust the pH value to 6-7, then adding succinic anhydride to the mixed solution, wherein the mass ratio of anthocyanin powder to succinic anhydride is 1:0.75, stirring the reaction in a 60°C water bath environment for 4-5 hours, cooling to room temperature, and finally filtering, and drying the filtered solid to obtain an antioxidant.

[0010] Metal ion modification of anthocyanins, including Mg 2+ or Ca 2+ Modified anthocyanins.

[0011] Use Mg 2+ Modified anthocyanin, comprising adding MgCl in a mass ratio of 1:3 2 and anthocyanin powder are dissolved in deionized water, stirred for reaction for 1 to 2 hours to obtain a chelating reaction product, and dried to remove water to obtain an antioxidant.

[0012] Use Ca 2+ Modified anthocyanins, comprising adding CaCl 2 and anthocyanin powder are dissolved in deionized water, stirred for reaction for 1 to 2 hours to obtain a chelating reaction product, and dried to remove water to obtain an antioxidant.

[0013] The second technical solution adopted by the present invention is that the long-acting and highly active antioxidant inhibitor prepared by the above preparation method is composed of an antioxidant and distilled water, the antioxidant concentration is 1-7wt%, and the antioxidant is formed by anthocyanin modified by auxiliary color effect.

[0014] The beneficial effect of the present invention is that anthocyanin is modified to prepare an antioxidant through the auxiliary color effect, the antioxidant activity of anthocyanin is significantly enhanced, and it is made into a long-acting and highly active antioxidant inhibitor, which can effectively inhibit coal spontaneous combustion and has good high-temperature stability. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 It is the oxygen consumption rate curve of the long-acting and highly active antioxidant inhibitor prepared in Comparative Example 1 and Examples 1-5 of the present invention; Figure 2 It is a comparison chart of the inhibition rates of the long-acting and highly active antioxidant inhibitors prepared in Comparative Example 1 and Examples 1-5 of the present invention. DETAILED DESCRIPTION

[0015] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0016] Example 1 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including amino acid modified anthocyanin, anthocyanin and L-proline are mixed in a round-bottom flask at a molar ratio of 1:750, deionized water is added to dissolve, and the pH of the mixed solution is adjusted to 2 with a hydrochloric acid solution, and then the round-bottom flask is placed in a water bath for continuous stirring and heating reaction, the heating temperature is 90°C, the reaction time is 6h, and after the reaction is completed, it is cooled to room temperature and finally dried to obtain the antioxidant.

[0017] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-lasting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 5wt%.

[0018] Example 2 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanins through a co-pigmentation effect, including organic acid-modified anthocyanins, dissolving malic acid, pyridine and anthocyanins in a 50% ethanol solution, the concentration of malic acid is 8.7 g / L, the concentration of anthocyanins is 2 g / L, the volume ratio of pyridine to ethanol solution is 1:3, stirring the reaction in a 50° C. water bath environment for 5 hours, then removing pyridine and ethanol under negative pressure conditions using a rotary evaporator, and finally vacuum drying to obtain the antioxidant.

[0019] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-lasting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 5wt%.

[0020] Example 3 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including anthocyanin modified with succinic anhydride, dissolving anthocyanin powder in a 30% methanol solution to form a mixed solution, the anthocyanin concentration in the mixed solution is 16 g / L, and then adding a hydrochloric acid solution to adjust the pH value to 6, and then adding succinic anhydride to the mixed solution, the mass ratio of anthocyanin powder to succinic anhydride is 1:0.75, stirring the reaction in a 60°C water bath environment for 4 hours, cooling to room temperature, and finally filtering, and drying the filtered solid to obtain an antioxidant.

[0021] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-lasting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 5wt%.

[0022] Example 4 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Mg 2+ Modified anthocyanins were prepared by mixing MgCl 2 The anthocyanin powder is dissolved in deionized water and stirred for reaction for 1 hour to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0023] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-lasting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 5wt%.

[0024] Example 5 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Ca 2+ Modified anthocyanins were prepared by mixing CaCl with a mass ratio of 1:3 2 The anthocyanin powder is dissolved in deionized water and stirred for 2 hours to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0025] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-lasting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 5wt%.

[0026] Example 6 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including amino acid modified anthocyanin, anthocyanin and L-proline are mixed in a round-bottom flask at a molar ratio of 1:750, deionized water is added to dissolve, and the pH of the mixed solution is adjusted to 3 with a hydrochloric acid solution, and then the round-bottom flask is placed in a water bath for continuous stirring and heating reaction, the heating temperature is 92°C, the reaction time is 7h, and the reaction is cooled to room temperature after the reaction is completed, and finally dried to obtain the antioxidant.

[0027] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 wt%.

[0028] Example 7 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanins through a co-pigmentation effect, including organic acid-modified anthocyanins, dissolving malic acid, pyridine and anthocyanins in a 50% ethanol solution, the concentration of malic acid is 8.8 g / L, the concentration of anthocyanins is 3 g / L, the volume ratio of pyridine to ethanol solution is 1:3, stirring the reaction in a 50° C. water bath environment for 6 hours, then using a rotary evaporator under negative pressure conditions to remove pyridine and ethanol, and finally vacuum drying to obtain the antioxidant.

[0029] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 wt%.

[0030] Example 8 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including anthocyanin modified with succinic anhydride, dissolving anthocyanin powder in a 30% methanol solution to form a mixed solution, the anthocyanin concentration in the mixed solution is 17 g / L, and then adding a hydrochloric acid solution to adjust the pH value to 7, and then adding succinic anhydride to the mixed solution, the mass ratio of anthocyanin powder to succinic anhydride is 1:0.75, stirring the reaction in a 60°C water bath environment for 5 hours, cooling to room temperature, and finally filtering, and drying the filtered solid to obtain an antioxidant.

[0031] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 wt%.

[0032] Example 9 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Mg 2+ Modified anthocyanins were prepared by mixing MgCl 2 The anthocyanin powder is dissolved in deionized water and stirred for 2 hours to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0033] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 wt%.

[0034] Example 10 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Ca 2+ Modified anthocyanins were prepared by mixing CaCl with a mass ratio of 1:3 2 The anthocyanin powder is dissolved in deionized water and stirred for reaction for 1 hour to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0035] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 wt%.

[0036] Embodiment 11 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including amino acid modified anthocyanin, anthocyanin and L-proline are mixed in a round-bottom flask at a molar ratio of 1:750, deionized water is added to dissolve, and the pH of the mixed solution is adjusted to 3 with a hydrochloric acid solution, and then the round-bottom flask is placed in a water bath for continuous stirring and heating reaction, the heating temperature is 85°C, the reaction time is 8h, the reaction is cooled to room temperature after the reaction is completed, and finally dried to obtain the antioxidant.

[0037] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 7 wt%.

[0038] Example 12 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanins through a co-pigmentation effect, including organic acid-modified anthocyanins, dissolving malic acid, pyridine and anthocyanins in a 50% ethanol solution, the concentration of malic acid is 8.8 g / L, the concentration of anthocyanins is 3 g / L, the volume ratio of pyridine to ethanol solution is 1:3, stirring the reaction in a 50° C. water bath environment for 7 hours, then using a rotary evaporator under negative pressure conditions to remove pyridine and ethanol, and finally vacuum drying to obtain the antioxidant.

[0039] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 7 wt%.

[0040] Example 13 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, the antioxidant is formed by modifying anthocyanin through a co-coloring effect, including anthocyanin modified with succinic anhydride, dissolving anthocyanin powder in a 30% methanol solution to form a mixed solution, the anthocyanin concentration in the mixed solution is 17 g / L, and then adding a hydrochloric acid solution to adjust the pH value to 7, and then adding succinic anhydride to the mixed solution, the mass ratio of anthocyanin powder to succinic anhydride is 1:0.75, stirring the reaction in a 60°C water bath environment for 5 hours, cooling to room temperature, and finally filtering, and drying the filtered solid to obtain an antioxidant.

[0041] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 7 wt%.

[0042] Embodiment 14 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Mg 2+ Modified anthocyanins were prepared by mixing MgCl 2 The anthocyanin powder is dissolved in deionized water and stirred for 2 hours to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0043] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 7 wt%.

[0044] Embodiment 15 A method for preparing a long-acting and highly active antioxidant inhibitor comprises the following steps: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation reaction, including using Ca 2+ Modified anthocyanins were prepared by mixing CaCl with a mass ratio of 1:3 2 The anthocyanin powder is dissolved in deionized water and stirred for reaction for 1 hour to obtain a chelating reaction product, which is then dried to remove water to obtain an antioxidant.

[0045] Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 7 wt%.

[0046] Comparative Example 1 A method for preparing anthocyanin inhibitor for inhibiting coal spontaneous combustion comprises adding anthocyanin into distilled water and stirring to completely dissolve the anthocyanin to obtain the inhibitor for inhibiting coal spontaneous combustion, wherein the concentration of the antioxidant is 5wt%.

[0047] The antioxidant activity of anthocyanidins and the antioxidants prepared in Examples 1-5 was tested. The free radical elimination performance of anthocyanidins and the antioxidants prepared in Examples 1-5 was compared and analyzed by DPPH spectrometry. The DPPH free radical was configured into a 200 μmol / L ethanol solution, and the anthocyanidins to be tested and the antioxidants prepared in Examples 1-5 were configured into solutions of different concentrations for testing. 2 mL of DPPH ethanol solution and 2 mL of the solution to be tested were added to test tubes, respectively, and the mixture was mixed evenly. The residual amount was tested after standing in a dark place for 30 min.

[0048] The calculation formula of the substance's ability to eliminate DPPH free radicals is as follows: (1) S A is the DPPH elimination rate, %; A i A is the absorbance of the sample at 517 nm. 0 is the absorbance of DPPH solution at 517 nm.

[0049] The calculated free radical scavenging rates of anthocyanidins and the antioxidants prepared in Examples 1-5 are shown in Table 1.

[0050] Table 1 Free radical scavenging rates of anthocyanins and antioxidants prepared in Examples 1-5

[0051] As can be seen from Table 1, anthocyanins and the antioxidants prepared in Examples 1-5 have the ability to eliminate DPPH free radicals, and the elimination rate is significantly enhanced with the increase in concentration. Compared with ordinary anthocyanins, the antioxidants prepared in Examples 1-5 have a stronger ability to eliminate DPPH free radicals, indicating that co-pigmented modified anthocyanins can enhance antioxidant activity, among which L-proline modified anthocyanins have the best antioxidant activity enhancement effect at all concentrations.

[0052] In order to test the effect of the antioxidant inhibitor of the present invention on inhibiting coal spontaneous combustion, non-sticky coal and long flame coal samples were collected from different coal seam mining areas in the Jurassic period in northern Shaanxi, sealed and packed in sealed plastic bags and brought back to the laboratory, the surface part was peeled off, and the samples with a particle size of 200 mesh were crushed and sieved. Then, the samples were placed in a vacuum drying oven and dried at room temperature for 24 hours to remove external moisture in the coal; a part of the coal was treated with the antioxidant inhibitor prepared in Comparative Example 1 and Examples 1 to 5 as the inhibited coal sample, and the other part was untreated as the raw coal sample.

[0053] According to the gas concentration and flow rate at the inlet and outlet of the coal sample reactor, the oxygen consumption rate of coal at different temperatures is calculated. The specific calculation formula is shown in formula (2): (2) In the formula is the oxygen consumption rate, in mol·g -1 ·min -1 ; V in is the reactor inlet flow rate, in mL·min -1 ; C in is the oxygen concentration at the reactor inlet; V out is the reactor outlet flow rate, in mL·min -1 ; C out is the oxygen concentration at the reactor outlet; m out is the mass of coal loaded into the reactor, in g.

[0054] By monitoring the inlet and outlet gas flow rates of the reactor, it was found that the inlet and outlet gas flow rates were similar, so the formula (2) was improved as shown in formula (3): (3) In the formula, is the gas flow rate at the reactor inlet and outlet, in mL·min-1; is the oxygen concentration difference between the reactor inlet and outlet, %.

[0055] The calculation results are as follows Figure 1 shown.

[0056] Oxygen is a key factor in coal oxidation. When the active functional groups in coal react with oxygen in the air, the consumption of oxygen and the release of gaseous products can reflect the degree of spontaneous combustion of coal. 2 The oxygen consumption rate can reflect the intensity of the coal oxidation and heating process. Figure 1 It can be seen that the inhibitors prepared in Comparative Example 1 and Examples 1-5 significantly reduced the oxygen consumption rate during coal spontaneous combustion and inhibited the coal oxidation process. Moreover, the antioxidant inhibitors prepared in Examples 1-5 had a better inhibitory effect on coal oxidation than the inhibitor in Comparative Example 1.

[0057] The inhibition rate is an intuitive indicator to measure the inhibitory effect of the inhibitor in inhibiting the spontaneous combustion of coal. According to industry standards, the inhibition rate of the inhibitor refers to the difference in the volume of CO gas produced by the original coal sample and the inhibited coal sample under specific laboratory conditions and the percentage of the volume of CO gas produced by the original coal sample. The inhibition rate reflects the changes in the index gas before and after the coal is inhibited. The higher the inhibition rate, the stronger the inhibitory effect of the inhibitor, and vice versa. The specific formula is as follows:

[0058] Where I is the resistance, V 阻 V is the volume of CO produced by the inhibited coal sample; 原 is the volume of CO produced by the raw coal sample.

[0059] The average inhibition rate of the antioxidant inhibitors prepared in Comparative Example 1 and Examples 1-5 during the oxidation process from 30°C to 300°C is calculated as follows: Figure 2 shown.

[0060] Depend on Figure 2 It can be seen that compared with anthocyanins, the antioxidant inhibitors prepared from anthocyanins modified by different auxiliary color action methods have significantly improved inhibition rates, indicating that the antioxidant inhibitors prepared by the method of the present invention can effectively inhibit the spontaneous combustion of coal and have good stability at high temperatures.

Claims

1. A method for preparing a long-lasting and highly active antioxidant inhibitor, characterized in that: The following steps are involved: Step 1, preparing an antioxidant, wherein the antioxidant is formed by modifying anthocyanin through a co-pigmentation effect, including anthocyanin modified with amino acids, anthocyanin modified with organic acids, anthocyanin modified with succinic anhydride, or anthocyanin modified with metal ions; Step 2, adding the antioxidant prepared in step 1 into distilled water, stirring to completely dissolve the antioxidant, thereby obtaining a long-acting and highly active antioxidant inhibitor, wherein the antioxidant concentration is 1 to 7 wt%.

2. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 1, characterized in that: The amino acid modified anthocyanidin comprises mixing anthocyanidin and L-proline in a round-bottom flask at a molar ratio of 1:750, adding deionized water to dissolve, adjusting the pH of the mixed solution to 2-3 with a hydrochloric acid solution, placing the round-bottom flask in a water bath for continuous stirring and heating reaction, cooling to room temperature after the reaction is completed, and finally drying to obtain an antioxidant.

3. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 2, characterized in that: The round-bottom flask is placed in a water bath for continuous stirring and heating reaction at a heating temperature of 85 to 95° C. for a reaction time of 6 to 8 hours.

4. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 1, characterized in that: The organic acid modified anthocyanin comprises dissolving malic acid, pyridine and anthocyanin in a 50% ethanol solution, wherein the concentration of malic acid is 8.7-8.8 g / L, the concentration of anthocyanin is 2-3 g / L, the volume ratio of pyridine to ethanol solution is 1:3, stirring the reaction in a 50° C. water bath environment for 5 h-7 h, then removing pyridine and ethanol under negative pressure using a rotary evaporator, and finally vacuum drying to obtain an antioxidant.

5. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 1, characterized in that: The succinic anhydride modified anthocyanin comprises dissolving anthocyanin powder in a 30% methanol solution to form a mixed solution, wherein the anthocyanin concentration in the mixed solution is 16-17 g / L, then adding a hydrochloric acid solution to adjust the pH value to 6-7, then adding succinic anhydride to the mixed solution, wherein the mass ratio of anthocyanin powder to succinic anhydride is 1:0.75, stirring the reaction in a 60° C. water bath environment for 4-5 hours, cooling to room temperature, and finally filtering, and drying the filtered solid to obtain an antioxidant.

6. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 1, characterized in that: The metal ion modified anthocyanin comprises Mg 2+ or Ca 2+ Modified anthocyanins.

7. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 6, characterized in that: With the Mg 2 + The modified anthocyanin comprises dissolving MgCl2 and anthocyanin powder in a mass ratio of 1:3 in deionized water, stirring and reacting for 1 to 2 hours to obtain a chelating reaction product, and drying and removing water to obtain an antioxidant.

8. The method for preparing the long-acting and highly active antioxidant inhibitor according to claim 6, characterized in that: With the Ca 2 + The modified anthocyanin comprises dissolving CaCl2 and anthocyanin powder in a mass ratio of 1:3 in deionized water, stirring and reacting for 1 to 2 hours to obtain a chelating reaction product, and drying and removing water to obtain an antioxidant.

9. The long-acting and highly active antioxidant inhibitor prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The invention is composed of antioxidant and distilled water, wherein the concentration of the antioxidant is 1-7 wt %, and the antioxidant is formed by modifying anthocyanin through auxiliary coloring effect.

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