A composite inhibitor for preventing and treating coal spontaneous combustion based on antioxidant regeneration and a preparation method thereof
By using a composite inhibitor of primary antioxidant and regenerator, the problems of high cost and short lifespan of chemical inhibitors are solved, achieving active regeneration of the inhibitor and long-term inhibition of coal spontaneous combustion.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LIAONING TECHNICAL UNIVERSITY
- Filing Date
- 2026-02-23
- Publication Date
- 2026-06-23
Smart Images
Figure CN122256002A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of coal spontaneous combustion inhibition technology, and specifically relates to a composite inhibitor for preventing coal spontaneous combustion based on the regeneration effect of antioxidants and its preparation method. Background Technology
[0002] Coal energy still occupies an important position in my country's energy sector. Spontaneous combustion of coal in mines is one of the major hazards in coal mining. It not only wastes a large amount of coal resources but also releases toxic gases or triggers gas explosions, causing serious casualties. Among various coal spontaneous combustion control technologies, fire inhibitors have advantages such as simple operation, wide application range, and high inhibition efficiency. Therefore, fire inhibitor technology has broad application prospects in the prevention and control of mine fires.
[0003] Physical inhibitors played a crucial role in the early development of fire prevention technology. However, in practical applications, multiple sprayings are often required to maintain their inhibitory effect, and they also exhibit strong corrosive effects on spraying equipment. Subsequently, researchers continuously developed chemical inhibitors as alternatives. Although chemical inhibitors offer significantly better inertization effects than other types of inhibitors, they are more expensive, and once consumed in the reaction, their active centers cannot be replenished, causing them to lose their inhibitory effect. Therefore, if a method can be developed to revitalize and regenerate the active centers of chemical inhibitors, the cost of using high-efficiency inhibitors can be reduced, and their inhibitory lifespan and cycle extended. Summary of the Invention
[0004] This invention addresses the challenges of current chemical inhibitors, such as their inability to achieve industrial application, high cost, and short lifespan. It proposes a composite inhibitor for preventing coal spontaneous combustion based on the regeneration effect of antioxidants, along with its preparation method. This method enables the chemical inhibitor to be activated and regenerated, thereby maximizing its long-term inhibitory effect on coal-oxygen complex reactions.
[0005] To achieve the above objectives, the technical solution involved in this invention is as follows:
[0006] A composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants, comprising a primary antioxidant and a regenerator. The primary antioxidant captures free radicals in coal oxygen, while the regenerator regenerates the oxidized primary antioxidant.
[0007] Optionally, the primary antioxidant is a natural polyphenolic antioxidant, selected from one or more of reduced glutathione, tocopherol, tea polyphenols, butylated hydroxytoluene, and tert-butylhydroquinone, wherein reduced glutathione, tocopherol, and tea polyphenols are water-soluble antioxidants, and butylated hydroxytoluene and tert-butylhydroquinone are fat-soluble antioxidants; the regenerator is selected from one or more of dihydrolipoic acid, ascorbic acid, and glutathione reductase.
[0008] Optionally, the molar ratio of the main antioxidant to the regenerator is 1:0.5 to 1:2, preferably 1:1.
[0009] This invention also provides a method for preparing the aforementioned composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants, comprising the following steps:
[0010] Step 1: Add the main antioxidant to the solvent, stir and dissolve it completely to prepare a main antioxidant solution;
[0011] Step 2: Add the regenerator to the main antioxidant solution, mix well, and then perform a water bath to obtain a regenerated composite inhibitor solution.
[0012] Optionally, in step 1, the solvent is deionized water or anhydrous ethanol, and the appropriate solvent is selected according to the solubility of the primary antioxidant. That is, for water-soluble primary antioxidants, deionized water is selected as the solvent; for fat-soluble primary antioxidants, anhydrous ethanol is selected as the solvent.
[0013] In step 1, the stirring time is 20-30 min, and the molar concentration of the main antioxidant in the solvent is 1-2 mol / L.
[0014] Optionally, in step 2, the stirring time is 20-30 minutes, the water bath temperature is 25-45°C, and the water bath time is 6-12 hours. The composite inhibitor solution should be stored in a sealed container below 20°C.
[0015] This invention also provides the application of the composite inhibitor in preventing spontaneous combustion of coal.
[0016] The regeneration process in this invention mainly consists of the following two steps:
[0017] The first step is the inhibition reaction of the primary antioxidant: the primary antioxidant captures oxygen free radicals and converts them into the oxidized form of the primary antioxidant. The oxygen free radicals can be hydroxyl, ether radicals, hydrocarbon radicals, etc. Taking the reduced glutathione (GSH) as the primary antioxidant as an example, the reaction formula is shown in formula (1). In the formula, GSSG is the oxidized glutathione.
[0018] 2GSH+2•OH→GSSG+2H2O (1)
[0019] The second step of the regeneration reaction: After adding the regenerator, the regenerator restores the deactivated oxidized primary antioxidant to a primary antioxidant with antioxidant capacity. Taking the primary antioxidant-regenerator as reduced glutathione (GSH) and dihydrolipoic acid (DHLA) as an example, the regenerator restores the oxidized form of glutathione to reduced glutathione and lipoic acid (LA) with antioxidant capacity, as shown in formula (2).
[0020] DHLA+GSSG→LA+2GSH (2)
[0021] Compared with existing inhibition technologies, the present invention has the following advantages:
[0022] Current research on chemical inhibitors still focuses on their high cost and relatively short inhibitory lifespan. This invention is the first to propose introducing "antioxidant regeneration" into the field of coal spontaneous combustion prevention. It overturns the traditional model where inhibitors become inactive as soon as they take effect, ensuring the long-term high efficiency of chemical inhibitors and thus extending their excellent inhibitory effect. Attached Figure Description
[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0024] Figure 1 The graph shows the change in free radical scavenging rate of the antioxidant solution in Test Example 1 and Example 1.
[0025] Figure 2 This is a graph showing the change in regeneration efficiency of the regenerator against the antioxidant solution in Example 1.
[0026] Figure 3 The graph shows the change in free radical scavenging rate of the antioxidant solution in Test Example 1 and Example 2.
[0027] Figure 4 This is a graph showing the change in regeneration efficiency of the regenerator against the antioxidant solution in Example 2.
[0028] Figure 5 The graph shows the change in free radical scavenging rate of the antioxidant solution in Test Example 1 and Example 3.
[0029] Figure 6 This is a graph showing the change in regeneration efficiency of the regenerator against the antioxidant solution in Example 3.
[0030] Figure 7 The graph shows the changes in CO concentration released from the inhibited coal samples before and after regeneration in Comparative Example 1 and Test Examples 2 and 3. Detailed Implementation
[0031] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.
[0032] A composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants, comprising a primary antioxidant and a regenerator. The primary antioxidant is selected from one or more of reduced glutathione, tocopherol, tea polyphenols, butylated hydroxytoluene, and tert-butylhydroquinone; the regenerator is selected from one or more of dihydrolipoic acid, ascorbic acid, and glutathione reductase.
[0033] The molar ratio of the main antioxidant to the regenerator is 1:0.5 to 1:2. This ratio can be adjusted according to the actual situation, with a molar ratio of 1:1 being the optimal for inhibition.
[0034] The present invention will be further described below with reference to the following specific embodiments.
[0035] Example 1
[0036] Three groups of 5 mL solutions of 1 mol / L reduced glutathione were placed in 10 mL centrifuge tubes as the primary antioxidants. 0.5 g, 1.0 g, and 2.0 g of dihydrolipoic acid were added as regenerants, respectively. The solutions were thoroughly mixed and reacted in a 25°C water bath for 6 h. After centrifugation at 1500 r / min for 10 min, the supernatant was collected, and its antioxidant capacity and regeneration effect were assessed. This was denoted as the regeneration group R. 1i .
[0037] Example 2
[0038] Three groups of 5 mL 1 mol / L reduced glutathione solutions were placed in 10 mL centrifuge tubes, and 1.0 g of the regenerant dihydrolipoic acid was added. After thorough mixing, the solutions were reacted in water baths at 25, 35, and 45 °C for 6 h, respectively. The supernatants were collected after centrifugation at 1500 r / min for 10 min, and their antioxidant capacity and regeneration effect were assessed. This was denoted as regeneration group R. 2i .
[0039] Example 3
[0040] Two groups of 5 mL 1 mol / L reduced glutathione solutions were placed in 10 mL centrifuge tubes, and 1.0 g of the regenerant dihydrolipoic acid was added. After thorough mixing, the solutions were reacted in a 25℃ water bath for 6 h and 12 h, respectively. The supernatant was collected after centrifugation at 1500 r / min for 10 min, and its antioxidant capacity and regeneration effect were assessed. This was denoted as the regeneration group R. 3i .
[0041] Test Example 1
[0042] Reduced glutathione was used as the primary antioxidant. It was added to deionized water and stirred to ensure complete dissolution, resulting in a 2 wt% aqueous solution. The free radical scavenging ability of the prepared single primary antioxidant aqueous solution and the composite inhibitor prepared in the examples was tested.
[0043] Test Example 2
[0044] Reduced glutathione (rGSH) was used as the primary antioxidant. It was added to deionized water and stirred to ensure complete dissolution, yielding a 2 wt% aqueous solution. 10 g of the RGSH solution was sprayed onto the surface of a 50 g coal sample and stirred thoroughly to prepare a GSH-inhibited coal sample. The GSH-inhibited coal sample was then vacuum-dried at 38 °C, followed by a programmed temperature rise experiment to compare the differences in CO concentration during the oxidation process of each inhibited coal sample.
[0045] Test Example 3
[0046] Take 10g of an aqueous solution of 2 wt% reduced glutathione and 10g of an aqueous solution of 2 wt% regenerator dihydrolipoic acid. Mix the two evenly and spray them onto the surface of 50g of coal sample. Stir well to prepare an inhibited coal sample. Place it in a fume hood for full inhibition for 24 h, dry it under vacuum at 38 ℃, and then conduct a programmed temperature rise experiment. Investigate whether the regenerator can restore the activity of reduced glutathione and thus continue to exert its inhibition effect.
[0047] Comparative Example 1
[0048] Dissolve 15 g of MgCl2 in 100 g of deionized water and mix thoroughly to prepare a 15% MgCl2 solution. Spray 10 g of the solution onto the surface of a 50 g coal sample and stir well to prepare a MgCl2-inhibited coal sample. Dry the MgCl2-inhibited coal sample under vacuum at 38 °C, and then conduct a programmed temperature rise experiment to compare the differences in CO concentration during the oxidation process of each inhibited coal sample.
[0049] In this invention, reduced glutathione and magnesium chloride were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with an AR purity and CAS number: 70-18-8; dihydrolipoic acid was purchased from Shanghai Yuanye Biotechnology Co., Ltd., with CAS number: 462-20-4.
[0050] Performance testing:
[0051] The free radical scavenging ability, regeneration ability, and coal spontaneous combustion inhibition effect of the inhibitors in the examples and test examples were tested. The specific steps are as follows:
[0052] Step 1: Antioxidant and regeneration capacity test
[0053] The salicylic acid method was used. 1.0 mL of a 1 mol / L antioxidant solution was taken, and 1.0 mL of 6 mmol / L ferrous sulfate heptahydrate and 1.0 mL of 6 mmol / L H₂O₂ were added sequentially. The mixture was allowed to stand at room temperature for 10 min, then 1.0 mL of 6 mmol / L salicylic acid aqueous solution was added. After thorough mixing, the mixture was heated in a 37 ℃ water bath for 30 min, and the absorbance (A) was measured at 510 nm. S Regenerant was added to the above solution, and the absorbance A was measured at the same wavelength after the reaction. Ri As the regeneration group, the absorbance A0 measured with H2O instead of the sample solution served as the blank group, and the absorbance A1 measured with H2O instead of H2O2 served as the control group. Five replicate experiments were performed. The OH removal rate (denoted as D, %) and regeneration capacity were calculated using the following formulas (denoted as RA, %):
[0054]
[0055]
[0056] Among them, D S The hydroxyl scavenging rate represents the GSH sample group; D R The hydroxyl group scavenging rate represents the regeneration group; D SA This represents the hydroxyl group clearance rate after GSH becomes ineffective.
[0057] The free radical scavenging rate and regeneration efficiency of the antioxidants in Test Example 1 and Examples 1-3 were calculated as follows: Figure 1-6 As shown.
[0058] Depend on Figures 1-6 It can be seen that, compared with single reduced glutathione, the antioxidant capacity is significantly improved after the addition of the regenerator, and the regeneration efficiency is inversely proportional to the free radical scavenging capacity. Specifically, the antioxidant exhibits the best free radical scavenging capacity and regeneration efficiency when the regenerator dosage is 1.0 g, the reaction temperature is 35℃, and the reaction time is 6 h. This indicates that the method proposed in this invention has a certain degree of rationality in solution free radical systems.
[0059] Step 2: Coal sample collection and flame retardant effect testing
[0060] Coal sample selection: Fresh coal samples were collected from Ciyaogou Coal Mine in accordance with the national standard GB / T482-2008 "Methods for collecting coal samples from coal seams". The samples were wrapped in plastic wrap and prepared in accordance with GB474-2008 "Methods for preparing coal samples". The oxide layer on the surface of the coal block was ground off, and the middle part was crushed and screened to prepare coal samples with a particle size of 35-60 mesh, which were then stored in a vacuum environment.
[0061] The inhibited coal samples from Test Examples 2 and 3 and Comparative Example 1 were placed in coal sample containers for programmed temperature increase experiments. The initial temperature was 30 °C, the heating rate was 1 °C / min, and the experiment ended at approximately 200 °C. The CO concentration was recorded every 10 °C using a gas chromatograph. The CO concentration curves released during the oxidation process of the inhibited coal samples from 30 °C to 300 °C are shown in [Figure number missing]. Figure 7 .
[0062] Depend on Figure 7 It can be seen that, compared with the coal samples inhibited by magnesium chloride and reduced glutathione, the CO concentration released by the coal samples after adding the regenerator was significantly reduced. This indicates that the method for regenerating antioxidant inhibitors proposed in this invention can not only be applied to solution systems, but also effectively inhibit coal spontaneous combustion, thereby improving the inhibitory effect of the antioxidant and indirectly extending its inhibition life.
[0063] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants, characterized in that, The composite inhibitor includes a primary antioxidant and a regenerator.
2. The composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to claim 1, characterized in that, The primary antioxidant is a natural polyphenolic antioxidant, selected from one or more of reduced glutathione, tocopherol, tea polyphenols, butylated hydroxytoluene, and tert-butylhydroquinone.
3. The composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to claim 1, characterized in that, The regenerant is selected from one or more of dihydrolipoic acid, ascorbic acid, and glutathione reductase.
4. The composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to any one of claims 1 to 3, characterized in that, The molar ratio of the main antioxidant to the regenerator is 1:0.5 to 1:2, preferably 1:
1.
5. The preparation method of the composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to any one of claims 1 to 4, characterized in that, Includes the following steps: Step 1: Add the main antioxidant to the solvent, stir and dissolve it completely to prepare an aqueous solution of the main antioxidant; Step 2: Add the regenerator to the aqueous solution of the main antioxidant, mix well, and then place in a water bath to obtain a regenerated composite inhibitor solution.
6. The preparation method of the composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to claim 5, characterized in that, In step 1, the solvent is deionized water or anhydrous ethanol.
7. The preparation method of the composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to claim 5, characterized in that, In step 1, the stirring time is 20-30 min, and the molar concentration of the main antioxidant in the solvent is 1-2 mol / L.
8. The preparation method of the composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to claim 5, characterized in that, In step 2, the stirring time is 20-30 minutes, the water bath temperature is 25-45℃, and the water bath time is 6-12 hours.
9. The preparation method of the composite inhibitor for preventing spontaneous combustion of coal based on the regeneration effect of antioxidants according to any one of claims 5 to 8, characterized in that, The composite inhibitor solution is stored in a sealed container at a temperature below 20°C.
10. The application of the composite inhibitor according to any one of claims 1 to 4 in preventing spontaneous combustion of coal.