A carbon-fluorine / hydrocarbon quaternary hybrid high-activity wetting-enhancing mine spray dust suppressant, its preparation method and application

Abstract

The present invention discloses a carbon-fluorine-carbon-hydrogen quaternary hybrid highly active wetting-enhancing type mine spray dust suppressant and its preparation method and application. (1) Preparation of reaction intermediate: Add propanediamine to a reaction vessel, stir, and dropwise add triethylamine. After the addition is complete, dropwise add a perfluorobutanesulfonyl fluoride solution. After the addition is complete, react for 1.5 - 3 h, then raise the temperature to room temperature and react for 3 - 5 h. After the reaction is complete, add acetone for recrystallization and filter to obtain the intermediate. (2) Preparation of the final product: Add an alcohol solution of 1,3-propane sultone to a reaction vessel, and then dropwise add an alcohol solution of the intermediate at room temperature. After the addition is complete, raise the temperature to 55 - 65 °C and continue to react for 24 - 48 h. After the reaction is complete, add an excessive amount of sodium carbonate solution and stir, filter, distill off methanol from the filtrate, and then perform recrystallization with a mixed solvent of methanol and ether. Reduce the number of fluorine-containing carbon atoms, improve the degradability of the fluorosurfactant, and add oxygen-containing functional groups as much as possible in a smaller molecular structure, so as to efficiently settle coal dust and reduce coal dust pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of dust suppressants, and specifically to a carbon-fluorine-carbon-hydrogen quaternary hybrid high-activity moisturizing type spray dust suppressant for mining, and a preparation method and application thereof. Background Art

[0002] In 2021, global coal production reached 8.173 billion tons, a year-on-year increase of 6.0%. With this came more serious dust pollution, and the resulting occupational health, environmental pollution, and loss of life and property have attracted much attention. Coal mine dust has become the number one culprit endangering the occupational health of miners, seriously affecting coal mine production safety. Surfactant-enhanced spray technology is one of the most economical and efficient dust reduction technologies and is widely used in underground dust control. The use of spray dust suppressants, especially different types of surfactants, has a direct impact on the spray dust reduction effect.

[0003] At present, the research reports on spray dust suppressants in the prior art mainly include: CN 111484830 A discloses a high-penetration coal dust suppressant, which uses a traditional anionic surfactant as a surfactant and a penetrant; CN101717617A discloses a dust suppressant, which is a mixture of 0.04-0.06% sodium diisooctyl sulfosuccinate, 0.04-0.06% dodecyl betaine, 99.547-9991% water and 0.111-0.333% calcium chloride according to weight percentage. The above inventions all have common problems such as large surface tension of conventional hydrocarbon chain surfactants.

[0004] Therefore, it is of great significance to develop a high-activity and low-surface tension mining spray dust suppressant. Summary of the invention

[0005] In order to solve the above technical problems, the purpose of the present invention is to provide a carbon-fluorine-carbon-hydrogen quaternary hybrid high-activity moisturizing type mining spray dust suppressant and its preparation method and application, reduce the number of fluorine-containing carbon atoms, improve the degradability of fluorine-containing surfactants, add oxygen-containing functional groups as much as possible in smaller molecular structures, thereby efficiently precipitating coal dust and reducing coal dust pollution.

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing a carbon-fluorine-carbon-hydrogen quaternary hybrid high-activity moisturizing type mining spray dust suppressant: characterized in that it is prepared according to the following method:

[0007] (1) Preparation of reaction intermediate: Add propylene diamine to a reaction vessel, stir, control the temperature at about 10°C, add triethylamine dropwise, and after the addition is complete, add perfluorobutylsulfonyl fluoride solution dropwise. After the addition is complete, control the temperature at 0-10°C, react for 1.5-3h, then heat to room temperature and react for 3-5h. After the reaction is complete, add acetone for recrystallization, and filter to obtain the intermediate;

[0008] (2) Preparation of the final product: Add an alcohol solution of 1,3 - propane sultone into a reaction vessel, then dropwise add an alcohol solution of the intermediate at room temperature. After the addition, raise the temperature to 55 - 65 °C and continue the reaction for 24 - 48 h. After the reaction is completed, add an excessive amount of sodium carbonate solution and stir, then filter. The filtrate is distilled to remove methanol, and then recrystallized with a mixed solvent of methanol and ether, and filtered and dried to obtain a powdery solid, namely the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing type mine spray dust suppressant.

[0009] In the above - mentioned scheme: The molar ratio of perfluorobutanesulfonyl fluoride to propylenediamine is 2:1 - 1.2, and the addition amount of triethylamine is 0.1 - 5% of the mass of perfluorobutanesulfonyl fluoride.

[0010] In the above - mentioned scheme: The solvent used in the perfluorobutanesulfonyl fluoride solution is one of dichloromethane and chloroform.

[0011] In the above - mentioned scheme: The molar ratio of 1,3 - propane sultone to the intermediate is 2 - 2.5:1.

[0012] In the above - mentioned scheme: In step (2), the alcohol is one of methanol, ethanol, propanol, and isopropanol. Of course, it can also be other small - molecule alcohols.

[0013] In the above - mentioned scheme: The volume ratio of methanol to ether in the mixed solvent of methanol and ether is 1:1.

[0014] A fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing type mine spray dust suppressant prepared by the preparation method of the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing type mine spray dust suppressant described above.

[0015] An application of the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing type mine spray dust suppressant described above as a spray dust suppressant in coal seam mines.

[0016] To solve the problems that the traditional dust suppressants have a large surface tension and an unsatisfactory wetting effect, considering that fluorocarbon surfactants have excellent surface activity, high surface energy, thermal stability, and chemical stability, the present invention selects a suitable intermediate group, thereby effectively combining the advantages of hydrocarbon - type surfactants and short - chain fluorocarbon surfactants to prepare a fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing type mine spray dust suppressant. On the one hand, it reduces the number of fluorine - containing carbon atoms to improve the degradability of fluorosurfactants, and on the other hand, it adds oxygen - containing functional groups as much as possible in a smaller molecular structure, so as to efficiently settle coal dust and reduce coal dust pollution.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] (1) The dust suppressant molecules prepared by the present invention contain 4 strongly wettable hydrophilic groups in a smaller structure, which can significantly improve the wettability of the solution.

[0019] (2) The prepared fluorocarbon-hydrocarbon four-chain hybrid spray dust suppressant organically combines the advantages of high surface activity of fluorocarbon materials and low cost of hydrocarbon materials, has a lower critical micelle concentration than single hydrocarbon and single fluorocarbon surfactants, has a simple preparation process, and has characteristics such as good stability, high surface activity, and strong wetting and penetration ability.

[0020] (3) Through calculation, the negative extreme value of the electrostatic potential of this molecule is close to -67 kcal / mol, much higher than that of other surfactants, can efficiently adsorb water molecules and can reduce the surface tension of the solution to below 20 mN / m at a lower concentration.

[0021] (4) The dust suppressant prepared by the present invention uses C4 perfluorobutanesulfonyl fluoride as a raw material, and synthesizes a hybrid dust suppressant through reactions such as quaternization, avoiding the generation of C8 chains, having no biological cumulative toxicity, and meeting environmental protection requirements. Detailed implementation mode

[0022] The present invention will be further described below in conjunction with examples.

[0023] Example 1

[0024] Preparation of fluorocarbon-hydrocarbon quaternary hybrid high-activity wetting-enhancing type mine spray dust suppressant:

[0025] (1) 5.04 g (0.0166 mol) of short-chain fluorocarbon material, 1.44 g (0.0118 mol) of 1,3-propane sultone, and 1.12 g of sodium carbonate.

[0026] (2) Preparation of reaction intermediate: Take a 250 ml three-necked flask, add 0.64 g of propylenediamine (0.0086 mol) into it, start magnetic stirring, with a rotation speed of 80 r / min, ice bath, control the temperature at 0-10 °C, and add triethylamine at 0.1% of the mass of the short-chain fluorocarbon material, then slowly add a saturated mixture of 5.04 g of perfluorobutanesulfonyl fluoride and dichloromethane dropwise under ice bath conditions. After the addition is completed, control the temperature at 0-10 °C under ice bath and react for 3 h, then raise the temperature to room temperature and react for 5 h. After the reaction is completed, recrystallize with acetone and filter to obtain the intermediate.

[0027] (3) Preparation of the final product: Slowly add dropwise a mixed solution containing the intermediate (3.01 g) and methanol (solution concentration not limited) to a mixed solution of 1,3 - propanesultone (1.44 g) and methanol. The addition is completed after 30 min. Then raise the temperature to 55 °C and continue the reaction for 48 h. After the reaction is completed, add a solution containing sodium carbonate (1.12 g, molecular weight 105.99, 0.01 mol) and stir for 1 h at a rotation speed of 100 r / min. Filter and remove excess methanol, etc. through a rotary evaporator. Finally, recrystallize 2 - 4 times with a mixed solvent of methanol / ether with a volume ratio of 1 / 1, filter, and dry to obtain a powdery solid, namely the carbon - fluorine - carbon - hydrogen quaternary hybrid highly active wetting - enhancing mine spray dust suppressant.

[0028] Example 2

[0029] Preparation of the carbon - fluorine - carbon - hydrogen quaternary hybrid highly active wetting - enhancing mine spray dust suppressant:

[0030] (1) 6.04 g (0.02 mol) of short - chain carbon - fluorine material, 2.44 g of 1,3 - propanesultone, 2.12 g of sodium carbonate.

[0031] (2) Preparation of the reaction intermediate: Take a 250 - ml three - necked flask, add 0.74 g of propanediamine (0.01 mol) into it, start magnetic stirring at a rotation speed of 90 r / min, control the temperature at 0 - 10 °C in an ice bath, and add dropwise triethylamine with a mass of 5% of perfluorobutanesulfonyl fluoride. Then slowly add dropwise a mixed solution of 6.04 g of perfluorobutanesulfonyl fluoride and chloroform (saturated solution) under ice - bath conditions. After the addition is completed, react for 1.5 h in the ice bath and then raise the temperature to room temperature and react for 3 h. After the reaction is completed, recrystallize with acetone and filter to obtain the intermediate.

[0032] (3) Preparation of the final product: Slowly add dropwise a mixed solution containing the intermediate (6.38 g, 0.01 mol) and ethanol to a mixed solution of 1,3 - propanesultone (2.44 g, 0.02 mol) and ethanol. After 30 min, raise the temperature to 60 °C and continue the reaction for 36 h. After the reaction is completed, add a solution containing sodium carbonate (2.12 g) and stir for 2 h at a rotation speed of 130 r / min. Filter and remove excess ethanol, etc. through a rotary evaporator. Finally, recrystallize 2 - 4 times with a mixed solvent of methanol / ether with a volume ratio of 1:1, filter, and dry to obtain a powdery solid, namely the carbon - fluorine - carbon - hydrogen quaternary hybrid highly active wetting - enhancing mine spray dust suppressant.

[0033] Example 3

[0034] Preparation of the carbon - fluorine - carbon - hydrogen quaternary hybrid highly active wetting - enhancing mine spray dust suppressant:

[0035] (1) Preparation of reaction intermediate: Take a 250 ml three-necked flask, add 0.8 g of propanediamine (0.0108 mol) into it, start magnetic stirring at a speed of 100 r / min, control the temperature at 0 - 10 °C in an ice bath, dropwise add triethylamine with 2% perfluorobutanesulfonyl fluoride, and then slowly dropwise add a mixed solution of 6.10 g of perfluorobutanesulfonyl fluoride and dichloromethane under ice bath conditions. After the addition is complete, react for 3 h in an ice bath, and then raise the temperature to room temperature and react for 5 h. After the reaction is complete, perform recrystallization with acetone and filter to obtain the intermediate.

[0036] (2) Preparation of the final product: Slowly dropwise add a mixed solution containing the intermediate (5.23 g, 0.0082 mol) and propanol to a mixed solution containing 1,3 - propanesultone (2.5 g, 0.02049 mol) and propanol. After 30 min, raise the temperature to 65 °C and continue the reaction for 48 h. After the reaction is complete, add a solution containing sodium carbonate (2.2 g) and stir for 3 h at a speed of 150 r / min. Filter and remove the excess propanol and others through a rotary evaporator. Finally, perform recrystallization 2 - 4 times with a mixed solvent of methanol / ether 1:1, filter, and dry to obtain a powdery solid, namely the fluorocarbon-hydrocarbon quaternary hybrid highly active wetting-enhancing mine spray dust suppressant.

[0037] Determine the dust suppression ability of the dust suppressants prepared in Examples 1 - 3

[0038] During use, dilute it 5000 times with water, that is, add 2.5 kg of water to 1 g of the dust suppressant.

[0039] 1. Determination of surface tension

[0040] Use a ZTZL2000 surface tensiometer to measure the surface tension of the solutions in Examples 1 - 3;

[0041] Table 1 Experimental results of surface tension

[0042]

[0043] Apply the dust suppressants prepared in Examples 1 - 3 on-site, and measure the dust concentrations under the conditions of no dust prevention measures taken at the working face, only using water spray, and spraying after adding the dust suppressants in Examples 1 - 3 of the present invention to the clear water, as shown in Table 2.

[0044] Table 2 Dust concentrations at different working locations

[0045]

[0046] As can be seen from Table 2, after applying the dust suppressants prepared in Examples 1-3, the dust reduction rates of total dust and respirable dust at the working face driver's position increased by 30.49% and 12.63%, 38.46% and 22.11%, 32.51% and 18% respectively compared with that of clear water. The dust reduction efficiency was effectively improved, showing great progress.

Claims

1. Preparation method of a carbon-fluorine / carbon-hydrogen four-component hybrid highly active wetting-enhancing mine spray dust suppressant: It is characterized in that, It is prepared according to the following method: (1) Preparation of reaction intermediate: Add propanediamine into a reaction vessel, stir, control the temperature at 0 - 10 °C, dropwise add triethylamine. After the addition is complete, dropwise add a perfluorobutanesulfonyl fluoride solution. After the addition is complete, control the temperature at 0 - 10 °C and react for 1.5 - 3 h, then raise the temperature to room temperature and react for 3 - 5 h. After the reaction is complete, add acetone for recrystallization and filter to obtain the intermediate; (2) Preparation of the final product: Add an alcohol solution of 1,3 - propane sultone into a reaction vessel, and then at room temperature, dropwise add an alcohol solution of the intermediate. After the addition is complete, raise the temperature to 55 - 65 °C and continue to react for 24 - 48 h. After the reaction is complete, add an excessive amount of sodium carbonate solution and stir, filter, distill off methanol from the filtrate, and then perform recrystallization with a mixed solvent of methanol and ether, filter and dry to obtain a powdery solid, namely the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing mine spray dust suppressant; the molar ratio of perfluorobutanesulfonyl fluoride to propanediamine is 2:1 - 1.2, and the addition amount of triethylamine is 0.1 - 5% of the mass of perfluorobutanesulfonyl fluoride.

2. The preparation method of the fluorocarbon-hydrocarbon quaternary hybrid highly active wetting-enhancing mine spray dust suppressant according to claim 1, characterized in that: The solvent used in the perfluorobutanesulfonyl fluoride solution is one of dichloromethane and chloroform.

3. The preparation method of the fluorocarbon-hydrocarbon quaternary hybrid highly active wetting-enhancing mine spray dust suppressant according to any one of claims 1-2: It is characterized in that: The molar ratio of 1,3 - propane sultone to the intermediate is 2 - 2.5:

1.

4. The preparation method of the fluorocarbon-hydrocarbon quaternary hybrid high-activity wetting-enhancing mine spray dust suppressant according to claim 3, characterized in that: In step (2), the alcohol is one of methanol, ethanol, propanol, and isopropanol.

5. The preparation method of the fluorocarbon-hydrocarbon quaternary hybrid high-activity wetting-enhancing mine spray dust suppressant according to claim 4, characterized in that: The volume ratio of methanol to ether in the mixed solvent of methanol and ether is 1:

1.

6. A fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing mine spray dust suppressant prepared by the preparation method of the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing mine spray dust suppressant according to any one of claims 1 - 5.

7. Use of the fluorocarbon - hydrocarbon quaternary hybrid highly active wetting - enhancing mine spray dust suppressant according to claim 6 as a spray dust suppressant in coal seam mines.

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