CN111849270A - Nitrogen, phosphorus and silicon synergistic coal flame-retardant dust suppressant and preparation method thereof - Google Patents

Nitrogen, phosphorus and silicon synergistic coal flame-retardant dust suppressant and preparation method thereof Download PDF

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CN111849270A
CN111849270A CN202010745746.0A CN202010745746A CN111849270A CN 111849270 A CN111849270 A CN 111849270A CN 202010745746 A CN202010745746 A CN 202010745746A CN 111849270 A CN111849270 A CN 111849270A
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retardant
flame
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nitrogen
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CN111849270B (en
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来水利
陈功
杨欣
李晨辉
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Shaanxi University of Science and Technology
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Abstract

The invention belongs to the field of coal flame-retardant dust suppressant, and particularly discloses a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant and a preparation method thereof, wherein the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following raw materials in parts by mass: 0.08 to 0.12 part of phosphorus flame retardant, 0.10 to 0.14 part of nitrogen-containing silane coupling agent, 0.01 to 0.05 part of aldehyde compound, 100.0 to 200.0 parts of solvent, 0.18 to 0.36 part of silicon flame retardant, 0.1 to 0.4 part of pH regulator, 83.0 to 125.0 parts of deionized water, 57.0 to 95.0 parts of alcohol, 1.0 to 2.0 parts of natural polymer, 10.0 to 20.0 parts of monomer, 4.0 to 8.0 parts of pH buffer, 0.1 to 0.4 part of initiator, 0.02 to 0.08 part of cross-linking agent, 0.2 to 0.4 part of surfactant and 0.2 to 1.0 part of plasticizer. The nitrogen-containing silane coupling agent is grafted on phosphorus flame retardant molecules by using an aldehyde compound, then the nitrogen-containing silane coupling agent is hydrolyzed and undergoes an inter-hydroxyl dehydration reaction with surface hydroxyl groups on a silicon flame retardant to obtain a nitrogen-phosphorus-silicon synergistic flame retardant, and finally the nitrogen-phosphorus-silicon synergistic flame retardant is organically combined with natural polymers, monomers, glycerol, surfactants and other dust suppression components in the same system through a polymer free radical polymerization reaction, so that the nitrogen-phosphorus-silicon synergistic flame retardant has two performances of flame retardance and dust suppression.

Description

Nitrogen, phosphorus and silicon synergistic coal flame-retardant dust suppressant and preparation method thereof
Technical Field
The invention belongs to the technical field of coal flame-retardant dust suppressant, and particularly relates to a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant and a preparation method thereof.
Background
China is a large coal resource consumption country, a large amount of dust is generated in the processes of mining, transporting, storing and burning coal, not only can the coal resource be seriously wasted, but also the surrounding environment can be greatly polluted, the excessive coal dust can cause dust explosion, and the life safety of people is threatened. Meanwhile, the spontaneous combustion of coal also threatens the life of operators and the safety of mining equipment in the mining and storage of coal, and causes a great deal of economic loss and resource waste.
At present, most of China uses a dust suppressant and a flame retardant in a compounding way, and most of the flame retardants rely on imports and are high in cost. At present, hard shell type dust suppressant in the market is more in application and poor in pressure resistance, a cured layer of a product sprayed with the dust suppressant is brittle and is easy to crack after being vibrated and wind power in transportation, so that the dust suppressant effect is lost, and the cost is high.
Disclosure of Invention
The invention aims to provide a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant and a preparation method thereof, and the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant is low in cost, flexible in film forming and strong in dust suppression performance and has two performances of flame retardance and dust suppression.
The invention is realized by the following technical scheme:
the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following raw materials in parts by mass:
0.08 to 0.12 part of phosphorus flame retardant, 0.10 to 0.14 part of nitrogen-containing silane coupling agent, 0.01 to 0.05 part of aldehyde compound, 100.0 to 200.0 parts of solvent, 0.18 to 0.36 part of silicon flame retardant, 0.1 to 0.4 part of pH regulator, 83.0 to 125.0 parts of deionized water, 57.0 to 95.0 parts of alcohol compound, 1.0 to 2.0 parts of natural polymer, 10.0 to 20.0 parts of monomer, 4.0 to 8.0 parts of pH buffer, 0.1 to 0.4 part of initiator, 0.02 to 0.08 part of cross-linking agent, 0.2 to 0.4 part of surfactant and 0.2 to 1.0 part of plasticizer.
Further, the phosphorus flame retardant is DOPO.
Further, the nitrogen-containing silane coupling agent is gamma-aminopropyltriethoxysilane.
Further, the aldehyde compound is at least one of terephthalaldehyde, benzaldehyde, formaldehyde, glutaraldehyde and p-hydroxybenzaldehyde.
Further, the silicon flame retardant is nano SiO2At least one of kaolin, diatomite, montmorillonite and attapulgite.
Further, the natural polymer is at least one of sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof, and chitosan.
Further, the pH regulator is at least one of acetic acid and hydrochloric acid;
the pH buffering agent is sodium hydroxide;
the solvent is at least one of absolute ethyl alcohol, benzene, toluene, trichloromethane, acetone, cyclohexane and tetrahydrofuran;
the alcohol compound is at least one of methanol and ethanol;
the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;
the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite;
the cross-linking agent is at least one of N, N' -methylene-bisacrylamide and dimethyldiallylammonium chloride;
the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;
the plasticizer is glycerol.
The invention also discloses a preparation method of the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant, which comprises the following steps:
(1) mixing 0.10-0.14 part of nitrogen-containing silane coupling agent, 0.01-0.05 part of aldehyde compound and 30.0-60.0 parts of solvent, and reacting at 60-120 ℃ for 4-8h to obtain solution A;
mixing 0.08-0.12 part of phosphorus flame retardant and 20.0-40.0 parts of solvent to obtain solution B;
dripping the solution B into the solution A, and reacting at 60-120 ℃ for 8-16h to obtain a crude product;
washing and filtering the crude product, and drying at 60-80 ℃ for 12-24h to obtain a flame-retardant intermediate;
(2) adding 57.0-95.0 parts of alcohol compound and 3.0-5.0 parts of deionized water into the flame-retardant intermediate, then adding a pH regulator to adjust the pH value to 3.0-4.0, and performing ultrasonic hydrolysis for 1-2 hours to obtain a solution C;
introducing inert gas into the solution C, adding 50.0-100.0 parts of solvent and 0.18-0.36 part of silicon flame retardant, reacting at 70-120 ℃ for 8-24h, washing to remove unreacted substances, performing suction filtration, and drying at 60-80 ℃ to obtain the flame retardant;
(3) mixing 1-2 parts of natural polymer, 0.2-0.8 part of flame retardant and 40-80 parts of deionized water to obtain a solution D;
mixing 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 20.0-40.0 parts of deionized water and 0.02-0.08 part of cross-linking agent to obtain solution E;
mixing 0.1-0.4 part of initiator and 10.0-20.0 parts of deionized water to obtain a solution F;
introducing inert gas into the solution D, adding the solution E and the solution F into the solution D, and preserving the heat for 4-6h at the temperature of 50-60 ℃ to obtain a solution G;
(4) and then adding 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant.
Further, in the step (1), preparing a solution A under the protection of inert gas;
in the step (3), the preparation of the solution E is carried out under the ice-water bath condition.
Further, in the step (2), the mass ratio of the alcohol compound to the deionized water is 19: 1.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant, which comprises a phosphorus flame retardant, a nitrogen-containing silane coupling agent, an aldehyde compound, a solvent, a silicon flame retardant, a pH regulator, deionized water, an alcohol compound, a natural polymer, a monomer, a pH buffering agent, an initiator, a cross-linking agent, a surfactant and a plasticizer. The nitrogen-containing silane coupling agent is grafted on phosphorus flame retardant molecules by using an aldehyde compound, then the nitrogen-containing silane coupling agent is hydrolyzed and undergoes an inter-hydroxyl dehydration reaction with surface hydroxyl groups on a silicon flame retardant to obtain a nitrogen-phosphorus-silicon synergistic flame retardant, and finally the nitrogen-phosphorus-silicon synergistic flame retardant is organically combined with natural polymers, monomers, plasticizers, surfactants and other dust suppression components in the same system through a polymer free radical polymerization reaction, so that the nitrogen-phosphorus-silicon synergistic flame retardant has two performances of flame retardance and dust suppression. The flame-retardant dust suppressant has the functions of wetting, bonding, condensing, retaining water and the like, can condense and bond coal dust particles quickly after being sprayed, enhances the capture capacity of water to the coal dust due to good wettability, and achieves the effect of quickly reducing dust. After spraying, a layer of soft and compact polymer film is formed on the surface of the pulverized coal, and the pulverized coal has excellent mechanical property, flexibility, anti-vibration property and anti-wind erosion property, and is not easy to break due to wind erosion and vibration. Not only can play the effect of preventing coal dust from floating, but also can effectively slow down the evaporation of water to achieve the purpose of locking water, thereby greatly prolonging the dust suppression period. The traditional phosphorus flame retardant has good char forming property and self-extinguishing property, but the compatibility with materials is poor due to large addition amount; the nitrogen flame retardant is commonly used in combination with the phosphorus flame retardant; most of silicon flame retardants are derived from minerals such as silicon dioxide, and the like, and have the characteristics of abundant resources, low cost, high flame retardant efficiency, environmental friendliness and the like, and the silicon flame retardants have good compatibility with materials and small influence on mechanical properties. The flame-retardant dust suppressant introduces nitrogen, phosphorus and silicon elements, is an efficient nitrogen-phosphorus-silicon synergistic flame-retardant system, can overcome the defects of low flame-retardant level, small limiting oxygen index, large addition amount and high cost of a single flame retardant, has excellent flame-retardant performance, and can achieve the effect of isolating oxygen by a high-molecular film formed after spraying, thereby preventing coal spontaneous combustion. The flame-retardant dust suppressant is made of an environment-friendly degradable material, and does not generate toxic and harmful gases when coal is combusted. The coal dust can be effectively slowed down and the coal can be prevented from spontaneous combustion in the processes of coal mining, storage, transportation and combustion, so that the air pollution and the waste of coal resources are reduced, and the method has great practical significance and application prospect.
Furthermore, the materials adopted by the natural polymer and the silicon flame retardant are from nature, have rich resources, low price, no pollution to the environment and good biocompatibility.
The invention also discloses a preparation method of the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant, which comprises the steps of grafting a nitrogen-containing silane coupling agent on phosphorus flame retardant molecules by using an aldehyde compound to obtain a flame-retardant intermediate, hydrolyzing the flame-retardant intermediate, and performing dehydration reaction between the hydrolyzed flame-retardant intermediate and surface hydroxyl groups on a silicon flame retardant to obtain the nitrogen-phosphorus-silicon synergistic flame retardant; finally, the flame retardant, natural polymers, monomers, glycerol, surfactant and other dust suppression components are organically combined in the same system through polymer free radical polymerization reaction, so that the flame retardant has two performances of flame retardance and dust suppression. The flame retardant is prepared by reacting several flame retardant components to obtain a flame retardant intermediate and finally preparing the flame retardant, and has better compatibility with materials.
Further, in the preparation of the solution A, the inert gas is introduced for the purpose of evacuating air to prevent-NH-present on the nitrogen-containing silane coupling agent2The C ═ N bond formed by the reaction with the aldehyde is oxidized by oxygen;
the monomer is easy to volatilize due to a large amount of heat generated during neutralization, so that the monomer can be prevented from volatilizing during neutralization in an ice-water bath.
Further, when the solution C is prepared, the mass ratio of the alcohol compound to the deionized water is 19:1, and the hydrolysis reaction is faster at the ratio, so that the hydrolysis is facilitated.
Drawings
FIG. 1 is a reaction scheme of the flame retardant dust suppressant of the present invention;
FIG. 2 is an infrared spectrum of KH550-DOPO as a flame retardant intermediate;
FIG. 3 is an XRD pattern of KH550-DOPO, a flame retardant intermediate;
FIG. 4 is an infrared spectrum of the flame retardant dust suppressant;
FIG. 5 is an XRD pattern of the flame retardant dust suppressant;
FIG. 6 shows the surface morphology of the pulverized coal after spraying water (a) and the flame retardant and dust suppressant (b), respectively;
FIG. 7 shows the results of the flame retardant performance test of the flame retardant dust suppressant.
Detailed Description
The invention discloses a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant, which comprises the following raw materials in parts by mass:
0.08-0.12 part of phosphorus flame retardant, 0.10-0.14 part of nitrogen-containing silane coupling agent, 0.01-0.05 part of aldehyde compound, 100.0-200.0 parts of solvent, 0.18-0.36 part of silicon flame retardant, 0.1-0.4 part of pH regulator, 83.0-125.0 parts of deionized water, 57.0-95.0 parts of alcohol compound, 1.0-2.0 parts of natural polymer, 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 0.1-0.4 part of initiator, 0.02-0.08 part of cross-linking agent, 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer.
Specifically, the phosphorus flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
Specifically, the nitrogen-containing silane coupling agent is gamma-aminopropyltriethoxysilane (KH 550).
Specifically, the aldehyde compound is at least one of terephthalaldehyde, benzaldehyde, formaldehyde, glutaraldehyde and p-hydroxybenzaldehyde.
Specifically, the solvent is at least one of absolute ethyl alcohol, benzene, toluene, chloroform, acetone, cyclohexane and tetrahydrofuran.
Specifically, the silicon-based flame retardant is nano SiO2At least one of kaolin, diatomite, montmorillonite and attapulgite.
Specifically, the pH regulator is at least one of acetic acid and hydrochloric acid.
Specifically, the alcohol compound is at least one of methanol and ethanol.
Specifically, the natural polymer is at least one of sodium alginate, starch and its derivatives, cellulose and its derivatives, and chitosan.
Specifically, the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid.
Specifically, the pH buffer is sodium hydroxide.
Specifically, the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite.
Specifically, the crosslinking agent is at least one of N, N' -methylene bisacrylamide and dimethyldiallylammonium chloride.
Specifically, the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
Specifically, glycerin is used as the plasticizer.
The invention also discloses a preparation method of the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant, which comprises the following steps:
(1) adding 0.10-0.14 part of nitrogen-containing silane coupling agent, 0.01-0.05 part of aldehyde and 30.0-60.0 parts of solvent into a three-neck flask filled with inert gas, and reacting for 4-8h in an oil bath at 60-120 ℃ to obtain a solution A; the inert gas is introduced into the three-neck flask to exhaust air, so as to prevent the C ═ N bond formed in the reaction from being oxidized by oxygen.
Then 0.08-0.12 part of phosphorus flame retardant is weighed and fully dissolved by 20.0-40.0 parts of solvent to obtain solution B;
slowly dripping the solution B into a three-neck flask by using a dropping funnel for 30-60min, and reacting at 60-120 ℃ for 8-16h to obtain a crude product;
and adding the crude product into a solvent, washing for three times, carrying out suction filtration, and drying at the temperature of 60-80 ℃ for 12-24h to obtain the flame-retardant intermediate.
-NH on nitrogen-containing silane coupling agent2Reacting with aldehyde to generate a C ═ N bond, which is convenient for introducing DOPO, and reacting with DOPO to obtain a flame-retardant intermediate; the slow addition is to prevent the reaction from being too fast and the exothermic heat of reaction from causing local excessive temperature to form by-products.
(2) Adding a flame-retardant intermediate into a beaker, adding 57.0-95.0 parts of alcohol compound and 3.0-5.0 parts of deionized water into the flame-retardant intermediate, then adding 0.1-0.4 part of pH regulator to adjust the pH value to 3.0-4.0, and performing ultrasonic hydrolysis for 1-2 hours to obtain a solution C; the pH is adjusted to 3.0-4.0 to accelerate hydrolysis, which is favored under acidic conditions.
And then transferring the mixture into a three-neck flask filled with inert gas, adding 50.0-100.0 parts of solvent and 0.18-0.36 part of silicon flame retardant into the solution C, carrying out reflux reaction at 70-120 ℃ for 8-24h, washing with ethanol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60-80 ℃ for 8-12h to obtain the flame retardant.
The method mainly comprises the steps that methoxy and ethoxy on the flame retardant intermediate are hydrolyzed into hydroxyl through ultrasonic treatment, and then the hydroxyl on the flame retardant intermediate is dehydrated and combined with the hydroxyl on the silicon flame retardant to obtain the nitrogen-phosphorus-silicon flame retardant.
(3) Adding 1-2 parts of natural polymer, 0.2-0.8 part of flame retardant and 40-80 parts of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 20.0-40.0 parts of deionized water and 0.02-0.08 part of cross-linking agent in an ice-water bath to obtain solution E; the addition of the pH buffer serves to neutralize the acrylic acid, favoring the polymerization reaction under neutral conditions.
Dissolving 0.1-0.4 part of initiator and 10.0-20.0 parts of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F into the three-neck flask for 40-60min under the water bath condition of 50-60 ℃, and preserving heat for 4-6h to obtain a solution G;
the flame retardant and dust suppressant is prepared by reacting and combining flame retardant, natural polymer, monomer and the like through a free radical polymerization method.
(4) And then adding 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following steps:
(1) adding 0.12g of KH550, 0.03g of terephthalaldehyde and 30.0g of absolute ethyl alcohol into a three-neck flask filled with inert gas, and reacting for 6 hours in an oil bath at 78 ℃ to obtain a solution A;
then weighing 0.10g of DOPO, and fully dissolving with 20.0g of absolute ethyl alcohol to obtain a solution B;
slowly dripping the solution B into the solution A for 40min by using a dropping funnel, continuously reacting for 12h at 78 ℃ to obtain a crude product, adding absolute ethyl alcohol into the crude product, washing for three times, performing suction filtration, and drying for 12h at 60 ℃ to obtain a flame-retardant intermediate;
(2) adding a flame-retardant intermediate into a beaker, adding 57.0g of ethanol and 3.0g of deionized water into the flame-retardant intermediate, then adding 0.12g of acetic acid to adjust the pH value to 4.0, and performing ultrasonic hydrolysis for 2 hours to obtain a solution C; then transferred into a three-neck flask filled with inert gas, 50.0g of absolute ethyl alcohol and 0.20g of nano SiO are added into the solution C2Carrying out reflux reaction at 78 ℃ for 8h, washing with ethanol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60 ℃ for 12h to obtain the flame retardant;
(3) adding 2g of sodium alginate, 0.2g of flame retardant and 60g of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 20.0g of acrylic acid, 6.66g of sodium hydroxide, 30.0g of deionized water and 0.04g N, N' -methylenebisacrylamide in an ice-water bath to obtain a solution E;
dissolving 0.2g of potassium persulfate, 0.074g of sodium bisulfite and 10.0g of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F into the solution D for 40min under the water bath condition of 60 ℃, and preserving the temperature for 5h to obtain a solution G;
(4) and then adding 0.2G of sodium dodecyl benzene sulfonate and 0.5G of glycerol into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant.
Example 2
A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following steps:
(1) adding 0.14g of KH550, 0.042g of terephthalaldehyde and 30.0g of absolute ethyl alcohol into a three-neck flask filled with inert gas, and reacting for 6 hours in an oil bath at 78 ℃ to obtain a solution A;
then weighing 0.12g of DOPO, and fully dissolving the DOPO with 20.0g of absolute ethyl alcohol to obtain a solution B;
slowly dripping the solution B into the solution A for 40min by using a dropping funnel, continuously reacting at constant temperature for 12h to obtain a crude product, adding absolute ethyl alcohol into the crude product, washing for three times, performing suction filtration, and drying at 60 ℃ for 12h to obtain a flame-retardant intermediate;
(2) adding a flame-retardant intermediate into a beaker, adding 57.0g of ethanol and 3.0g of deionized water into the flame-retardant intermediate, then adding 0.12g of acetic acid to adjust the pH value to 4.0, and performing ultrasonic hydrolysis for 2 hours to obtain a solution C;
then transferred into a three-neck flask filled with inert gas, 50.0g of absolute ethyl alcohol and 0.20g of nano SiO are added into the solution C2Carrying out reflux reaction at 78 ℃ for 8h, washing with ethanol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60 ℃ for 12h to obtain the flame retardant;
(3) adding 1g of sodium alginate, 0.2g of flame retardant and 60g of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 10.0g of acrylic acid, 3.33g of sodium hydroxide, 30.0g of deionized water and 0.02g N, N' -methylene bisacrylamide in an ice-water bath to obtain a solution E;
dissolving 0.1g of potassium persulfate, 0.037g of sodium bisulfite and 10.0g of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F into the solution D for 30min under the water bath condition of 60 ℃, and preserving the temperature for 5h to obtain a solution G;
(4) and then adding 0.2G of sodium dodecyl benzene sulfonate and 0.5G of glycerol into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant.
Example 3
A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following steps:
(1) adding 0.10g of KH550, 0.044g of benzaldehyde and 30.0g of absolute ethyl alcohol into a three-neck flask filled with inert gas, and reacting in an oil bath at 78 ℃ for 6 hours to obtain a solution A;
then weighing 0.10g of DOPO, and fully dissolving with 20.0g of absolute ethyl alcohol to obtain a solution B;
slowly dripping the solution B into the solution A for 40min by using a dropping funnel, continuously reacting at constant temperature for 12h to obtain a crude product, adding absolute ethyl alcohol into the crude product, washing for three times, performing suction filtration, and drying at 60 ℃ for 12h to obtain a flame-retardant intermediate;
(2) adding a flame-retardant intermediate into a beaker, adding 57.0g of ethanol and 3.0g of deionized water into the flame-retardant intermediate, then adding 0.12g of acetic acid to adjust the pH value to 4.0, and performing ultrasonic hydrolysis for 2 hours to obtain a solution C;
then transferring the mixture into a three-neck flask filled with inert gas, adding 50.0g of absolute ethyl alcohol and 0.20g of kaolin into the solution C, carrying out reflux reaction at 78 ℃ for 8 hours, washing with ethyl alcohol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60 ℃ for 12 hours to obtain the flame retardant;
(3) adding 2g of sodium alginate, 0.4g of flame retardant and 60g of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 20.0g of acrylic acid, 6.66g of sodium hydroxide, 30.0g of deionized water and 0.04g N, N' -methylenebisacrylamide in an ice-water bath to obtain a solution E;
dissolving 0.2g of potassium persulfate, 0.074g of sodium bisulfite and 10.0g of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F into the solution D for 40min under the water bath condition of 60 ℃, and preserving the temperature for 5h to obtain a solution G;
(4) and then adding 0.2G of sodium dodecyl benzene sulfonate and 0.5G of glycerol into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant.
Example 4
A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following steps:
(1) adding 0.12g of KH550, 0.03g of terephthalaldehyde and 30.0g of toluene into a three-neck flask filled with inert gas, and reacting for 4 hours in an oil bath at 120 ℃ to obtain a solution A;
then weighing 0.10g of DOPO, and fully dissolving with 20.0g of toluene to obtain a solution B;
slowly dripping the solution B into the solution A for 40min by using a dropping funnel, continuously reacting at constant temperature for 8h to obtain a crude product, adding toluene into the crude product, washing for three times, performing suction filtration, and drying at 60 ℃ for 12h to obtain a flame-retardant intermediate;
(2) adding a flame-retardant intermediate into a beaker, adding 76.0g of ethanol and 4.0g of deionized water into the flame-retardant intermediate, then adding 0.16g of acetic acid to adjust the pH value to 4.0, and performing ultrasonic hydrolysis for 2 hours to obtain a solution C;
then transferred into a three-neck flask filled with inert gas, 50.0g of absolute ethyl alcohol and 0.20g of nano SiO are added into the solution C2Carrying out reflux reaction at 78 ℃ for 8h, washing with ethanol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60 ℃ for 12h to obtain the flame retardant;
(3) adding 2g of sodium alginate, 0.8g of flame retardant and 60g of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 20.0g of acrylic acid, 6.66g of sodium hydroxide, 30.0g of deionized water and 0.04g N, N' -methylenebisacrylamide in an ice-water bath to obtain a solution E;
dissolving 0.2g of ammonium persulfate, 0.074g of sodium bisulfite and 10.0g of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F for 40min under the water bath condition of 60 ℃, and preserving heat for 5h to obtain a solution G;
(4) and then adding 0.2G of sodium dodecyl benzene sulfonate and 0.5G of glycerol into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant.
Example 5
A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant comprises the following steps:
(1) adding 0.12g of KH550, 0.03g of terephthalaldehyde and 30.0g of absolute ethyl alcohol into a three-neck flask filled with inert gas, and reacting for 6 hours in an oil bath at 78 ℃ to obtain a solution A;
then weighing 0.10g of DOPO, and fully dissolving with 20.0g of absolute ethyl alcohol to obtain a solution B;
slowly dripping the solution B into the solution A for 40min by using a dropping funnel, continuously reacting at constant temperature for 12h to obtain a crude product, adding absolute ethyl alcohol into the crude product, washing for three times, performing suction filtration, and drying at 60 ℃ for 12h to obtain a flame-retardant intermediate;
(2) adding a flame-retardant intermediate into a beaker, adding 57.0g of ethanol and 3.0g of deionized water into the flame-retardant intermediate, then adding 0.12g of acetic acid to adjust the pH value to 4.0, and performing ultrasonic hydrolysis for 2 hours to obtain a solution C;
then transferred into a three-neck flask filled with inert gas, 50.0g of absolute ethyl alcohol and 0.20g of nano SiO are added into the solution C2Carrying out reflux reaction at 78 ℃ for 8h, washing with ethanol for three times to remove unreacted substances, carrying out suction filtration, and drying at 60 ℃ for 12h to obtain the flame retardant;
(3) adding 1g of carboxymethyl cellulose, 0.6g of flame retardant and 60g of deionized water into a three-neck flask, and stirring at room temperature to fully dissolve to obtain a solution D for later use;
stirring and dissolving 10.0g of acrylic acid, 3.33g of sodium hydroxide, 30.0g of deionized water, 1g of acrylamide and 0.03g of N, N' -methylene-bisacrylamide in an ice-water bath to obtain a solution E;
dissolving 0.1g of potassium persulfate, 0.037g of sodium bisulfite and 10.0g of deionized water to obtain a solution F;
introducing inert gas into the three-neck flask, slowly dropwise adding the solution E and the solution F into the solution D for 30min under the water bath condition of 60 ℃, and preserving the temperature for 5h to obtain a solution G;
(4) and then adding 0.2G of sodium dodecyl benzene sulfonate and 1.0G of glycerol into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely the nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant.
The flame-retardant intermediate and the flame-retardant dust suppressant obtained in examples 1 to 5 were subjected to structural characterization and performance tests, and the results are shown in fig. 2 to 6.
FIGS. 2 and 3 show FT-IR curves and XRD curves of the obtained flame-retardant intermediate KH550-DOPO and the raw material DOPO, respectively. From FIG. 2, it can be seen that 3057cm was obtained after the reaction-1On the benzene ring of (B)The absorption peak of saturated carbon-hydrogen bond is obviously weakened, 2922cm-1A saturated carbon-hydrogen bond absorption peak appears; 2436cm-1The absorption peak of P-H bond disappears; 1066cm-1A clear Si-O bond absorption peak appears. As can be seen from FIG. 3, before the reaction, DOPO had many sharp crystalline peaks, while KH550-DOPO had only a broad steamed bun-like dispersion peak and changed to an amorphous structure. Therefore, the flame-retardant intermediate KH550-DOPO can be successfully synthesized by the DOPO generation reaction.
Fig. 4 and 5 are respectively an FT-IR curve and an XRD curve of the flame-retardant dust suppressant. The non-flame retardant dust suppressant in FIG. 4 (b) represents the product obtained by reacting several dust suppressing components, i.e., natural polymer, monomer, pH buffer, initiator, crosslinking agent, surfactant and plasticizer, without adding a flame retardant. It can be seen from FIG. 4 that 3616cm after the reaction-1The absorption peak of sodium alginate-OH is obviously disappeared by 1605cm-1-COO in sodium alginate-The absorption peak is shifted to 1549cm-1And coincident with the-NH-peak at 1214cm-1Has an absorption peak of P ═ O bond (1044 cm)-1An Si-O bond absorption peak appears. As can be seen from fig. 5, the diffraction peak at 2 θ ═ 14.3 ° after the reaction disappeared, and a broad amorphous dispersion peak appeared at around 30 °; the diffraction peak of the DOPO group appears at 13.3 ° and the diffraction peak of the nano-silica appears at 22.0 °. From the results, the sodium alginate, the acrylic acid and the flame retardant are successfully reacted to obtain the flame-retardant dust suppressant.
Fig. 6(a) and (b) are the surface appearances of the pulverized coal after being sprayed with water and dried with 5% of the flame retardant dust suppressant, respectively. As can be seen from fig. 6(a), the surface of the pulverized coal is uneven and loose after water spraying, and a plurality of fine coal particles exist, and are easy to fly due to wind erosion and vibration; and after the flame-retardant dust suppressant is sprayed in the figure 6(b), a layer of compact film is formed on the surface of the coal powder to cover the surface of the coal powder, and the coal powder is tightly bonded together, so that the coal powder can be effectively prevented from floating around under the action of external force to cause air pollution and resource waste, and the film can also reduce the contact between the coal powder and oxygen and reduce the risk of spontaneous combustion of coal.
The invention also makes the following performance tests:
TB/T3210.1-2009 dust suppression technical conditions for railway coal transportation part 1: the dust suppressant specifies the product performance requirements of the dust suppressant for railway coal transportation, wherein the spraying amount is required to be not less than 1.5L/m2Time, wind erosion rate<1% and the cured layer thickness is not less than 10 mm. The weathering resistance and the cured layer thickness of the flame-retardant dust suppressant were tested according to the specified test methods.
1. Test of resistance to weathering
Selecting a coal sample of 10 meshes to 30 meshes, drying for 300min in an oven at the temperature of 50 ℃, and removing water. Appropriate amount of coal was put in 2 (300 mm. times.210 mm. times.30 mm) enamel trays respectively so that the coal bed surface was flush with the trays, and weighed respectively, wherein the coal mass was M1. Spraying 2% flame retardant dust suppressant (spraying amount is 1.5L/m) on the two trays respectively2) Drying in a drying oven at 50 deg.C for 120min, respectively blowing for 5min at the surface wind speed of 30M/s, weighing respectively, and weighing the rest coal2. Then, the wind erosion rate of the sample is respectively calculated according to the following formula:
Figure BDA0002608283240000141
in the formula:
e-sample wind erosion rate,%;
M1-mass of coal dust before erosion blowing, g;
M2mass of coal fines after erosion, g.
The weathering rate of sample 1 was found to be E1The weathering rate of sample 2 was E2And taking the average value.
2. Thickness test of cured layer
The thickness of the cured layer at 4 points was measured with a scale, and the average value was taken.
After the flame-retardant dust suppressant with the mass fraction of 2% is sprayed and dried, the surface of the coal seam is blown and eroded for 5min at the wind speed of 30m/s, the wind erosion rate is only 0.53%, and the thickness of the cured layer is 1.47cm, so that the requirement of TB/T3210.1-2009 on dust suppression performance is met.
3. Test for flame retardancy
Taking 2 parts of 30g of coal powder, respectively treating the coal powder by using a flame-retardant dust suppressant solution with the mass fraction of 2% and water (both 30g), drying, putting the coal powder into 2 three-neck flasks, connecting the flasks with an air suction pump, putting the flasks into a thermometer, setting the gas flow rate at 250mL/min, putting the flasks into an 80 ℃ oil bath kettle, detecting the CO concentration by using a CO gas detector, continuously increasing the temperature to 150 ℃, and respectively recording the CO concentrations at different temperatures. And analyzing and comparing the concentration difference of CO in the flame-retardant treatment and the water treatment to determine the flame-retardant effect, wherein the smaller the concentration of CO is, the better the flame-retardant effect is. The formula for calculating the resistivity is as follows:
Figure BDA0002608283240000142
in the formula:
z-inhibition ratio,%;
S1-the concentration of CO emitted from the water treated coal sample, g/L;
S2and treating the coal sample by using the flame-retardant dust suppressant to obtain the concentration of CO discharged by the coal sample in g/L.
The test result is shown in fig. 7, and it can be seen from fig. 7 that the inhibition rate of the coal sample treated by the flame-retardant dust suppressant with a mass fraction of 2% can reach 70.68% at 150 ℃, which indicates that the flame-retardant dust suppressant can prevent spontaneous combustion of coal to a certain extent. The phosphorus flame retardant acts with oxygen to form a protective layer such as phosphoric acid and polyphosphoric acid, so that the phosphorus flame retardant has the effects of isolating oxygen and reducing the release of carbon monoxide, can release PO & free radicals to capture H & free radicals and HO & free radicals released during combustion, and achieves the flame retardant effect; the nitrogen flame retardant is mainly a flame-retardant carbon layer generated during combustion and covers the surface of the pulverized coal to play a role in isolating oxygen; the silicon flame retardant is mainly used for transferring the flame retardant to the surface of coal powder during combustion, and enriching the flame retardant on the surface, so that the effect of reducing the contact of oxygen and combustible gas is achieved, and the flame retardant effect is achieved.

Claims (10)

1. The nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant is characterized by comprising the following raw materials in parts by mass:
0.08 to 0.12 part of phosphorus flame retardant, 0.10 to 0.14 part of nitrogen-containing silane coupling agent, 0.01 to 0.05 part of aldehyde compound, 100.0 to 200.0 parts of solvent, 0.18 to 0.36 part of silicon flame retardant, 0.1 to 0.4 part of pH regulator, 83.0 to 125.0 parts of deionized water, 57.0 to 95.0 parts of alcohol compound, 1.0 to 2.0 parts of natural polymer, 10.0 to 20.0 parts of monomer, 4.0 to 8.0 parts of pH buffer, 0.1 to 0.4 part of initiator, 0.02 to 0.08 part of cross-linking agent, 0.2 to 0.4 part of surfactant and 0.2 to 1.0 part of plasticizer.
2. The nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 1, wherein the phosphorus flame retardant is DOPO.
3. The nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 1, wherein the nitrogen-containing silane coupling agent is gamma-aminopropyltriethoxysilane.
4. The nitrogen phosphorus silicon synergistic coal flame retardant and dust suppression agent as claimed in claim 1, wherein the aldehyde compound is at least one of terephthalaldehyde, benzaldehyde, formaldehyde, glutaraldehyde and p-hydroxybenzaldehyde.
5. The nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 1, wherein the silicon flame retardant is nano SiO2At least one of kaolin, diatomite, montmorillonite and attapulgite.
6. The nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 1, wherein the natural polymer is at least one of sodium alginate, starch and derivatives thereof, cellulose and derivatives thereof, and chitosan.
7. The nitrogen phosphorus silicon synergistic coal flame retardant dust suppressant according to claim 1, wherein the pH regulator is at least one of acetic acid and hydrochloric acid;
the pH buffering agent is sodium hydroxide;
the solvent is at least one of absolute ethyl alcohol, benzene, toluene, trichloromethane, acetone, cyclohexane and tetrahydrofuran;
the alcohol compound is at least one of methanol and ethanol;
the monomer is at least one of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;
the initiator is potassium persulfate and sodium bisulfite, or ammonium persulfate and sodium bisulfite;
the cross-linking agent is at least one of N, N' -methylene-bisacrylamide and dimethyldiallylammonium chloride;
the surfactant is at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;
the plasticizer is glycerol.
8. A preparation method of a nitrogen-phosphorus-silicon synergistic coal flame-retardant dust suppressant is characterized by comprising the following steps:
(1) mixing 0.10-0.14 part of nitrogen-containing silane coupling agent, 0.01-0.05 part of aldehyde compound and 30.0-60.0 parts of solvent, and reacting at 60-120 ℃ for 4-8h to obtain solution A;
mixing 0.08-0.12 part of phosphorus flame retardant and 20.0-40.0 parts of solvent to obtain solution B;
dripping the solution B into the solution A, and reacting at 60-120 ℃ for 8-16h to obtain a crude product;
washing and filtering the crude product, and drying at 60-80 ℃ for 12-24h to obtain a flame-retardant intermediate;
(2) adding 57.0-95.0 parts of alcohol compound and 3.0-5.0 parts of deionized water into the flame-retardant intermediate, then adding a pH regulator to adjust the pH value to 3.0-4.0, and performing ultrasonic hydrolysis for 1-2 hours to obtain a solution C;
introducing inert gas into the solution C, adding 50.0-100.0 parts of solvent and 0.18-0.36 part of silicon flame retardant, reacting at 70-120 ℃ for 8-24h, washing to remove unreacted substances, performing suction filtration, and drying at 60-80 ℃ to obtain the flame retardant;
(3) mixing 1-2 parts of natural polymer, 0.2-0.8 part of flame retardant and 40-80 parts of deionized water to obtain a solution D;
mixing 10.0-20.0 parts of monomer, 4.0-8.0 parts of pH buffer, 20.0-40.0 parts of deionized water and 0.02-0.08 part of cross-linking agent to obtain solution E;
mixing 0.1-0.4 part of initiator and 10.0-20.0 parts of deionized water to obtain a solution F;
introducing inert gas into the solution D, adding the solution E and the solution F into the solution D, and preserving the heat for 4-6h at the temperature of 50-60 ℃ to obtain a solution G;
(4) and then adding 0.2-0.4 part of surfactant and 0.2-1.0 part of plasticizer into the solution G, and uniformly stirring to obtain a light yellow transparent viscous liquid, namely nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant.
9. The preparation method of the nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 8, wherein in the step (1), the solution A is prepared under the protection of inert gas;
in the step (3), the preparation of the solution E is carried out under the ice-water bath condition.
10. The preparation method of the nitrogen phosphorus silicon synergistic coal flame-retardant dust suppressant according to claim 8, wherein in the step (2), the mass ratio of the alcohol compound to the deionized water is 19: 1.
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