CN-121045794-B - High-temperature response type composite material for coal pile flame retardance and heat value release cooperative regulation and control as well as preparation method and application thereof

CN121045794BCN 121045794 BCN121045794 BCN 121045794BCN-121045794-B

Abstract

A high-temperature response type composite material for the synergistic regulation and control of coal pile flame retardance and heat value release, a preparation method and application thereof, wherein the material is formed by the synergy of modified inorganic particle filler and a composite high-heat value carrier, the modified inorganic particle filler comprises organically modified SiO 2 particles and MnFe 2 O 4 nano particles grafted with hydroxyl functional groups, and the composite high-heat value carrier consists of polyether, polydimethylsiloxane and white oil high-heat value oil phase. After the components are treated, a uniformly dispersed emulsion composite system with stable structure is formed, and the emulsion composite system has good seepage perfusion performance and environmental adaptability. At the normal temperature stage, the initial oxidation rate of the coal is reduced by blocking the diffusion paths of the moisture and the oxygen, so that the high-efficiency flame retardance is realized. In the high-temperature stage, the cracking and oxidation processes of coal and organic carriers are accelerated by catalysis, so that the problems of oil phase agglomeration and carbonization coking are inhibited, and the burnout rate and clean combustion performance are remarkably improved. The material system of the invention has the advantages of normal temperature flame retardance, high temperature combustion supporting, no carbon residue pollution and the like.

Inventors

QI XUYAO
CHEN MUJUN
XU DEXIN
NIE SHIBIN
LIU HUI
LI DAN
QI GUANSHENG
HU JIE

Assignees

中国矿业大学

Dates

Publication Date: 20260508
Application Date: 20250917

Claims (9)

1. A high-temperature response type composite material for the synergistic regulation and control of coal pile flame retardance and heat value release is characterized by comprising a mixed system formed by organic modified inorganic particle filler, a composite high-heat value carrier and an aromatic ether linking agent, wherein the organic modified inorganic particle filler comprises organic modified SiO 2 particles and MnFe 2 O 4 nano particles grafted with hydroxyl functional groups, the composite high-heat value carrier comprises polyether, polydimethylsiloxane and white oil high-heat value oil phase which are mixed in proportion, the aromatic ether linking agent is hydroquinone dihydroxyethyl ether or resorcinol-bis (beta-hydroxyethyl) ether, and the organic modified SiO 2 particles and MnFe 2 O 4 nano particles grafted with hydroxyl functional groups respectively account for 6-20% and 10-15% of the mass of the mixed system; the modification method of the organically modified SiO 2 granule comprises the steps of adding SiO 2 into absolute ethyl alcohol for ultrasonic dispersion, adding polyethylene glycol, stirring and reacting at 40-50 ℃, and washing and drying by deionized water to obtain the product; The modification method of the MnFe 2 O 4 nano-particles grafted with hydroxyl functional groups comprises the steps of dissolving Mn (NO 3 ) 2 ·4H 2 O and Fe (NO 3 ) 3 ·9H 2 O) in deionized water, controlling the pH value to be 10-11, stirring and reacting at 70 ℃ until the MnFe 2 O 4 nano-particles are fully formed and precipitated, adding polyvinyl alcohol and isophorone diisocyanate into a reaction system, and reacting at 50-60 ℃ under the protection of nitrogen.
2. The method for preparing the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 1, which is characterized by comprising the following steps: a. Adding SiO 2 into absolute ethyl alcohol for ultrasonic dispersion, adding polyethylene glycol, stirring and reacting at 40-50 ℃, and washing and drying by deionized water to obtain organic modified SiO 2 particles; b. Mn (NO 3 ) 2 ·4H 2 O and Fe (NO 3 ) 3 ·9H 2 O are dissolved in deionized water, the pH is controlled to be 10-11, stirring reaction is carried out at 70 ℃ until MnFe 2 O 4 nano-particles are fully formed and precipitated, polyvinyl alcohol and isophorone diisocyanate are added into a reaction system, and the reaction is carried out at 50-60 ℃ under the protection of nitrogen, so that MnFe 2 O 4 nano-particles with hydroxyl-containing functional groups grafted on the surfaces are obtained; c. adding polyether and polydimethylsiloxane into a reaction kettle according to a proportion, heating and stirring at 60-70 ℃ to form a uniform oil phase basic system, dripping a proper amount of deionized water into the uniform oil phase basic system, then adding a white oil high-heat-value oil phase, and continuously stirring at the same temperature to form a stable composite high-heat-value carrier; d. C, adding an aromatic ether linking agent into the composite high-heat-value carrier obtained in the step C, and stirring and reacting for 1-2 hours at 60-75 ℃ to obtain a mixed system, wherein the aromatic ether linking agent is hydroquinone dihydroxyethyl ether or resorcinol-bis (beta-hydroxyethyl) ether; e. Adding the organic modified SiO 2 particles prepared in the step a and the MnFe 2 O 4 nano particles grafted with the hydroxyl functional groups prepared in the step b into the mixed system obtained in the step d according to a proportion, and performing emulsification treatment for 1-2h at 60-75 ℃ under the stirring condition to obtain the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile, wherein the organic modified SiO 2 particles and the MnFe 2 O 4 nano particles grafted with the hydroxyl functional groups respectively account for 6-20% and 10-15% of the mass of the mixed system.
3. The preparation method of the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile, which is disclosed in claim 2, is characterized in that in the step a, the mass ratio of SiO 2 to polyethylene glycol is (0.5-2): 1, the stirring reaction is carried out for 2 hours, and the mass volume ratio of SiO 2 to absolute ethyl alcohol is 1g (13-32) ml.
4. The preparation method of the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 2 or 3, wherein in the step b, the mass ratio of Mn (NO 3 ) 2 ·4H 2 O to Fe (NO 3 ) 3 ·9H 2 O) is1 (1.5-2.5), the stirring reaction is carried out for 1.5 hours, and the mass volume ratio of Mn (NO 3 ) 2 ·4H 2 O to deionized water is 1g (12-19) ml.
5. The preparation method of the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 2 or 3, wherein in the step b, mn (NO 3 ) 2 ·4H 2 O, polyvinyl alcohol and isophorone diisocyanate are in a mass ratio of 10:1 (5-10), and the reaction is carried out for 2 hours under the protection of nitrogen.
6. The method for preparing the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 2 or 3, wherein in the step c, the polyether is selected from polypropylene glycol or polyethylene glycol, and the white oil type high-heat value oil phase is medical grade mineral oil or light paraffin oil.
7. The preparation method of the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 2 or 3, wherein in the step c, the mass ratio of polyether, polydimethylsiloxane and white oil type high-heat value oil phase in the composite high-heat value carrier is (4-14): (1-5): 1.
8. The method for preparing the high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile according to claim 2 or 3, wherein in the step d, the aromatic ether linking agent accounts for 2.4-2.8% of the composite high-heat value carrier by mass percent.
9. Use of a composite material according to claim 1 or a composite material prepared by a preparation method according to any one of claims 2-8 in flame retardance of a coal pile, wherein the composite material is sprayed to cover the surface of coal particles to form a hydrophobic oxygen diaphragm or injected into cracks of the coal pile in a pressurized pouring mode, and seepage is used for blocking an air leakage channel and replacing free oxygen in the pile.

Description

High-temperature response type composite material for coal pile flame retardance and heat value release cooperative regulation and control as well as preparation method and application thereof Technical Field The invention relates to the technical field of storage and transportation of coal piles and efficient combustion utilization, in particular to a high-temperature response type composite material for the cooperative regulation and control of flame retardance and heat value release of coal piles, and a preparation method and application thereof. Background Spontaneous combustion of coal piles is a common thermal disaster problem in coal transportation and open-air storage processes, particularly in port yards, railway transfer points and open-air coal piles, and due to long-time exposure to complex environments such as air, sunlight, rainwater and the like, the fire conditions caused by spontaneous combustion not only cause a great deal of loss of coal resources, but also seriously threaten the safety of operators and the surrounding ecological environment. Spontaneous combustion of coal mainly originates from low-temperature oxidation heat accumulation, and occurrence of the spontaneous combustion of coal has the characteristics of strong concealment, rapid development, difficult early warning and disposal and the like, and becomes one of key technical problems for restricting coal storage and transportation safety and improving economic benefit. In the current engineering, means such as film covering, inhibitor spraying and the like are often adopted for carrying out flame retardant treatment on coal piles, although the spontaneous combustion risk can be relieved to a certain extent, the problems of short action period, large influence by climate and site conditions, poor environmental adaptability and the like generally exist in the methods, partial materials are easy to disintegrate in a structure in a high-temperature environment, the flame retardant performance is reduced, and even the combustion-supporting effect can be caused by improper reaction. In addition, the traditional flame-retardant mode often neglects the utilization of the fuel value of coal as an energy source, so that the treated coal pile is difficult to directly burn and use, and the subsequent cleaning and fuel processing cost is increased. Therefore, there is a need to develop a functional composite material with good environmental adaptability, high Wen Xiangying characteristics and synergistic heat value regulation capability, which can effectively block and inhibit oxygen and flame for the surface and internal pores of a coal pile under normal temperature conditions, release high heat value components under high temperature conditions, promote combustion efficiency, realize dual targets from safe storage to efficient utilization, and meet the green, safe and efficient management requirements of coal in the transportation and open-air storage processes. Disclosure of Invention The invention aims to provide a high-temperature response type composite material for the cooperative regulation and control of coal pile flame retardance and heat value release, and a preparation method and application thereof, wherein the preparation method is simple and convenient, and the material cost is low; the prepared composite material has the characteristics of good high-temperature responsiveness, strong covering seepage capability, high film forming and blocking stability, high-efficiency catalytic heat value release and the like, and is suitable for the fields of open-air coal pile, flame-retardant protection in long-distance coal transportation, high-temperature high-efficiency combustion of coal in coal storage power plants and the like. In order to achieve the above purpose, the invention is realized by the following technical scheme: The high-temperature response type composite material for the synergistic regulation and control of the flame retardance and the heat value release of the coal pile is formed by the synergy of an organic modified inorganic particle filler and a composite high-heat value carrier, wherein the organic modified inorganic particle filler comprises organic modified SiO 2 particles and MnFe 2O4 nano particles grafted with hydroxyl functional groups, and the composite high-heat value carrier is formed by proportionally mixing polyether, polydimethylsiloxane and white oil high-heat value oil phase. In order to achieve the aim of the invention, the invention also provides a preparation method of the high-temperature response type composite material for the cooperative regulation and control of the flame retardance and the heat value release of the coal pile, which comprises the following steps: a. Adding SiO 2 into absolute ethyl alcohol for ultrasonic dispersion, adding polyethylene glycol, stirring and reacting at 40-50 ℃, and washing and drying by deionized water to obtain organic modified SiO 2 particles; b. Mn (