CN100507214C - Chemical fire retartant for preventing controlling coil mineral well coal self-igniting - Google Patents
Chemical fire retartant for preventing controlling coil mineral well coal self-igniting Download PDFInfo
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- CN100507214C CN100507214C CNB2006100953188A CN200610095318A CN100507214C CN 100507214 C CN100507214 C CN 100507214C CN B2006100953188 A CNB2006100953188 A CN B2006100953188A CN 200610095318 A CN200610095318 A CN 200610095318A CN 100507214 C CN100507214 C CN 100507214C
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Abstract
The present invention discloses one kind of chemical inhibitor for preventing and controlling the self combination of coal in coal mine. The chemical inhibitor is water solution of pH 3-5 and comprising surfactant in 0.5-1 wt%, polymer resin in 0.1 wt% and oxidant in certain concentration. During coal mining, water is injected to the coal bed, and the chemical inhibitor is spread to the residual coal and other easy-to-fire areas alone or after being mixed to other fire extinguishing material. The chemical inhibitor makes the different active structural radicals in coal body oxidized irreversibly to lose low temperature oxidation activity and lower the self combustion tendency of coal to avoid self combustion of coal completely. The present invention is simple, low in cost and suitable for coal mine operation.
Description
Technical field
The present invention relates to prevent and treat the retardant of coal mine coal spontaneous combustion, particularly the chemical retardant of control coal mine coal spontaneous combustion.
Background technology
Spontaneous combustionof coal is one of great disaster of coal mine.In China state-owned emphasis colliery, exist the mine of serious coal spontaneous combustion to account for 56% of mine sum, the fire that is caused by coal spontaneous combustion accounts for 90～94% of mine fire sum.The safety in production of coal mine is arrived in the spontaneous combustionof coal serious threat, and may cause that gas explosion causes great casualties, destroys resource apparatus and causes great economic loss etc.
The main principle of control spontaneous combustionof coal is to stop the generation of oxidation of coal process and elimination heat to gather.The retardant of physical type mainly is the inorganic salts retardant, comprises NaCl, MgCl
2, AlCl
3, Na
2SO
4Deng because this class material has stronger water imbibition, these materials are shed the coal body surface after, can keep the humidity on coal body surface within a certain period of time, temperature is not easy to rise when making the coal body low-temperature oxidation.The physics retardant only is to absorb airborne moisture to a certain extent to preserve moisture, can not stop low-temperature oxidation of coal to discharge heat, for oxidisability or the relatively more suitable situation of condition, the heat that oxidation produces quickens the coal body surface evaporation, and the moisture that absorbs is not enough the time, thereby the temperature of coal body equally also can rise gradually and cause the spontaneous combustion of coal, and under certain condition in the coal body an amount of moisture also help the low-temperature oxidation and the spontaneous combustion of coal.Therefore, the physics retardant can not fundamentally stop the low-temperature oxidation of coal, also just can not fundamentally stop the spontaneous combustion of coal to take place.
The gel-like fireproofing extinguishing materials that sodium alginate, water glass and super absorbent resin etc. are made for primary raw material also has certain resistance to turn usefulness into to coal spontaneous combustion, is to utilize colloid parcel coal body, makes isolated the coming of coal body and airborne oxygen reach the purpose of resistanceization.This class retardant cost height belongs to physics retardant type equally, and because the physicochemical change of mine pressure and coal itself under the coal mine, and the effect of parcel oxygen barrier is often destroyed to be fallen, and does not reach the purpose of preventing and treating coal spontaneous combustion.
Aging-proof agent is to be applied in the additive that prevents ageing of rubber, and the spontaneous combustion of bibliographical information with such material control coal arranged.But the oxidation generation spontaneous combustion of coal is different with the mechanism that rubber oxidation generation is worn out, the low-temperature oxidation of coal spontaneous combustion mainly is that active group and the oxygen generation oxidation reaction in the coal body structure causes, ageing of rubber has the effect of oxidation, but aging-proof agent is to add in the rubber production process in the rubber, this body structure of rubber is changed possess certain non-oxidizability, this mode of action with the coal spontaneous combustion retardant is obviously different.
Also have bibliographical information to utilize food antioxidant as the coal spontaneous combustion retardant.But food is generally protein and lipoid material, make a world of difference with the physical chemistry structure of coal, antioxidant itself also is easy to oxidation simultaneously, the time of antioxidant action is short, and the low-temperature oxidation of coal spontaneous combustion is tens of skies even the process of several months, therefore utilize antioxidant equally also to have many deficiencies, do not have theoretical foundation, weak effect as the coal spontaneous combustion retardant.
Summary of the invention
At the prior art problem, the invention provides a kind of chemical retardant of preventing and treating the coal spontaneous combustion of coal mine.Concrete technical scheme is as follows:
A kind of chemical retardant of preventing and treating the coal spontaneous combustion of coal mine, it is characterized in that be mass percent concentration in the chemical retardant of solvent in raw material at water, surfactant by 0.5～1%, 0.1% hydroscopic high-molecular resin and oxidant are formed, and pH value is between 3～5; Wherein said oxidant is stair oxidation agent or secondary oxidation agent, the spontaneous combustion tendency grade be the coal of easy spontaneous combustion to select the mass percent concentration of stair oxidation agent for use be 0.5～1%, the mass percent concentration of selecting the secondary oxidation agent for use is 1～2%; The spontaneous combustion tendency grade is that the coal of spontaneous combustion selects for use the mass percent concentration of stair oxidation agent to be respectively 0.3～0.5%, and the mass percent concentration of selecting the secondary oxidation agent for use is 0.5～1%; The spontaneous combustion tendency grade is that the coal that is difficult for spontaneous combustion selects for use the mass percent concentration of stair oxidation agent to be respectively 0.1～0.3%, and the mass percent concentration of selecting the secondary oxidation agent for use is 0.3～0.5%.
The mass percent concentration of described surfactant preferably is 0.5%.
The effect of surfactant is that the surface tension of the aqueous solution is reduced, chemical retardant solution not only can contact with the coal body surface like this, and can soak into the hole of coal body inside, the local chemical retardant that oxygen can be reached can both reach substantially, and easier the contact with coal body the chemistry resistance takes place turned usefulness into.All kinds of in cationic surfactant, anion surfactant, the zwitterionic surfactant all can be selected, only from economical, easily angle consider just passable, as neopelex, lauryl sodium sulfate etc.
Hydroscopic high-molecular resin can constantly absorb moisture from air makes coal body keep moistening always, be beneficial to chemistry resistance and turn into realizing, simultaneously the aqueous solution diaphragm of Xing Chenging to a certain extent secluding air enter coal body.Hydroscopic high-molecular resin selects the strong more effect of water absorbing capacity good more, and general water absorbing capacity can reach effect of the present invention more than 500 times.
Coal spontaneous combustion be owing to low-temperature oxidation of coal produce heat and under certain condition heat accumulation the coal body temperature self-ignition point that reaches coal that rises is gradually caused.There is the quantity difference in the texture of coal, structure that oxidation activity is different and group exist the active structure and the group that are easy to oxidation many more in a kind of coal, it is also many more fast more that this coal and oxygen generation oxidation produce heat, the spontaneous combustion tendency of coal is just strong more, and coal is just easier generation spontaneous combustion also.The tradesman falls into three classes the spontaneous combustion tendency of coal in view of the above, i.e. easily spontaneous combustion, spontaneous combustion, be difficult for spontaneous combustion.If with in the coal body particularly the coal body surface structure that is easy to oxidation destroy make its deactivation can not with oxygen generation oxidation reaction, thereby the spontaneous combustion tendency of coal is weakened, spontaneous combustion just under general condition can not take place in coal so, and this chemistry resistanceization is irreversible, and existing physics resistanceization is reversible, therefore just can fundamentally prevent and treat the generation of coal spontaneous combustion.
Based on above-mentioned theory, the nucleus of chemical retardant of the present invention is an oxidant, thereby its effect is different activities structure and the oxidized oxidisability that loses of group that makes in the coal body, and the spontaneous combustion tendency of coal is reduced, and this chemistry resistanceization is irreversible, thereby effectively reaches the purpose of anti-fire extinguishing.The selection principle of oxidant is that (1) is water-soluble; Nontoxic when (2) being diluted to working concentration; (3) oxidizing process is more lasting.Select a kind of the getting final product in stair oxidation agent or the secondary oxidation agent, the concentration of selected oxidant is adjusted accordingly according to coal ignitability's grade.To the strong stair oxidation agent of the best selective oxidation of the higher coal of spontaneous combustion tendency, as perchlorate; The permanganic acid salt; Peroxide etc.To the more weak secondary oxidation agent of the then general selective oxidation of the coal that is difficult for spontaneous combustion such as periodic acid, Peracetic acid, Calcium perchlorate etc.
For oxidant is better played a role, can utilize dilute sulfuric acid or hydrochloric acid to regulate, the pH value that makes chemical retardant is between 3～5.
Chemical retardant of the present invention makes coal body quilt chemistry resistanceization under controllable condition, and irreversible variation takes place.So-called under controlled condition, though be meant that chemical retardant will oxidation take place with coal and produce very small heat in the relatively shorter time, but the heat that produces is owing to there is large quantity of moisture, the existence of surfactant and water-absorbing resin, and the heat that produces also only can make the very small value of coal body temperature rising, and the local heat that spray is sprayed very fast by distinguished and admirable, water evaporates, conduction of heat etc. are taken away, therefore the heat of oxidant and oxidation of coal generation can not make the coal body temperature that obvious rising is arranged, and more can not cause coal body spontaneous combustion (place of spraying chemical retardant all is the place that heat is easy to scatter and disappear).Also just can not discharge heat again in case oxidation takes place fully for oxidant and coal.
The concrete grammar of invention is to utilize surfactant, the oxidant that can continue oxidation and macromolecule high-performance water-absorbing resin to be configured as the chemical retardant solution of pH value between 3～5 according to a certain percentage, in process of coal mining, pass through the pre-water filling in coal seam, something lost coal behind coal-face and other place that is easy to get angry are (such as Gao Maoqu, rib coal column crack and zone of fracture, store the coal bunker of coal) spray chemical retardant solution, also chemical retardant can be added to other fireproofing extinguishing materials and inject easily ignition zone as additive.As long as the consumption that sprays can complete moistening coal body.
In order to confirm to use the effect of retardant of the present invention, same at one time mine collected specimens coal, use retardant of the present invention to do contrast before and after handling:
Adopt following several modes to check the effect of chemical retardant control coal spontaneous combustion: 1) to utilize infrared spectrum to detect the situation that chemical retardant destroys active structure and group in the coal body, active structure and group are destroyed in the coal body of retardant processing back, the degree of being damaged is big more, and the resistanceization effect is good more; Mode comparative analysis coals such as the analysis of 2) utilization heat, coal spontaneous combustion process simulation and temperature programming are low-temperature oxidation quantity of heat production and heat production speed before the chemistry resistanceization and after the chemistry resistanceization, resistanceization back quantity of heat production and heat production speed all descend, and drop-out value is big more, shows that chemistry resistanceization effect is good more; 3) low-temperature oxidation of coal is carried out the index gas analysis, index gas such as resistanceization back CO produce total amount and descend under same test condition, and it is many more to descend, and shows that chemistry resistanceization effect is good more.
The invention has the beneficial effects as follows that thereby different activities structure and the irreversible reaction of the oxidized generation of group in the coal body lose oxidisability, the spontaneous combustion tendency of coal is reduced, thereby thoroughly prevent the spontaneous combustion of coal, simple to operate, it is convenient economical to draw materials, and is suitable for operation under the mine.
Specific embodiment
The hydroscopic high-molecular resin that takes by weighing 500 times of surfactant neopelexes, stair oxidation agent potassium permanganate, water absorbing capacity is dissolved in water and is configured to mass percentage concentration is respectively that 0.8%, 0.5%, 0.1% mixed solution is totally 2000 milliliters of chemical retardants, the PH that adds sulfuric acid regulation solution is 4, choosing spontaneous combustion tendency grade is sample coal 500 grams of easy spontaneous combustion, it is moistening fully with coal body that the chemical retardant of configuration is sprayed on coal body, sample coal before and after handling performs an analysis, and the result is as follows:
(1) utilizes the resistance rate assay method of CO generation to record the resistanceization rate and reach 93%;
(2) find that with the variation of texture of coal before and after the infrared spectrum analysis chemistry resistanceization some functional group that is easy to oxidation does not exist, the quantity that has obviously reduces, and the oxygen-containing functional group showed increased in the coal body, such as: aromatic hydrocarbons-CH class, the methyl class, methyl, methylene asymmetric stretching vibration class, methylene symmetrical stretching vibration class, C=C stretching vibration class in the aromatic rings, methylene scissoring vibration class, methyl scissoring vibration class, number of functional groups such as substituted benzene and methylene plane vibration class obviously reduce or disappear, and aromatic ketone, the aldehydes carbonyl, phenol, alcohol, ether, ester oxygen key class number of functional groups showed increased.
Claims (6)
1, a kind of chemical retardant of preventing and treating the coal spontaneous combustion of coal mine, it is characterized in that be mass percent concentration in the chemical retardant of solvent in raw material at water, surfactant by 0.5～1%, 0.1% hydroscopic high-molecular resin and oxidant are formed, and pH value is between 3～5; Wherein said oxidant is stair oxidation agent or secondary oxidation agent, the spontaneous combustion tendency grade be the coal of easy spontaneous combustion to select the mass percent concentration of stair oxidation agent for use be 0.5～1%, the mass percent concentration of selecting the secondary oxidation agent for use is 1～2%; The spontaneous combustion tendency grade is that the coal of spontaneous combustion selects for use the mass percent concentration of stair oxidation agent to be respectively 0.3～0.5%, and the mass percent concentration of selecting the secondary oxidation agent for use is 0.5～1%; The spontaneous combustion tendency grade is that the coal that is difficult for spontaneous combustion selects for use the mass percent concentration of stair oxidation agent to be respectively 0.1～0.3%, and the mass percent concentration of selecting the secondary oxidation agent for use is 0.3～0.5%.
2. the chemical retardant of control coal mine as claimed in claim 1 coal spontaneous combustion, the mass percent concentration of wherein said surfactant is 0.5%.
3. the chemical retardant of control coal mine as claimed in claim 1 coal spontaneous combustion, wherein said surfactant is a neopelex.
4. the chemical retardant of control coal mine as claimed in claim 1 coal spontaneous combustion, the water absorbing capacity of wherein said hydroscopic high-molecular resin is more than 500 times.
5. the chemical retardant of control coal mine as claimed in claim 1 coal spontaneous combustion, wherein said stair oxidation agent is a permanganate.
6. the chemical retardant of control coal mine as claimed in claim 1 coal spontaneous combustion, wherein said secondary oxidation agent is a periodic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100953188A CN100507214C (en) | 2006-12-21 | 2006-12-21 | Chemical fire retartant for preventing controlling coil mineral well coal self-igniting |
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| CNB2006100953188A CN100507214C (en) | 2006-12-21 | 2006-12-21 | Chemical fire retartant for preventing controlling coil mineral well coal self-igniting |
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| CN100999996A CN100999996A (en) | 2007-07-18 |
| CN100507214C true CN100507214C (en) | 2009-07-01 |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092879B (en) * | 2007-07-26 | 2010-06-02 | 康怀宇 | Method for injecting retarder to coal body |
| FR2949068B1 (en) * | 2009-08-11 | 2013-06-07 | Internat Environmental Corp Iec | TEMPERATURE WATER AS A MEANS FOR CONTROLLING FIRE AND EXPLOSION HAZARDS OF EXTRACTIVE ORGANIC MATERIALS |
| CN101787289B (en) * | 2010-01-07 | 2012-09-05 | 中国矿业大学 | Method for preparing fireproof and explosion suppression pulverized fuel ash carbon dioxide material |
| CN101793160B (en) * | 2010-01-29 | 2011-10-05 | 北京工业大学 | Environment-friendly flame-retardant high-molecular gel inhibitor for preventing coal from spontaneously combusting of coal mine |
| CN101766877B (en) * | 2010-02-05 | 2011-06-22 | 北京科技大学 | Inorganic salt type inhibitor for preventing and controlling spontaneous combustion of residual coal in goaf of coal mine |
| CN102966369B (en) * | 2012-12-10 | 2014-09-03 | 中国矿业大学 | Composite stopping agent preventing coal spontaneous combustion based on low-temperature oxidation mechanism of coal |
| CN103388486B (en) * | 2013-07-18 | 2015-09-09 | 北京工业大学 | Coal mining spraying wind leaking stoppage fireproofing extinguishing materials of a kind of excellent flame retardancy and preparation method thereof |
| CN104151952B (en) * | 2013-12-19 | 2017-05-03 | 山东科技大学 | Coal mine gangue hill anti-explosion stopping agent and treatment and early warning system |
| CN103756462A (en) * | 2014-01-03 | 2014-04-30 | 安徽理工大学 | Novel environment-friendly high molecular stopping agent capable of preventing mine coal from spontaneously combusting |
| CN104747228B (en) * | 2015-04-03 | 2018-02-02 | 安徽理工大学 | A kind of inhibition foam material for preventing and treating coal spontaneous combustion and preparation method thereof |
| CN106753439B (en) * | 2016-12-07 | 2018-10-12 | 中国矿业大学 | One kind preventing spontaneous combustionof coal compound retardant and preparation method thereof |
| CN106869988B (en) * | 2016-12-25 | 2019-03-26 | 广州发展燃料港口有限公司 | A kind of preparation method preventing spontaneous combustionof coal retardant |
| CN107035398B (en) * | 2017-06-16 | 2019-02-12 | 中国矿业大学 | A kind of compound retardant of physical-chemical and its preparation and application for preventing and treating low order coal spontaneous combustion |
| CN110005463B (en) * | 2019-04-15 | 2021-02-05 | 北京科技大学 | High polymer-based nano composite stopping agent for preventing spontaneous combustion of coal gangue |
| CN110219691B (en) * | 2019-06-27 | 2020-07-24 | 中国矿业大学 | Environment-friendly composite stopping agent for preventing coal spontaneous combustion and preparation method thereof |
| CN113294198B (en) * | 2021-05-20 | 2024-01-23 | 太原理工大学 | Soluble slow-release temperature-sensitive stopping agent and preparation method thereof |
| CN113372672B (en) * | 2021-05-21 | 2022-05-03 | 北京科技大学 | Modified antioxidant for inhibiting spontaneous combustion of coal and preparation method thereof |
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Owner name: CHINA COAL TECHNOLOGY ENGINEERING GROUP CHONGQING Free format text: FORMER NAME: CHINA COAL SCIENCE AND INDUSTRY GROUP CHONGQING RESEARCH INSTITUTE Owner name: COAL SCIENTIFIC RESEARCH INSTITUTE CHONGQING INSTI Free format text: FORMER NAME: CHONGQING BRANCH, COAL SCIENCE RESEARCH GENERAL INST. Owner name: CHINA COAL SCIENCE AND INDUSTRY GROUP CHONGQING RE Free format text: FORMER NAME: COAL SCIENTIFIC RESEARCH INSTITUTE CHONGQING INSTITUTE |
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