CN117404127A - Composite stopping agent for preventing and treating spontaneous combustion of coal and preparation method thereof - Google Patents
Composite stopping agent for preventing and treating spontaneous combustion of coal and preparation method thereof Download PDFInfo
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- CN117404127A CN117404127A CN202311599952.5A CN202311599952A CN117404127A CN 117404127 A CN117404127 A CN 117404127A CN 202311599952 A CN202311599952 A CN 202311599952A CN 117404127 A CN117404127 A CN 117404127A
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- 239000003245 coal Substances 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 38
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000012267 brine Substances 0.000 claims abstract description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 56
- 239000003112 inhibitor Substances 0.000 claims abstract description 55
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- -1 peroxy free radical Chemical group 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002440 industrial waste Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229920002907 Guar gum Polymers 0.000 claims description 4
- 229920002752 Konjac Polymers 0.000 claims description 4
- QRYRORQUOLYVBU-VBKZILBWSA-N carnosic acid Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 239000000230 xanthan gum Substances 0.000 claims description 4
- 229920001285 xanthan gum Polymers 0.000 claims description 4
- 235000010493 xanthan gum Nutrition 0.000 claims description 4
- 229940082509 xanthan gum Drugs 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003349 gelling agent Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- HOKKMGSILWBPLH-UHFFFAOYSA-N isoquinoline-4,5-diol Chemical compound N1=CC(O)=C2C(O)=CC=CC2=C1 HOKKMGSILWBPLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000252 konjac Substances 0.000 claims description 2
- 235000019823 konjac gum Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 47
- 230000003647 oxidation Effects 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 4
- 238000009736 wetting Methods 0.000 abstract description 4
- 230000010718 Oxidation Activity Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 abstract 5
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000013000 chemical inhibitor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229920002581 Glucomannan Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229940046240 glucomannan Drugs 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 2
- 235000005487 catechin Nutrition 0.000 description 2
- 229950001002 cianidanol Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 229920000591 gum Polymers 0.000 description 2
- 235000010485 konjac Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F5/00—Means or methods for preventing, binding, depositing, or removing dust; Preventing explosions or fires
- E21F5/02—Means or methods for preventing, binding, depositing, or removing dust; Preventing explosions or fires by wetting or spraying
- E21F5/06—Fluids used for spraying
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F17/00—Methods or devices for use in mines or tunnels, not covered elsewhere
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F5/00—Means or methods for preventing, binding, depositing, or removing dust; Preventing explosions or fires
Landscapes
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention discloses a compound inhibitor for preventing spontaneous combustion of coal and a preparation method thereof, which consists of industrial brine, gel, surfactant and antioxidant, wherein inorganic salt materials in the brine in the low-temperature oxidation stage of coal have the functions of wetting coal body, reducing temperature and isolating oxygen, and the antioxidant can consume the-OOCH on the surface of the coal 3 Active groups such as peroxy free radical ROO and the like, further reduce the combined action of the oxidation activity of coal, and play roles in inerting coal bodies and inhibiting oxidation processes; in the stage of spontaneous combustion and high-temperature oxidation of coal, brine can react with a gel agent to generate gel, the gel can reduce the loss of moisture of the inhibitor on one hand, strengthen the effect of the composite inhibitor on cooling and heat absorption generated in the coal oxidation heating process, and form a layer of viscous oxygen barrier film on the surface of residual coal on the other hand, so that the gel is prolongedThe self-heating oxidation process of the coal is slowed down, and the multi-layer secondary long-acting stopping and fire preventing and extinguishing effects of the composite stopping agent are realized; and the preparation cost is lower, thus being convenient for wide application.
Description
Technical Field
The invention belongs to the technical field of stopping agents, and particularly relates to a composite stopping agent for preventing spontaneous combustion of coal and a preparation method thereof.
Background
The inhibitor can prevent and extinguish fire by adding a certain agent to prevent or slow down the chemical reaction of coal oxygen. The stopping agent is prepared into liquid to be poured and sprayed on the surface of the residual coal frequently in the coal mine, and the residual coal generates an insulating film between the stopping agent and the air to prevent the coal from being contacted with oxygen, so that the accumulated coal is prevented from spontaneous combustion, and meanwhile, a liquid film formed by the stopping agent can produce the effects of absorbing heat and reducing temperature in the coal oxidation heat release process, so that the effect of delaying the coal oxidation temperature rise is achieved.
Currently, the conventional retarder for mines in China is mainly divided into two types, namely a physical retarder and a chemical retarder. Wherein the physical inhibitor mainly uses MgCl 2 、CaCl 2 The inorganic salt inhibitor such as solution covers the residual coal, the inorganic salt inhibitor has the effect of preventing the combination of coal and oxygen and delaying the oxidation of the coal on the surface of the coal by virtue of strong water absorption, and a single inorganic salt inhibitor is widely applied in engineering practice, but the mode needs high addition amount to achieve better flame retardant effect, the inhibition effect gradually weakens along with the evaporation of water, the water retention is poor, the effective inhibition time is limited, and the inorganic salt inhibitor is only used in the low-temperature oxidation stage of the coal and is not suitable for the high-temperature oxidation stage of the coal. The chemical inhibitor acts on the active groups on the surface of the coal by using the inhibitor, and the oxidizing property of the coal is changed by passivating the active group pair so as to inhibit spontaneous combustion of the coal. The antioxidant such as catechin, vitamin C and the like can react with active groups on the surface of coal to generate a relatively stable structure to reduce the oxidation activity, the oxidation heat release rate of the high-temperature oxidation stage of the coal can be remarkably reduced by the mode, the inhibition efficiency is high, the inhibition effect on the spontaneous combustion high-temperature oxidation stage of the coal is quite obvious, but the inhibition effect of the inhibition agent in the low-temperature oxidation stage of the coal is inferior to that of a conventional physical inhibition agent, and the cost is relatively high.
From the above, the current physical retarder has short duration and is only applicable to the low-temperature oxidation stage of coal; although the chemical inhibitor has long duration, the chemical inhibitor usually uses antioxidants such as catechin, vitamin C and the like as main base materials, the dosage is large, the cost is very high, and the chemical inhibitor is only suitable for the high-temperature oxidation stage of spontaneous combustion of coal and is difficult to realize large-scale application on site. Therefore, how to provide a new stopping agent, which can produce better stopping effect in the low-temperature oxidation stage of coal and the spontaneous combustion high-temperature oxidation stage of coal, has longer stopping time and lower cost, and is one of the research directions in the industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the composite stopping agent for preventing and curing the spontaneous combustion of coal and the preparation method thereof, which can generate multi-level stopping effect in the low-temperature oxidation stage of coal and the high-temperature oxidation stage of spontaneous combustion of coal, improve the stopping performance and the action time of the stopping agent material on the spontaneous combustion of coal, and have lower preparation cost and convenient wide application.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the composite stopping agent for preventing and treating spontaneous combustion of coal is characterized by comprising the following components in parts by weight:
1000-1200 parts of industrial brine, 20-60 parts of gel, 20-25 parts of surfactant and 25-35 parts of antioxidant.
Further, the industrial brine is industrial waste brine obtained by removing sulfate ions by adopting inorganic salt, and the inorganic salt is anhydrous calcium chloride. After the anhydrous calcium chloride and the industrial waste brine are mixed for reaction, sulfate ions in the brine can be effectively removed, and pollution of the sulfate ions to the groundwater environment during subsequent injection into a goaf for fire prevention and extinguishment is greatly reduced.
Further, the gel is one or more of guar gum, xanthan gum and konjac gum. By adopting the materials as the gel, the brine solution can induce acetyl on the molecular chain of glucomannan in the gel to fall off when the spontaneous combustion critical temperature of coal, and hydrogen bonds between partial molecular chain structures become microcrystalline structures, so that the microcrystalline is crosslinked to generate gel.
Further, the surfactant is one or a combination of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether or fatty alcohol polyoxyethylene ether sodium sulfate. Thus, the solution can be mixed more uniformly, and the action effect of the solution is improved.
Further, the antioxidant is one or two of 4, 5-dihydroxyisoquinoline, carnosic acid and 1, 8-naphthalene diol. By adding small amount of antioxidant, the coal surface-OOCH can be consumed 3 Active groups such as peroxy radical ROO, and the like, further inhibits the proceeding of the coal oxygen reaction, and improves the effect of the composite inhibitor for preventing and controlling the spontaneous combustion of coal.
The preparation method of the composite inhibitor for preventing and treating spontaneous combustion of coal comprises the following specific steps:
slowly mixing 1000-1200 parts of industrial brine and 40-50 parts of anhydrous calcium chloride for 15-20 min, and reacting sulfate ions in the brine with the anhydrous calcium chloride to generate calcium sulfate dihydrate precipitate;
filtering calcium sulfate dihydrate sediment in the industrial brine after reaction by utilizing filtering equipment, so that the content of sulfate radical in the industrial brine is reduced, the content of sulfate radical ions in a subsequently prepared composite inhibitor for preventing spontaneous combustion of coal is reduced, the influence of the sulfate radical ions on the surrounding environment after the coal is injected into a goaf is reduced, and the filtered industrial brine is stored for later use;
step three, sequentially adding 20-25 parts of surfactant and 25-35 parts of antioxidant into the industrial brine obtained in the step two according to the parts by weight, and continuously stirring and mixing for 10min at the normal temperature at 100r/min to obtain a uniformly mixed pretreatment inhibitor solution;
and step four, adding 20-60 parts by mass of gel into the pretreatment inhibitor solution obtained in the step three for mixing, uniformly stirring the mixed solution at room temperature at 60r/min, and performing ultrasonic dispersion for 20min to prepare the composite inhibitor for preventing and controlling spontaneous combustion of coal.
When the prepared composite stopping agent is applied to mine coal spontaneous combustion prevention, the specific process is as follows: and arranging pouring drilling holes on the working face along the brackets, designing one drilling hole (the distance is about 5-6 m) for every three brackets, controlling the pouring pressure to be not more than 3MPa, combining the air leakage quantity and the coal loss quantity of the goaf of the working face, pouring the composite stopping agent onto the coal loss surface of the goaf through the drilling holes by using the spraying equipment, and subsequently monitoring the index gas change condition in the natural oxidation process of the coal loss of the goaf.
Compared with the prior art, the beneficial effects of the scheme of the invention are as follows:
1. the invention takes the treated industrial waste brine as the basic raw material of the composite inhibitor, takes the gelling agent, the surfactant and the antioxidant as the main auxiliary additives for improving the inhibition performance of the composite inhibitor, fully utilizes waste industrial brine resources in the preparation and use processes of the material, improves the performance of the composite inhibitor on the basis of the waste brine resources, saves a large amount of water resources in the application process of preventing and controlling spontaneous combustion of coal, and greatly reduces the application cost of the inhibitor material because the consumption of the auxiliary additives is extremely small compared with that of the industrial waste brine.
2. At present, most of the stopping agent solutions adopted in the coal mine site are prepared by dissolving inorganic salt materials such as sodium chloride, magnesium chloride and the like into water to form the stopping agent solution, and brine is an aqueous solution containing high-concentration salts such as sodium chloride, magnesium chloride and the like; therefore, the brine is used as a base material of the inhibitor, and the brine can be used as a good physical inhibitor, on one hand, the inorganic salt material in the brine solution has the functions of absorbing water and wetting, firstly, a layer of water film can be formed on the surface of the coal body, the effects of wetting the coal body, reducing the temperature and isolating oxygen are achieved, and the effects of well inerting the coal body and inhibiting the oxidation process are achieved in the low-temperature oxidation stage of the coal. Secondly, the antioxidant added in the composite inhibitor can consume the coal surface-OOCH 3 The active groups such as peroxy radical ROO and the like further reduce the oxidation activity of coal, on the other hand, the composite inhibitor prepared by brine can prevent and treat spontaneous combustion of coal, a large amount of inorganic salt raw materials can be saved, and the aims of 'treating disaster with waste and changing waste into valuable' are fulfilled.
3. According to the invention, brine, a gel agent and the like are used as a composite stopping agent, the brine can not generate gel, but after the mixed components of konjak gum and xanthan gum or guar gum are added into a brine solution, and after the residual coal is oxidized and heated to 60-80 ℃ (namely, the coal spontaneous combustion high-temperature oxidation stage), inorganic salt substances such as magnesium chloride, calcium chloride and the like contained in the brine can induce acetyl on the molecular chain of glucomannan in the gel agent (namely, the konjak gum and the xanthan gum or the guar gum) to fall off, hydrogen bonds between molecular chain structures of the gel agent become microcrystalline structures, and the microcrystalline is further crosslinked and converted into gel, so that on one hand, the water loss of the stopping agent can be reduced, and the effect of the composite stopping agent on cooling and heat absorption of the coal oxidation and heating process is enhanced; on the other hand, the gel can form a layer of viscous oxygen-isolating film on the surface of the residual coal, so that the proceeding of the self-heating oxidation process of the coal is delayed, and the multi-layer long-acting stopping and fire preventing and extinguishing effects of the composite stopping agent are realized.
4. The whole preparation process is simple, has no damage to underground coal mine environment, stratum and groundwater, and is environment-friendly. In the low-temperature oxidation stage of coal, the composite inhibitor is based on the properties of the inorganic salt solution and the added antioxidant component, and has the water absorption and wetting physical inhibition performance of the physical inhibitor, and the passivation or elimination of the chemical inhibitor, namely-OOCH 3 The chemical resistance of the peroxy radical ROO and other groups is more favorable for the efficient resistance of goaf residual coal; when the coal is oxidized and heated to a certain degree to reach the stage of spontaneous combustion and high-temperature oxidation of the coal, the brine solution can carry out secondary resistance on the residual coal by inducing the gelling agent, so that a multi-level resistance effect can be generated in the stages of low-temperature oxidation of the coal and spontaneous combustion and high-temperature oxidation of the coal, the resistance performance and the action time of the composite resistance agent on spontaneous combustion of the coal are improved, the preparation cost is lower, and the composite resistance agent is convenient for wide application.
Drawings
FIG. 1 is a flow chart of the preparation process of the composite retarder of the invention.
FIG. 2 is a schematic diagram of the retarding mechanism of the composite retarder of the present invention.
FIG. 3 is a graph showing the change in the CO production of raw coal and coal treated with the composite retarder of examples 1 to 3.
FIG. 4 is a graph showing the change in the amount of CO gas produced after the coal is treated with the conventional retarder and the composite retarder of example 3.
Detailed Description
The present invention will be further described below.
Example 1, comprising the steps of:
step one, taking 1200 kg of industrial brine and 50 kg of anhydrous calcium chloride, stirring at 40r/min, mixing for 15-20 min, and reacting sulfate ions in the brine to generate calcium sulfate dihydrate precipitate;
filtering the calcium sulfate dihydrate precipitate in the industrial brine after the reaction by using filtering equipment, so as to reduce the sulfate radical content in the industrial brine, and preserving the filtered industrial brine for later use;
sequentially adding 25 kg of surfactant and 35 kg of antioxidant into industrial brine with sulfate removed, and continuously stirring and mixing for 10min at normal temperature at 100r/min to obtain a uniformly mixed pretreatment inhibitor solution;
and step four, adding 60 kg of gel into the pretreatment inhibitor solution, uniformly stirring the obtained mixed solution at room temperature at 60r/min, and performing ultrasonic dispersion for 20min to form a composite inhibitor for storage.
Example 2, comprising the steps of:
step one, taking 1100 kg of industrial brine and 45 kg of anhydrous calcium chloride, stirring at 40r/min, mixing for 15-20 min, and reacting sulfate ions in the brine to generate calcium sulfate dihydrate precipitate;
filtering the calcium sulfate dihydrate precipitate in the industrial brine after the reaction by using filtering equipment, so as to reduce the sulfate radical content in the industrial brine, and preserving the filtered industrial brine for later use;
sequentially adding 22.5 kg of surfactant and 30 kg of antioxidant into industrial brine with sulfate removed, and continuously stirring and mixing for 10min at normal temperature at 100r/min to obtain a uniformly mixed pretreatment inhibitor solution;
and step four, adding 40 kg of gel into the pretreatment inhibitor solution, uniformly stirring the obtained mixed solution at room temperature at 60r/min, and performing ultrasonic dispersion for 20min to form a composite inhibitor for storage.
Example 3, comprising the steps of:
step one, 1000 kg of industrial brine and 40 kg of anhydrous calcium chloride are taken and stirred at 40r/min, mixed for 15-20 min, sulfate ions in the brine react to generate calcium sulfate dihydrate precipitate;
filtering the calcium sulfate dihydrate precipitate in the industrial brine after the reaction by using filtering equipment, so as to reduce the sulfate radical content in the industrial brine, and preserving the filtered industrial brine for later use;
sequentially adding 20 kg of surfactant and 25 kg of antioxidant into industrial brine with sulfate removed, and continuously stirring and mixing for 10min at normal temperature at 100r/min to obtain a uniformly mixed pretreatment inhibitor solution;
and step four, adding 20 kg of gel into the pretreatment inhibitor solution, uniformly stirring the obtained mixed solution at room temperature at 60r/min, and performing ultrasonic dispersion for 20min to form a composite inhibitor for storage.
The test proves that:
test one:
crushing the collected coal sample to a standard sieve of 0.25-0.5 mm, placing the crushed coal sample into an oven, vacuum drying the crushed coal sample for 48 hours at 40 ℃, and sealing the crushed coal sample for later use. Then, the composite inhibitor prepared in each of examples 1 to 3 was treated with the composite inhibitor prepared in each of examples 1 to 3 at room temperature for 48 hours, and first, the composite inhibitor prepared in each of examples 1 to 3 was immersed in coal at a mass ratio of 5:3 at room temperature and allowed to stand for 8 hours, and then the mixture of the coal and the inhibitor solution was filtered with filter paper, according to general technical conditions for the spontaneous combustion prevention and control inhibitor for coal, to obtain a coal sample. Finally, the treated coal and raw coal are dried in vacuum at 40 ℃ to remove moisture until the quality of the coal is unchanged, and finally raw coal, coal samples treated in example 1, example 2 and example 3 are obtained, temperature programming experiments are carried out on 4 kinds of coal samples, the amounts of CO produced by different coal samples in the oxidation temperature increasing process are compared, and the comparison result is shown in figure 3.
As is evident from fig. 3, CO is an index gas for increasing the temperature of coal oxidation, and CO generated in the oxidation reaction process of the coal sample tends to increase gradually with the increase of temperature, and the CO generated amount reflects the oxidation reaction degree of the coal to a certain extent, so as to further explain the oxidation reaction difficulty of the coal sample. Compared with raw coal, the CO amount generated by the coal sample treated by the inhibitor solution prepared by the invention at the same temperature is greatly reduced, but the change trend is similar to that of the raw coal, so that the composite inhibitor provided by the invention can generate an obvious flame-retardant effect on the raw coal. When the temperature rises to about 200 ℃, the CO production of the coal sample treated by the composite inhibitor is obviously slower than that of raw coal, which shows that the composite inhibitor prepared by the three embodiments has better inhibition effect in the low-temperature oxidation stage of coal and the spontaneous combustion high-temperature oxidation stage of coal, and the best effect of the embodiment 1.
And (2) testing II:
crushing the collected coal sample to a standard sieve of 0.25-0.5 mm, placing the crushed coal sample into an oven, vacuum drying the crushed coal sample for 48 hours at 40 ℃, and sealing the crushed coal sample for later use. Then, at room temperature, naCl and MgCl with 20% mass concentration are used respectively 2 The inhibitor prepared in example 3 was mixed with the coal sample for 48 hours to obtain raw coal, naCl and MgCl 2 And the coal samples processed in the example 3 are subjected to temperature programming experiments, and the CO amounts generated in the oxidation temperature increasing processes of different coal samples are compared, so that the comparison result is shown in figure 4.
As can be seen from the results of FIG. 4, naCl, mgCl during the low temperature oxidation stage 2 The inhibition effect of the treated coal sample is lower than that of raw coal, and the CO production amount of the treated coal sample in the embodiment 3 is lower than that of the conventional inhibitor solution, so that the inhibitor prepared in the embodiment 3 has better inhibition effect in the low-temperature oxidation stage than that of the conventional inhibitor; at 60-80 deg.C (i.e. high-temperature oxidation stage of spontaneous combustion of coal), naCl and MgCl 2 The difference between the CO production of the treated coal sample and the raw coal is small, and the CO production of the treated coal sample in the embodiment 3 obviously tends to increase slowly, because inorganic salt substances such as magnesium chloride and calcium chloride contained in the composite retarder in the embodiment 3 induce acetyl on the molecular chain of glucomannan in the gel to fall off in the oxidation heating process of the coal, hydrogen bonds between molecular chain structures of the glucomannan become microcrystalline structures, the microcrystalline structures are crosslinked to convert gel, on one hand, the loss of moisture of the retarder can be reduced, and the effect of cooling and absorbing heat is generated in the oxidation heating process of the coal; on the other hand, the gel can be formed on the surface of the residual coalAn oxygen barrier film is formed to further delay the coal autothermal oxidation process as shown in fig. 2, so that the CO production in example 3 is significantly reduced, and the stopping agent in example 3 has a good inhibition effect on the coal autothermal oxidation process. And the data of the first test are combined, the stopping effect of the embodiment 2 is similar to that of the embodiment 3 in each stage, and the embodiment 1 is better than that of the embodiment 3, so that two tests prove that the composite stopping agent prepared by the invention has multi-layer stopping effect in the low-temperature oxidation stage and the high-temperature oxidation stage of coal spontaneous combustion, the stopping performance and the acting time of the composite stopping agent on the spontaneous combustion of the coal are improved, and the adopted material cost is lower, so that the composite stopping agent is convenient for wide application.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (6)
1. The composite stopping agent for preventing and treating spontaneous combustion of coal is characterized by comprising the following components in parts by weight:
1000-1200 parts of industrial brine, 20-60 parts of gel, 20-25 parts of surfactant and 25-35 parts of antioxidant.
2. The composite inhibitor for preventing spontaneous combustion of coal according to claim 1, wherein the industrial brine is industrial waste brine from which sulfate ions are removed by using inorganic salt, and the inorganic salt is anhydrous calcium chloride.
3. The composite stopping agent for preventing spontaneous combustion of coal according to claim 1, wherein the gelling agent is one or more of guar gum, xanthan gum and konjac gum.
4. The composite inhibitor for preventing spontaneous combustion of coal according to claim 1, wherein the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether or sodium fatty alcohol polyoxyethylene ether sulfate.
5. The composite inhibitor for preventing spontaneous combustion of coal according to claim 1, wherein the antioxidant is one or a combination of two of 4, 5-dihydroxyisoquinoline, carnosic acid and 1, 8-naphthalene diol.
6. A method for preparing a composite inhibitor for preventing spontaneous combustion of coal according to any one of claims 1 to 5, which comprises the following specific steps:
slowly mixing 1000-1200 parts of industrial brine and 40-50 parts of anhydrous calcium chloride for 15-20 min, and reacting sulfate ions in the brine with the anhydrous calcium chloride to generate calcium sulfate dihydrate precipitate;
filtering the calcium sulfate dihydrate precipitate in the industrial brine after the reaction by using filtering equipment, so as to reduce the sulfate radical content in the industrial brine, and preserving the filtered industrial brine for later use;
step three, sequentially adding 20-25 parts of surfactant and 25-35 parts of antioxidant into the industrial brine obtained in the step two according to the parts by weight, and continuously stirring and mixing for 10min at the normal temperature at 100r/min to obtain a uniformly mixed pretreatment inhibitor solution;
and step four, adding 20-60 parts by mass of gel into the pretreatment inhibitor solution obtained in the step three for mixing, uniformly stirring the mixed solution at room temperature at 60r/min, and performing ultrasonic dispersion for 20min to prepare the composite inhibitor for preventing and controlling spontaneous combustion of coal.
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