CN110219691B - Environment-friendly composite stopping agent for preventing coal spontaneous combustion and preparation method thereof - Google Patents
Environment-friendly composite stopping agent for preventing coal spontaneous combustion and preparation method thereof Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000009841 combustion method Methods 0.000 title description 2
- 238000002485 combustion reaction Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001868 water Inorganic materials 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
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- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims abstract description 37
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims abstract description 37
- 229940114124 ferulic acid Drugs 0.000 claims abstract description 37
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000001785 ferulic acid Nutrition 0.000 claims abstract description 37
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims abstract description 37
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 22
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 22
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 22
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 13
- 235000015099 wheat brans Nutrition 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 29
- 230000005764 inhibitory process Effects 0.000 abstract description 28
- 230000003647 oxidation Effects 0.000 abstract description 27
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- 238000012360 testing method Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 8
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- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 6
- 229930003268 Vitamin C Natural products 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 235000019154 vitamin C Nutrition 0.000 description 6
- 239000011718 vitamin C Substances 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- 229930002877 anthocyanin Natural products 0.000 description 2
- 235000010208 anthocyanin Nutrition 0.000 description 2
- 239000004410 anthocyanin Substances 0.000 description 2
- 150000004636 anthocyanins Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000002925 chemical effect Effects 0.000 description 2
- -1 hydroxyl free radical Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 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 1
- 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 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000007162 Ferula assa foetida Nutrition 0.000 description 1
- 244000228957 Ferula foetida Species 0.000 description 1
- 235000012850 Ferula foetida Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013000 chemical inhibitor Substances 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0007—Solid extinguishing substances
- A62D1/0014—Powders; Granules
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (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
An environment-friendly composite stopping agent for preventing coal spontaneous combustion and a preparation method thereof, wherein the stopping agent is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is 1: (3-5): (3-5): (4-6), wherein the water accounts for 50-67% of the environment-friendly composite inhibitor by mass; the composite super absorbent resin is compounded by polyethylene glycol, polyvinyl alcohol and acrylic acid with a neutralization degree of 70%. Mixing and stirring the raw materials in proportion for 45-60 min at room temperature to form a colloidal composite stopping agent, drying at a constant temperature of 75-85 ℃ until the mass reduction ratio per hour is less than 3%, and grinding into powder with the particle size of less than 1 mm. The inhibitor has good stability and strong oxidation resistance, can reduce the production cost, fully prevent the spontaneous combustion of coal, improve the inhibition effect and prolong the service life of the inhibitor; the preparation process is simple and can realize high-efficiency production.
Description
Technical Field
The invention belongs to the field of spontaneous combustion inhibition of coal mine fire prevention and extinguishment, and particularly relates to an inhibitor and a preparation method thereof, in particular to an environment-friendly composite inhibitor for preventing and controlling coal spontaneous combustion and a preparation method thereof.
Background
Coal is still one of main energy sources and industrial raw materials in the present stage and quite a long time later in China, and occupies a main position in an energy structure, but the coal faces serious natural coal ignition threat for a long time in the processes of mining, storing and applying, and the safe production and sustainable development of coal mines are seriously influenced. The spontaneous combustion of coal not only causes the loss of a large amount of coal resources and equipment, but also generates toxic and harmful gas which poses serious life threat to underground workers. Therefore, the adoption of an efficient means to prevent and control the spontaneous combustion of the coal has important significance for reducing the economic loss of the coal industry and improving the guarantee level of the life safety of workers.
Coal spontaneous combustion is essentially a kinetic process of coal low-temperature oxidation temperature rise, according to the widely accepted coal oxidation hypothesis at present, chemical adsorption and oxidation reaction of coal and oxygen are key reasons for coal spontaneous combustion generation and development, and from the microscopic viewpoint, the coal spontaneous combustion reaction mainly comprises chemical reaction of key active groups (such as methyl, methylene, lipoxyl oxygen free radicals and the like) in coal and oxygen. Therefore, the coal spontaneous combustion prevention and control can be subjected to root management from the aspect of free radical consumption.
The antioxidant is one of chemical inhibitors, and is used for firstly reacting with active groups on the surface of coal to generate relatively stable chain rings, destroying or reducing the number of the active groups in the coal in advance and inhibiting the coal from generating chemical adsorption; or the free radicals are captured through chemical reaction to generate a stable transition intermediate product, and the chain reaction process of coal oxidation is cut off, so that the spontaneous combustion of coal is prevented.
At present, the antioxidant inhibitors such as catechin, vitamin C and anthocyanin which have been studied have outstanding inhibition effects in inhibiting active groups on the surface of coal and blocking spontaneous combustion chain reaction of coal, but have the following limitations: the antioxidant is unstable in chemical property and easy to oxidize; the molecular structure of the material has more hydroxyl groups, and the hydroxyl groups can not play a role in inhibition at a high temperature stage and can promote spontaneous combustion; some stopping agents such as anthocyanin are difficult to popularize and use on site due to high price; in addition, the coal mine site environment is complex and changeable, and only the chemical inhibition effect of the antioxidant is used for preventing and controlling the spontaneous combustion of coal, so that the problems of non-ideal inhibition effect, short inhibition life and the like exist.
Disclosure of Invention
The invention aims to provide an environment-friendly composite stopping agent for preventing coal spontaneous combustion and a preparation method thereof, the stopping agent has good stability and strong oxidation resistance, can reduce the production cost, fully prevent the coal spontaneous combustion, improve the stopping effect and prolong the service life of the stopping agent; the preparation method is simple, and the environment-friendly composite stopping agent can be efficiently produced and processed.
In order to achieve the purpose, the environment-friendly composite stopping agent is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): (3-5): (3-5): (4-6), wherein the water accounts for 50-67% of the environment-friendly composite inhibitor by mass; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5.
preferably, the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is 1: 3: 4: and 4, the water accounts for 60 percent of the mass of the environment-friendly composite stopping agent.
Preferably, the ferulic acid is extracted from wheat bran.
The invention also provides a preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion, which comprises the following steps:
(1) crushing wheat bran in a crusher for 10min, sieving to obtain 50-70 mesh wheat bran, adding water, heating and stirring for 30min while maintaining the temperature at 50-70 deg.C to control the concentration of the wheat bran mixture at 80 g/L, and adding 40 mmol/L ZnCl2Then, using 1 mol/L hydrochloric acid solution to adjust the pH value of the wheat bran mixed solution to 4-6, finally adding 3% of xylanase solution by mass fraction, and carrying out enzymolysis for 6 hours at the constant temperature of 45-55 ℃, wherein the main component of the final precipitate is ferulic acid;
(2) preparing the composite super absorbent resin: mixing acrylic acid with a neutralization degree of 70% with water according to a proportion, heating to 50 ℃, adding a polyethylene glycol solution under a constant temperature condition, and stirring for 15 min; heating to 65-75 ℃, adding polyvinyl alcohol, reacting for 2 hours, stopping stirring when the color of the solution turns yellow, and standing for 35min to precipitate the composite super absorbent resin;
(3) preparation of the composite stopping agent: at room temperature, adding sodium bicarbonate, ammonium bicarbonate, water and ferulic acid prepared in the step (1) into the composite super absorbent resin prepared in the step (2) in proportion, and stirring for 45-60 min to form a colloidal composite stopping agent; and (3) drying the colloidal composite stopping agent at a constant temperature in an environment of 75-85 ℃ until the mass reduction ratio of the colloidal composite stopping agent per hour is less than 3%, and grinding the dried product into powder with the particle size of less than 1mm to obtain the composite stopping agent.
Preferably, in the step (1), wheat bran of 60 meshes is selected by a sieve; the temperature was kept constant at 60 ℃ during stirring.
Preferably, the pH value of the wheat bran mixed solution is adjusted to 5 in the step (1); the xylanase solution is subjected to enzymolysis at a constant temperature of 50 ℃.
Preferably, in the step (2), the mixed solution of acrylic acid with 70% neutralization degree and polyethylene glycol is heated to 70 ℃ and then polyvinyl alcohol is added.
Preferably, the colloidal composite stopping agent is formed after stirring for 60min in the step (3); and (3) placing the colloidal composite stopping agent in an environment of 80 ℃ for constant-temperature drying.
Compared with the prior art, the invention has the following advantages:
(1) and (6) root source processing. The invention uses ferulic acid extracted from natural grains as a main inhibition component for the first time, the ferulic acid has stable chemical property and strong oxidation resistance, and can effectively inhibit or eliminate main active groups (such as methyl, methylene, hydroxyl free radical, carboxyl free radical, peroxy radical and the like) in the coal oxidation action, thereby inhibiting or cutting off the coal oxidation composite chain reaction process and realizing the high-efficiency prevention and control of coal spontaneous combustion in chemical essence.
(2) Physical and chemical synergy. The composite super absorbent resin has a spatial three-dimensional interpenetrating network structure, and can be used as a carrier to embed ferulic acid serving as a main component of an antioxidant and sodium bicarbonate and ammonium bicarbonate serving as main components of a fire extinguishing agent into the three-dimensional structure of the resin so as to obtain cage-shaped protection, thereby realizing the high-efficiency combination of fire prevention and fire extinguishing and prolonging the inhibition life of the antioxidant; in addition, the composite super absorbent resin is prepared by taking polyethylene glycol, polyvinyl alcohol, acrylic acid with 70% neutralization degree and water as raw materials, has the advantages of super water absorption and water retention capacity, environmental friendliness, good water solubility and biodegradability, overcomes the defects that hydrogel is directly generated in the previous process for preparing the water absorbent resin, and the final product is difficult to take out of a reactor due to high viscosity or gel, and realizes industrial continuous production.
(3) Green and harmless, low cost and strong popularization. The raw materials used in the invention have rich sources, are green and environment-friendly, have low cost, simple preparation process and no pollution; the asafetida can be prepared by chemical synthesis, can be extracted from natural plant wheat bran by adding corresponding enzyme, and has the advantages of low cost, wide source and convenient popularization.
From the perspective of consuming key groups in coal, the invention prepares the environment-friendly composite stopping agent which is efficient, stable and low in cost and has the synergistic effect of chemical stopping and physical stopping through a stopping effect test, and realizes green and efficient prevention and control of coal spontaneous combustion disasters.
Detailed Description
The present invention will be described in further detail with reference to examples.
Comparative example 1
According to incomplete statistics, the physical stopping agent in the application of the existing coal mine field stopping agent belongs to CaCl2Most commonly, it is preferred because of its low cost, wide source, and simple process, and is a typical comparative example of the present invention. Firstly, collecting a coal sample from a mining area with serious natural coal ignition, sealing the coal sample, and sending the coal sample to a laboratory, and then preparing the coal sample into a coal sample with a particle size of 60 meshes according to a preparation method GB474-2008 of the coal sample; secondly, a part of untreated original coal samples are stored in vacuum for later use and used as a comparative example of subsequent tests; then a part of the original coal sample is taken and used as a physical stopping agent CaCl2After treatment, the samples were stored under vacuum for later testing as a comparative example.
Respectively taking an original coal sample and CaCl2The method comprises the steps of treating a coal sample in a inhibition manner, measuring the distribution and the content of radicals in different coals by a Fourier transform infrared spectrometer according to the test steps of coal oxidation kinetics theory and application published by scientific publishing agency, 2012 and 12 months, measuring the oxygen consumption and the cross point temperature at 70 ℃ in the oxidation heating process of different coals by a coal spontaneous combustion tendency oxidation kinetics measuring instrument, further calculating to obtain a coal spontaneous combustion tendency oxidation kinetics judgment index, measuring the CO generation rate and the inhibition rate thereof by a coal spontaneous combustion characteristic comprehensive measuring device, and comparing relevant data with the inhibition effect of the embodiment of the invention as shown in Table 2.
Comparative example No. two
In addition to the selection of physical stopping agents as comparative examples, the selection of vitamin C, a chemical stopping agent that has been widely adopted in mining areas, was used as comparative example. Vitamin C is widely applied to the fields of biomedicine, corrosion prevention, aging resistance and the like due to the strong oxidation resistance, has strong free radical scavenging capacity, and can be used as another typical comparative example of the invention by effectively blocking the chain reaction of lipid oxygen free radicals in coal to generate stable ether bonds so as to inhibit the development of low-temperature oxidation reaction of the coal.
The coal sample collection and preparation process of the comparative example is completely the same as that of the comparative example 1, vitamin C is added into the selected part of original coal samples according to the proportion of 6 percent of the total mass ratio, and the inhibition treated coal samples are stored in a vacuum environment for later use. Taking a resistance chemical treatment coal sample, adopting a Fourier transform infrared spectrometer to measure the distribution and the content of radicals in coal according to the test steps described in coal oxidation kinetics theory and application published by scientific publishing house 2012, 12 months, adopting a coal spontaneous combustion tendency oxidation kinetics determinator to measure the oxygen consumption at 70 ℃ and the cross point temperature in the coal oxidation heating process, further calculating to obtain a coal spontaneous combustion tendency oxidation kinetics judgment index, adopting a coal spontaneous combustion characteristic comprehensive determination device to measure the CO generation rate and the resistance rate thereof, and obtaining relevant data shown in Table 2 for comparing the resistance chemical effect with the resistance chemical effect of the embodiment of the invention.
Example one
An environment-friendly composite stopping agent for preventing coal spontaneous combustion, which is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): 5: 3: 6, the water accounts for 50 percent of the mass of the environment-friendly composite stopping agent; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5; the ferulic acid is extracted from testa Tritici.
The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion comprises the following steps:
(1) the ferulic acid is prepared by pulverizing testa Tritici for 10min in a mincing machine, sieving to obtain 50 mesh testa Tritici, adding water, heating and stirring for 30min while keeping constant temperature at 50 deg.C to control the testa Tritici mixture concentration at 80 g/L, and adding 40 mmol/L ZnCl2Then, using 1 mol/L hydrochloric acid solution to adjust the pH value of the wheat bran to 6, finally adding 3% xylanase solution by mass fraction and carrying out enzymolysis for 6h at the constant temperature of 55 ℃, wherein the main component of the final precipitate is the required antioxidant ferulic acid;
(2) preparing the composite super absorbent resin: mixing acrylic acid with a neutralization degree of 70% with water according to a proportion, heating to 50 ℃, adding a polyethylene glycol solution under a constant temperature condition, and stirring for 15 min; then heating to 75 ℃, adding polyvinyl alcohol for reaction for 2h, stopping stirring when the color of the solution turns yellow, and standing for 35min to precipitate the composite super absorbent resin;
(3) preparation of the composite stopping agent: at room temperature, adding sodium bicarbonate, ammonium bicarbonate, water and ferulic acid prepared in the step (1) into the composite super absorbent resin prepared in the step (2) in proportion, and stirring for 45min to form a colloidal composite stopping agent; and (3) drying the colloidal composite stopping agent at a constant temperature in an environment of 85 ℃ until the mass reduction ratio of the colloidal composite stopping agent per hour is less than 3%, and grinding the dried product into powder with the particle size of less than 1mm to obtain the composite stopping agent.
The coal sample collection and preparation process of this example is completely the same as that of comparative example 1, the inhibitor prepared in this example is added to a selected portion of the original coal sample in a proportion of 6% by total mass, and the inhibition treated coal sample is stored in a vacuum environment for use. Taking a resistance chemical treatment coal sample, measuring the distribution and the content of radicals in coal by adopting a Fourier transform infrared spectrometer according to the test steps in the theory and the application of coal oxidation kinetics published by the scientific publishing company in 12 months 2012, measuring the oxygen consumption and the cross point temperature at 70 ℃ in the coal oxidation temperature rise process by adopting a coal spontaneous combustion tendency oxidation kinetics measuring instrument, further calculating to obtain a coal spontaneous combustion tendency oxidation kinetics judgment index, and measuring the CO generation rate and the resistance chemical rate by adopting a coal spontaneous combustion characteristic comprehensive measuring device, wherein the relevant data are shown in a table 2. When the inhibitor is applied on site, the inhibitor product prepared by the method is mixed with water in a mass ratio of 1:100 in areas with fire hazard, and then the inhibitor product is practically applied in a pouring mode.
Example two
An environment-friendly composite stopping agent for preventing coal spontaneous combustion, which is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): 4: 5: 5, the water accounts for 55 percent of the mass of the environment-friendly composite stopping agent; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5; the ferulic acid is extracted from testa Tritici.
The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion is basically the same as the embodiment, and different preparation process conditions are shown in Table 1.
The effect test of this embodiment refers to the test processes of preparation of coal sample, radical distribution/oxygen consumption/cross point temperature/coal spontaneous combustion tendency oxidation kinetics determination index/CO generation rate/inhibition rate of inhibition coal sample, and the like, and is the same as the first embodiment, and when the method is applied in the actual field, the method is also consistent with the first embodiment. The relevant data are shown in table 2.
EXAMPLE III
An environment-friendly composite stopping agent for preventing coal spontaneous combustion, which is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): 3: 4: 6, the water accounts for 63 percent of the mass of the environment-friendly composite stopping agent; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5; the ferulic acid is extracted from testa Tritici.
The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion is basically the same as the embodiment, and different preparation process conditions are shown in Table 1.
The effect test of this embodiment refers to the test processes of preparation of coal sample, radical distribution/oxygen consumption/cross point temperature/coal spontaneous combustion tendency oxidation kinetics determination index/CO generation rate/inhibition rate of inhibition coal sample, and the like, and is the same as the first embodiment, and when the method is applied in the actual field, the method is also consistent with the first embodiment. The relevant data are shown in table 2.
Example four
An environment-friendly composite stopping agent for preventing coal spontaneous combustion, which is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): 3: 4: 4, the water accounts for 60 percent of the mass of the environment-friendly composite stopping agent; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5; the ferulic acid is extracted from testa Tritici.
The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion is basically the same as the embodiment, and different preparation process conditions are shown in Table 1.
The effect test of this embodiment refers to the test processes of preparation of coal sample, radical distribution/oxygen consumption/cross point temperature/coal spontaneous combustion tendency oxidation kinetics determination index/CO generation rate/inhibition rate of inhibition coal sample, and the like, and is the same as the first embodiment, and when the method is applied in the actual field, the method is also consistent with the first embodiment. The relevant data are shown in table 2.
EXAMPLE five
An environment-friendly composite stopping agent for preventing coal spontaneous combustion, which is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): 3: 5: 5, the water accounts for 67 percent of the environment-friendly composite stopping agent by mass; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5; the ferulic acid is extracted from testa Tritici.
The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion is basically the same as the embodiment, and different preparation process conditions are shown in Table 1.
The effect test of this embodiment refers to the test processes of preparation of coal sample, radical distribution/oxygen consumption/cross point temperature/coal spontaneous combustion tendency oxidation kinetics determination index/CO generation rate/inhibition rate of inhibition coal sample, and the like, and is the same as the first embodiment, and when the method is applied in the actual field, the method is also consistent with the first embodiment. The relevant data are shown in table 2.
Table 1 different preparation process conditions of example two to example five
TABLE 2 Oxidation characteristics of the original coal sample and the different hindered coal samples
Note: 1. the determination criterion of the coal spontaneous combustion tendency judgment index is 'oxidation kinetics determination method of coal spontaneous combustion tendency AQ/T1068-2008'; 2. the determination of the stopping rate is based on general technical conditions MT/T700-1997 of stopping agents for coal mine fire prevention.
Table 2 shows the coal compositions of the examplesThe comparative analysis of the test results of flame retardant effect shows that the first to fifth examples and the conventional commonly used physical retardant CaCl2Compared with the original coal sample, the active group content in the coal sample treated by the inhibitor is reduced, particularly the content of methyl/methylene is obviously reduced, the temperature of a cross point is increased, the judgment index of spontaneous combustion tendency is increased, the inhibition rate is increased, the trend is more and more obvious along with the increase of the addition proportion of ferulic acid, and the novel antioxidant inhibitor has better inhibition effect; meanwhile, after the coal sample is blocked by the vitamin C, the contents of methyl and methylene are higher than those of the raw coal, and compared with the first to fifth examples, the blocking effect is not obvious.
In the above examples, the fourth example had the best effect, with CaCl2Compared with the coal sample treated by the stopping agent, the methyl/methylene content of the treated coal sample is reduced by 48 percent, the hydroxyl content is reduced by 45 percent, the carboxyl content is reduced by 40 percent, the temperature of a cross point is increased by 49 ℃, the spontaneous combustion tendency judgment index is increased to 1184, namely the easy spontaneous combustion coal sample is changed into the difficult spontaneous combustion coal sample after being stopped, and the stopping efficiency is improved by 38 percent; compared with the coal sample treated by the vitamin C inhibitor, the methyl/methylene content of the treated coal sample is reduced by 55%, the hydroxyl content is reduced by 17%, the carboxyl content is reduced by 21%, the temperature of a cross point is increased by 35 ℃, the spontaneous combustion tendency judgment index is increased to 1184, and the inhibition efficiency is improved by 17%.
Analysis of the inhibition effect test result shows that the main active groups with the coal oxygen action can be effectively removed, so that the coal oxygen composite chain reaction is interrupted, and the coal spontaneous combustion efficient control in chemical essence is realized; and because of the high water absorption and retention property of the composite super absorbent resin, the composite super absorbent resin can fully exert the fire prevention and extinguishing effects of water, so that the product has both chemical inhibition effect and physical inhibition effect. In addition, the preparation process is simple and convenient, the preparation material is cheap and environment-friendly, and the popularization and application prospect is wide.
Claims (8)
1. An environment-friendly composite stopping agent for preventing coal spontaneous combustion is characterized in that the environment-friendly composite stopping agent is prepared from composite super absorbent resin, ferulic acid, sodium bicarbonate, ammonium bicarbonate and water; the mass ratio of the ferulic acid to the composite super absorbent resin to the sodium bicarbonate to the ammonium bicarbonate is (1): (3-5): (3-5): (4-6), wherein the water accounts for 50-67% of the environment-friendly composite inhibitor by mass; the composite super absorbent resin is prepared by compounding polyethylene glycol, polyvinyl alcohol, acrylic acid with a neutralization degree of 70% and water, wherein the mass ratio of the polyethylene glycol to the polyvinyl alcohol to the acrylic acid with a neutralization degree of 70% to the water is 1: 1.5: 10: 5.
2. the environment-friendly composite stopping agent for preventing and treating spontaneous combustion of coal as claimed in claim 1, wherein the mass ratio of ferulic acid to composite super absorbent resin, sodium bicarbonate and ammonium bicarbonate is 1: 3: 4: and 4, the water accounts for 60 percent of the mass of the environment-friendly composite stopping agent.
3. The environment-friendly composite stopping agent for preventing and treating spontaneous combustion of coal as claimed in claim 1 or 2, wherein the ferulic acid is prepared by extracting from wheat bran.
4. The preparation method of the environment-friendly composite stopping agent for preventing coal spontaneous combustion is characterized by comprising the following steps:
(1) the ferulic acid is prepared by pulverizing testa Tritici for 10min in a blender, sieving to obtain 50-70 mesh testa Tritici, adding water, heating and stirring for 30min while keeping constant temperature at 50-70 deg.C to control testa Tritici mixture concentration at 80 g/L, and adding 40 mmol/L ZnCl2Then, using 1 mol/L hydrochloric acid solution to adjust the pH value of the wheat bran mixed solution to 4-6, finally adding 3% of xylanase solution by mass fraction, and carrying out enzymolysis for 6 hours at the constant temperature of 45-55 ℃, wherein the main component of the final precipitate is ferulic acid;
(2) preparing the composite super absorbent resin: mixing acrylic acid with a neutralization degree of 70% with water according to a proportion, heating to 50 ℃, adding polyethylene glycol under a constant temperature condition, and stirring for 15 min; heating to 65-75 ℃, adding polyvinyl alcohol, reacting for 2 hours, stopping stirring when the color of the solution turns yellow, and standing for 35min to precipitate the composite super absorbent resin;
(3) preparation of the composite stopping agent: at room temperature, adding sodium bicarbonate, ammonium bicarbonate, water and ferulic acid prepared in the step (1) into the composite super absorbent resin prepared in the step (2) in proportion, and stirring for 45-60 min to form a colloidal composite stopping agent; and (3) drying the colloidal composite stopping agent at a constant temperature in an environment of 75-85 ℃ until the mass reduction ratio of the colloidal composite stopping agent per hour is less than 3%, and grinding the dried product into powder with the particle size of less than 1mm to obtain the composite stopping agent.
5. The method for preparing the environment-friendly composite stopping agent for preventing the spontaneous combustion of the coal as claimed in claim 4, wherein in the step (1), wheat bran of 60 meshes is selected by a sieve; the temperature was kept constant at 60 ℃ during stirring.
6. The method for preparing the environment-friendly composite stopping agent for preventing and treating spontaneous combustion of coal as claimed in claim 4 or 5, wherein in the step (1), the pH value of wheat bran mixed liquor is adjusted to 5; the xylanase solution is subjected to enzymolysis at a constant temperature of 50 ℃.
7. The preparation method of the environment-friendly composite stopping agent for preventing and treating spontaneous combustion of coal as claimed in claim 4 or 5, wherein in the step (2), the polyvinyl alcohol is added after the temperature of the mixed solution of acrylic acid with 70% neutralization degree and polyethylene glycol is raised to 70 ℃.
8. The preparation method of the environment-friendly composite stopping agent for preventing and treating spontaneous combustion of coal as claimed in claim 4 or 5, wherein the colloidal composite stopping agent is formed after stirring in the step (3) for 60 min; and (3) placing the colloidal composite stopping agent in an environment of 80 ℃ for constant-temperature drying.
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