CN102336994B - Polyvinyl alcohol foam oxygen insulation material and preparation method and application thereof - Google Patents
Polyvinyl alcohol foam oxygen insulation material and preparation method and application thereof Download PDFInfo
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- CN102336994B CN102336994B CN 201110182699 CN201110182699A CN102336994B CN 102336994 B CN102336994 B CN 102336994B CN 201110182699 CN201110182699 CN 201110182699 CN 201110182699 A CN201110182699 A CN 201110182699A CN 102336994 B CN102336994 B CN 102336994B
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 101
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 101
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 93
- 239000001301 oxygen Substances 0.000 title claims abstract description 93
- 239000006260 foam Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000012774 insulation material Substances 0.000 title abstract 4
- 239000003245 coal Substances 0.000 claims abstract description 79
- 239000002904 solvent Substances 0.000 claims abstract description 38
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005187 foaming Methods 0.000 claims abstract description 16
- 230000004888 barrier function Effects 0.000 claims description 78
- 239000000463 material Substances 0.000 claims description 70
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002485 combustion reaction Methods 0.000 claims description 23
- 230000002269 spontaneous effect Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- -1 olefin sulfonate Chemical class 0.000 claims description 20
- 229910021538 borax Inorganic materials 0.000 claims description 17
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 17
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 17
- 239000004328 sodium tetraborate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 239000004088 foaming agent Substances 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 239000006261 foam material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyvinyl alcohol foam oxygen insulation material, which comprises a component (A) and a component (B), wherein the component (A) comprises a solvent, and 3-8 percent by weight of polyvinyl alcohol, 0.5-1.5 percent by weight of linear hydrocarbon organic alcohol or ester and 0.04-0.10 percent by weight of foaming agent based on the total amount of the solvents contained in the component (A) and the component (B); the component (B) comprises 0.1-0.3 percent by weight of borate based on the total amount of solvents contained in the component (A) and the component (B); and the mass ratio of the solvent contained in the component (A) to the solvent contained in the component (B) is (5-9):1. A method for preparing the polyvinyl alcohol foam oxygen insulation material comprises the following steps of: dissolving polyvinyl alcohol into the solvent at constant temperature 70-95 DEG C, performing return flow agitation for 30-60 minutes, cooling to room temperature, and adding the linear hydrocarbon organic alcohol or ester and the foaming agent to obtain the component (A); adding borate into the solvent to obtain the component (B); and foaming the component (A), spraying onto a coal surface and spraying the component (B) to form a foam gel oxygen insulation material layer which plays a good role in sealing and insulating oxygen on the coal surface.
Description
Technical field
The present invention relates to a kind of fire-retardant material, relate in particular to a kind of polyvinyl alcohol (PVA) oxygen barrier material that is used to prevent spontaneous combustion of coal.
Background technology
Spontaneous combustion of coal is one of great disaster that threatens colliery and coal fortune safety.In China state-owned emphasis colliery, exist the mine of spontaneous fire danger to account for 51.3%,, seriously threatening the people's lives and property safety because the fire that spontaneous combustion of coal causes accounts for more than 90% of total fire number.Spontaneous combustion of coal produces a large amount of SO
2, H
2S, CO and CO
2Gas, serious environment pollution.Coal and airborne oxygen generation redox reaction are the major causes of coal self-heating, spontaneous combustion, and the reaction process of therefore controlling coal and oxygen is the self-heating of prevention coal, the important means of spontaneous combustion.Contact, reduce concentration of oxygen in the dump by what intercept oxygen in coal and the air, can suppress and slow down the oxidation heat liberation speed of coal, thereby effectively suppress the coal temperature rise, reach the purpose of preventing dump self-heating, spontaneous combustion.Being used to of using at present stops the stopping agent kind of coal oxidation spontaneous combustion to mainly contain inorganic salt (CaCl for example
2, MgCl
2, NaCl etc.) aqueous solution, Ca (OH)
2Solution, silicon gel etc., adopt these stopping agents to play certain effect for the control of the spontaneous combustion of coal mine, but in the standing storage of coal and long-distance transport process, there are shortcomings such as material settling out is poor, adaptive surface is little, therefore unsatisfactory for the control of spontaneous combustion of coal in the standing storage of coal and the long-distance transport process, and described stopping agent can cause the ash content in the coal to increase, and influences the quality of coal.In addition, coal stack and the process of transportation in slide because the coal seam may appear in factor affecting such as gravity, the oxygen barrier material that therefore also requires to cover the coal surface has mechanical property preferably.Prevailing organic foam fire retardant material on market at present, low as heat resisting temperatures such as polystyrene foam, polyvinyl chloride foam, polyurethane foams, emit a large amount of heats after the burning, produce black smoke poison gas, both caused environmental pollution, also become one of principal element that causes casualties in the fire, therefore be unsuitable for as the material that in coal long-distance transport process, prevents spontaneous combustion of coal.
The present inventor finds that after deliberation polyvinyl alcohol (PVA) has minimum oxygen permeability coefficient as a kind of high molecular polymer, film-forming properties preferably, environmentally safe, therefore can choose polyvinyl alcohol is base-material, develops a kind of polyvinyl alcohol oxygen barrier covering material that prevents that spontaneous combustion of coal from using.The inventor further discovers, with when adding the formulated polyvinyl alcohol modification frothing solution of properties-correcting agent and whipping agent and after the foam device foaming, be sprayed at the coal surface, though can obtain certain oxygen barrier effect, but the foam materials that forms is extremely unstable, break easily, can't be used for the standing storage and the long-distance transport process of coal; Consider that polyvinyl alcohol is very sensitive to borate, cause gelation easily, to be sprayed on the coal surface as the formulated modified polyvinyl alcohol oxygen barrier gelatinous material of setting accelerator by adding properties-correcting agent and borate, can form gel-film on the surface, coal seam, but such oxygen barrier gelatinous material is because mobile poor, cause when at the certain thickness gel-film of coal surface coverage, the usage quantity of oxygen barrier material is bigger, and use cost increases.Therefore, in order to overcome above-mentioned technological deficiency, need the polyvinyl alcohol oxygen barrier material that a kind of stability of exploitation is strong, the oxygen barrier performance is high, not only can suppress the spontaneous combustion problem of coal in long-term storage and transport process effectively, and under the prerequisite of the sealing oxygen barrier layer that covers coal of the same area surface and acquisition same thickness, can reduce the use cost of oxygen barrier material.
Summary of the invention
One of purpose of the present invention provides a kind of novel polyvinyl alcohol foam oxygen barrier material.
Another object of the present invention provides a kind of method for preparing polyvinyl alcohol foam oxygen barrier material.
Polyvinyl alcohol foam oxygen barrier material provided by the present invention comprises component (A) and component (B), wherein, comprise solvent in the described component (A) and in component (A) and (B) total amount of contained solvent be the polyvinyl alcohol of 100wt% 3-8wt%, the whipping agent of the organic pure and mild 0.04-0.10wt% of straight chain hydrocarbon of 0.5-1.5wt%, comprise solvent in the described component (B) and in component (A) and (B) total amount of contained solvent be the borate of 100wt% 0.1-0.3wt%, and in the described component (A) in contained solvent and the component (B) mass ratio of contained solvent be 5-9: 1.
A preferred implementation according to polyvinyl alcohol foam oxygen barrier material provided by the present invention, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3-6, the carbonatoms of the organic alcohol of more preferably described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3, and further the organic alcohol of preferred described straight chain hydrocarbon is glycerol.
According to a preferred implementation of polyvinyl alcohol foam oxygen barrier material provided by the present invention, component (A) and (B) in contained solvent be water, more preferably deionized water.
In polyvinyl alcohol foam oxygen barrier material provided by the invention, described whipping agent is this area anionic whipping agent commonly used, for example sodium laurylsulfonate, α-sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfonate, sodium lignosulfonate etc.
According to a preferred implementation of polyvinyl alcohol foam oxygen barrier material provided by the present invention, described borate is alkali metal borate or alkaline earth metal borate, more preferably alkali metal borate, more preferably Sodium Tetraborate.
In the method for the aforesaid polyvinyl alcohol foam oxygen barrier of preparation provided by the present invention material, described component (A) makes as follows: under 70-95 ℃ steady temperature, polyvinyl alcohol is dissolved in the solvent, reflux and stirred 30-60 minute, be cooled to room temperature, add organic alcohol of straight chain hydrocarbon or straight chain hydrocarbon organic ester again, stir, add whipping agent then, promptly get component (A); Described component (B) makes as follows: borate is added in the solvent, stir, promptly get component (B).
In polyvinyl alcohol foam oxygen barrier preparation methods provided by the present invention, in two independent step, prepare component (A) and (B) respectively, do not have particular requirement in proper order for component (A) and preparation (B), and the component that makes (A) and component (B) has indefinite stability in storage when separating mutually.In the use of component (A) and component (B), component (A) in case will form gel fast with component (B) combination, provides polyvinyl alcohol foam oxygen barrier material of the present invention after foaming.
A preferred implementation according to preparation method provided by the present invention, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3-6, the carbonatoms of the organic alcohol of more preferably described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3, and further the organic alcohol of preferred described straight chain hydrocarbon is glycerol.
According to a preparation method's provided by the present invention preferred implementation, contained solvent is water, more preferably deionized water in component (A) and the component (B); Contained whipping agent is this area anionic whipping agent commonly used, for example sodium laurylsulfonate, α-sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfonate, sodium lignosulfonate etc. in the component (A).
According to a preparation method's provided by the present invention preferred implementation, described borate is alkali metal borate or alkaline earth metal borate, more preferably alkali metal borate, more preferably Sodium Tetraborate.
In the present invention, term " the organic alcohol of straight chain hydrocarbon " is meant that the hydrogen atom on the saturated carbon atom is replaced formed compound by hydroxyl in the straight chain hydrocarbon molecule.
In addition, the present invention also provides described polyvinyl alcohol foam oxygen barrier material to be used to prevent the purposes of spontaneous combustion of coal.Particularly, the foam that described component (A) is obtained after the foam device foaming is sprayed on the coal surface, forms foam surface, then described component (B) is sprayed on the described foam surface, forms polyvinyl alcohol foam oxygen barrier material.
In the present invention, do not require, in the scope of foamy cell diameter at 1.0-3.0mm of preferred ingredient (A) through obtaining after the described foam device foaming for the type of foam device.The present inventor finds after deliberation, if the cell diameter that obtains after the foam device foaming is bigger, the foam that then makes is extremely unstable, and the disruptive phenomenon takes place easily; If too little through the cell diameter that obtains after the foam device foaming, the resistance that then foams is bigger, the foaming difficulty.When component (A) when the foamy cell diameter that obtains is 1.0-3.0mm after foaming, the stable performance of the final polyvinyl alcohol foam oxygen barrier material that forms, anti-spontaneous combustion better effects if.
Compared with prior art, advantage of the present invention and beneficial effect are as follows:
(1) in the present invention, has minimum oxygen permeability coefficient, film-forming properties preferably, environmentally safe as the polyvinyl alcohol of the base-material of preparation oxygen barrier material.Therefore, has fabulous oxygen barrier performance by its oxygen barrier material that makes, and the consumption of polyvinyl alcohol is the (total amount of contained solvent based on component (A) and (B) seldom, promptly based on the amount of contained solvent in the polyvinyl alcohol oxygen barrier material, the content of polyvinyl alcohol is 3-8wt%), the burning back can be ignored the influence of ature of coal, and environmentally safe.
(2) in the present invention, adopt organic alcohol of straight chain hydrocarbon or straight chain hydrocarbon organic ester polyvinyl alcohol to be carried out modification as properties-correcting agent, the amount of hydroxyl is significantly increased, increase the associating intensity of hydrogen bond, can improve the plasticity of polyvinyl alcohol film on the one hand significantly, satisfy in the Coal Transport process mechanics requirement to the polyvinyl alcohol film that covers the coal surface, on the other hand, when making its formation bubble jet be sprinkled upon the coal surface when adding whipping agent in polyvinyl alcohol modification solution and by foam device, formed polyvinyl alcohol foam and lump coal have stronger bonding force, can stick to the coal surface well.
(3) in the present invention, utilized polyvinyl alcohol water solution very sensitive to borate, cause the principle of gelation easily, adopt borate as setting accelerator, borate is sprayed on the polyvinyl alcohol foam surface, form the frothy gel layer, eliminated foam materials because of the crackly phenomenon of unstable properties, and the good toughness of gel coat, the quality densification, can suppress oxygen better enters in the coal, reduce the low-temperature oxidation speed of reaction of coal and oxygen, reduce oxidation heat liberation, be implemented in the purpose that prevents spontaneous combustion of coal in coal standing storage and the long-distance transport process.
(4) in the present invention, the total amount of contained solvent is 100wt% in component (A) and (B), the content of the polyvinyl alcohol in the component (A) is 3-8wt%, boratory content in the component (B) is 0.1-0.3wt%, when the boratory component (B) that will comprise above-mentioned content is sprayed on the foam surface that the component (A) by the polyvinyl alcohol that comprises above-mentioned content forms, described polyvinyl alcohol foam material all irreversibly forms the frothy gel layer in the very short time (about 5-10 is in second), thereby makes the oxygen barrier material can cover the coal surface equably.In addition, described borate is sprayed at the better mobile of formed frothy gel layer on the described polyvinyl alcohol foam material.Therefore, than only passing through to add properties-correcting agent and the formulated polyvinyl alcohol gel oxygen barrier material of setting accelerator, when covering coal of the same area surface and forming the oxygen barrier layer of same thickness, the consumption of oxygen barrier material of the present invention still less, thereby reduced the control cost that in coal standing storage and long-distance transport process, prevents spontaneous combustion of coal.
Description of drawings
Fig. 1 is that wherein A, B are hot face as the casing synoptic diagram of the coal sampling mill in the oxygen barrier performance testing device of the present invention, and some 1-5 is the collection point of gas, the coordinate of point 1 is (250,300,450), the coordinate of point 2 is (50,300,300), the coordinate of point 3 is (250,300,300), the coordinate of point 4 is (450,300,300), the coordinate of point 5 is (250,300,50).
Embodiment
Further describe the present invention below by specific embodiment, but should not be construed as limiting the scope of the invention.Only otherwise depart from basic design of the present invention and restricted portion, the modification, replacement, the change that utilize ordinary skill knowledge and customary means to make all fall into protection scope of the present invention.
The used easy spontaneous combustion coal sample of embodiment and Comparative Examples is a Firing Shenhua Coal, and its coal data is listed in table 1.
Its raw material source is as follows in embodiment and the Comparative Examples:
Granule of polyvinyl alcohol (available from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure)
Glycerol (available from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure)
Sodium Tetraborate (available from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure)
Sodium laurylsulfonate (available from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure)
Sodium lignosulfonate (available from Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure)
Table 1 is the coal analysis of spontaneous combustion coal sample easily
Mechanics Performance Testing
According to the sample standard fabrication sample in the GB/T 1040-92 plastic tensile service check method.Carry out tension test at ambient temperature on WDW-20 microcomputer control electronics universal testing machine, trial speed is 100mm/min.
The thermal stability test
Polyvinyl alcohol oxygen barrier material is made the sample of length * wide * thick=100mm * 100mm * 1mm, then at room temperature, it is warming up to 60 ℃, measure and write down the length and the wide variety rate of sample respectively with the speed of 2 ℃/min; Continue to be warming up to 90 ℃ with identical temperature rise rate then, measure and write down the length and the wide variety rate of sample respectively.
The oxygen barrier performance test
Carry out in the homemade experimental installation of cabin of oxygen barrier performance detection in simulation shipping process, described experimental installation is made up of coal sampling mill, temperature element, GC-9160 gas-chromatography and computer.Casing as described coal sampling mill is of a size of 600mm * 600mm * 600mm, the easy spontaneous combustion lump coal of the 130kg that in the casing of coal sampling mill, packs into (granularity is the Firing Shenhua Coal of 20-50cm), adopt the nature accumulation mode, the coal surface covers the thick polyvinyl alcohol oxygen barrier material of about 5mm fully, as shown in Figure 1, choose intravital 5 the different test point of case, got the gas sample every 2 days and on the GC-9160 gas chromatograph, detect O in the coal sampling mill
2Change in concentration, the mean value of getting 5 test point are carried out 40 days oxygen barrier performance test altogether as final test result.
Embodiment 1
Under 90 ℃ steady temperature, in the 160kg of high-speed stirring deionized water, add the 8kg granule of polyvinyl alcohol, it is dissolved fully, be mixed with the homogeneous polyethylene alcohol solution, after reducing to room temperature, adding 2kg glycerol and stirring are dissolved it fully, add the 0.08kg sodium laurylsulfonate, slowly stir, be mixed with the polyvinyl alcohol modification frothing solution; In the 30kg deionized water, add the 0.3kg Sodium Tetraborate, be stirred to evenly, be mixed with the Sodium Tetraborate aqueous solution.The polyvinyl alcohol modification frothing solution for preparing is foamed in foam device, and be that the steel pipe of 80mm is sprayed to the dump surface with its conveying by pump and diameter, form foam surface, by pump the Sodium Tetraborate aqueous solution evenly is sprayed to foam surface then, about 5-10 second, the surface of inherent dump formed the PVA oxygen barrier foam materials 1 that a layer thickness is about 5mm, and covered the required polyvinyl alcohol modification frothing solution in the coal surface of unit surface and the gross weight of the Sodium Tetraborate aqueous solution is 0.56kg/m
2
Embodiment 2
Under 80 ℃ steady temperature, in the deionized water of the 160kg of high-speed stirring, add the 8kg granule of polyvinyl alcohol, it is dissolved fully, is mixed with the homogeneous polyethylene alcohol solution, reduce to room temperature after, adding the 2kg glycerol and stirring dissolves it fully, add the 0.1kg sodium lignosulfonate, slowly stir, be mixed with the polyvinyl alcohol modification frothing solution; In the 30kg deionized water, add the 0.6kg Sodium Tetraborate, be stirred to evenly, be mixed with the Sodium Tetraborate aqueous solution.The polyvinyl alcohol modification frothing solution for preparing is foamed in foam device, and be that the steel pipe of 80mm is sprayed to the dump surface with its conveying by pump and diameter, form foam surface, by pump the Sodium Tetraborate aqueous solution evenly is sprayed to foam surface then, about 5-10 second, the surface of inherent dump formed the PVA foam oxygen barrier material 2 of the about 5mm of a layer thickness, and covered the surperficial required polyvinyl alcohol modification frothing solution of the coal of unit surface and the total amount of the Sodium Tetraborate aqueous solution is 0.56kg/m
2
Comparative Examples
Under 90 ℃ steady temperature, in the 160kg of high-speed stirring deionized water, add the 8kg granule of polyvinyl alcohol, it is dissolved fully, be mixed with the homogeneous polyethylene alcohol solution, after reducing to room temperature, adding 2kg glycerol and stirring are dissolved it fully, slowly stir, and are mixed with the polyvinyl alcohol modification aqueous solution; In the 30kg deionized water, add the 0.3kg Sodium Tetraborate, be stirred to evenly, be mixed with the Sodium Tetraborate aqueous solution.The polyvinyl alcohol modification aqueous solution and the Sodium Tetraborate aqueous solution equal-volume that prepare are mixed mutually, stir, promptly get the PVA gel, be that the steel pipe of 80mm is sprayed to the dump surface with its conveying by pump and diameter then, form the PVA gel-film of the about 5mm of thickness, the amount that wherein covers the surperficial required PVA gel of the coal of unit surface is 5.0kg/m
2
PVA foam oxygen barrier material 1-2 and PVA gel are carried out Mechanics Performance Testing respectively, the test result that obtains is listed in the table 2 respectively, PVA foam oxygen barrier material 1 and 2 thermal stability test result are listed in the table 3, and the oxygen barrier The performance test results of PVA foam oxygen barrier material 1 is listed in the table 4.
Table 2 Mechanics Performance Testing result
| Performance index | PVA foam oxygen barrier material 1 | PVA foam oxygen barrier material 2 | The PVA gel |
| Tensile strength/MPa | 7.08 | 10.83 | 32.71 |
| Tensile break stress/MPa | 6.63 | 10.52 | 28.06 |
| Stretching yield stress/MPa | / | / | 14.41 |
| Elongation at break/% | 279 | 353 | 202 |
Table 3 thermal stability test result
Table 4 oxygen barrier The performance test results
Covering coal of the same area surface and forming under the prerequisite of oxygen barrier material layer of same thickness, the consumption (0.56kg/m of the PVA foam oxygen barrier material that makes by the embodiment of the invention 1 and 2
2) be starkly lower than the PVA gel (5.0kg/m that makes by Comparative Examples
2) consumption, significantly reduced the control cost that in coal standing storage and long-distance transport process, prevents spontaneous combustion of coal.In addition, by the Mechanics Performance Testing result of table 2 as seen: the PVA foam oxygen barrier bill of material that makes by the present invention reveals plasticity preferably, can satisfy in the coal long-distance transport process mechanical property requirements to the oxygen barrier glued membrane that covers the coal surface.By the heat stability testing result of table 3 as seen: when temperature was 60 ℃, the tensile strain rate of the sample that is made by PVA foam oxygen barrier material 1 of the present invention was 5.25%, and the wide variety rate is 5.41%; When temperature was 90 ℃, the tensile strain rate of this sample was 7.20%, and the wide variety rate is 7.49%, be that temperature rises 30 ℃, the size changing rate of material is less than 2%, and therefore PVA foam oxygen barrier material of the present invention has good thermostability, can satisfy the service requirements under the atmospheric environment.By the oxygen barrier The performance test results of table 4 as seen: PVA foam oxygen barrier material of the present invention is covered the coal surface, can make the oxygen concentration in the coal seam reduce to about 5v% from about 21v%, and finish until experimental period (40 days) from beginning in the 4th day of experiment, Nei oxygen concentration all is controlled at below the 6v% during this period of time, and the oxygen barrier material layer on dump surface does not have breakage, illustrates that the stability of polyvinyl alcohol oxygen barrier material of the present invention can satisfy the requirement that prevents spontaneous combustion of coal in coal long-distance transport process.
Claims (32)
1. polyvinyl alcohol foam oxygen barrier material, it is characterized in that, described foam oxygen barrier material comprises component (A) and component (B), comprise solvent in the described component (A) and in component (A) and (B) total amount of contained solvent be the polyvinyl alcohol of 100wt% 3-8wt%, the whipping agent of the organic pure and mild 0.04-0.10wt% of straight chain hydrocarbon of 0.5-1.5wt%, comprise solvent in the described component (B) and in component (A) and (B) total amount of contained solvent be the borate of 100wt% 0.1-0.3wt%, and the mass ratio of contained solvent is 5-9:1 in component (A) and the component (B);
The foam that described component (A) is obtained after the foam device foaming is sprayed on the coal surface, forms foam surface, then described component (B) is sprayed on the described foam surface, forms polyvinyl alcohol foam oxygen barrier material;
Wherein, component (A) foamy cell diameter of obtaining after foaming is 1.0-3.0mm.
2. polyvinyl alcohol foam oxygen barrier material according to claim 1 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3-6.
3. polyvinyl alcohol foam oxygen barrier material according to claim 2 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3.
4. polyvinyl alcohol foam oxygen barrier material according to claim 2 is characterized in that the organic alcohol of described straight chain hydrocarbon is glycerol.
5. polyvinyl alcohol foam oxygen barrier material according to claim 2 is characterized in that, described component (A) and (B) in contained solvent be water.
6. polyvinyl alcohol foam oxygen barrier material according to claim 5 is characterized in that, described component (A) and (B) in contained solvent be deionized water.
7. polyvinyl alcohol foam oxygen barrier material according to claim 5 is characterized in that described whipping agent is selected from sodium laurylsulfonate, α-sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfonate or sodium lignosulfonate.
8. polyvinyl alcohol foam oxygen barrier material according to claim 7 is characterized in that described borate is alkali metal borate or alkaline earth metal borate.
9. polyvinyl alcohol foam oxygen barrier material according to claim 7 is characterized in that described borate is an alkali metal borate.
10. polyvinyl alcohol foam oxygen barrier material according to claim 7 is characterized in that described borate is a Sodium Tetraborate.
11. method for preparing polyvinyl alcohol foam oxygen barrier material as claimed in claim 1, it is characterized in that, described component (A) makes as follows: under 70-95 ℃ steady temperature, polyvinyl alcohol is dissolved in the solvent, refluxes and stirred 30-60 minute, be cooled to room temperature, add the organic alcohol of straight chain hydrocarbon again, stir, add whipping agent then, promptly get component (A); Described component (B) makes as follows: borate is added in the solvent, stir, promptly get component (B);
The foam that described component (A) is obtained after the foam device foaming is sprayed on the coal surface, forms foam surface, then described component (B) is sprayed on the described foam surface, forms polyvinyl alcohol foam oxygen barrier material.
12. preparation method according to claim 11 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3-6.
13. preparation method according to claim 12 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3.
14. preparation method according to claim 12 is characterized in that, the organic alcohol of described straight chain hydrocarbon is glycerol.
15. preparation method according to claim 12 is characterized in that, described component (A) and (B) in contained solvent be water.
16. preparation method according to claim 15 is characterized in that, described component (A) and (B) in contained solvent be deionized water.
17. preparation method according to claim 15 is characterized in that, described whipping agent is selected from sodium laurylsulfonate, α-sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfonate or sodium lignosulfonate.
18. polyvinyl alcohol foam oxygen barrier material according to claim 17 is characterized in that described borate is alkali metal borate or alkaline earth metal borate.
19. polyvinyl alcohol foam oxygen barrier material according to claim 17 is characterized in that described borate is an alkali metal borate.
20. polyvinyl alcohol foam oxygen barrier material according to claim 17 is characterized in that described borate is a Sodium Tetraborate.
21. a polyvinyl alcohol foam oxygen barrier material is used to prevent the purposes of spontaneous combustion of coal, it is characterized in that, described foam oxygen barrier material comprises component (A) and component (B), comprise solvent in the described component (A) and in component (A) and (B) total amount of contained solvent be the polyvinyl alcohol of 100wt% 3-8wt%, the whipping agent of the organic pure and mild 0.04-0.10wt% of straight chain hydrocarbon of 0.5-1.5wt%, comprise solvent in the described component (B) and in component (A) and (B) total amount of contained solvent be the borate of 100wt% 0.1-0.3wt%, and the mass ratio of contained solvent is 5-9:1 in component (A) and the component (B);
The foam that described component (A) is obtained after the foam device foaming is sprayed on the coal surface, forms foam surface, then described component (B) is sprayed on the described foam surface, forms polyvinyl alcohol foam oxygen barrier material;
Wherein, component (A) foamy cell diameter of obtaining after foaming is 1.0-3.0mm.
22. purposes according to claim 21 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3-6.
23. purposes according to claim 22 is characterized in that, the carbonatoms of the organic alcohol of described straight chain hydrocarbon is that 3-6 and hydroxyl value are 3.
24. purposes according to claim 22 is characterized in that, the organic alcohol of described straight chain hydrocarbon is glycerol.
25. purposes according to claim 22 is characterized in that, described component (A) and (B) in contained solvent be water.
26. purposes according to claim 25 is characterized in that, described component (A) and (B) in contained solvent be deionized water.
27. purposes according to claim 25 is characterized in that, described whipping agent is selected from sodium laurylsulfonate, α-sodium olefin sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfonate or sodium lignosulfonate.
28. purposes according to claim 27 is characterized in that, described borate is alkali metal borate or alkaline earth metal borate.
29. purposes according to claim 27 is characterized in that, it is characterized in that, described borate is an alkali metal borate.
30. purposes according to claim 27 is characterized in that, it is characterized in that, described borate is a Sodium Tetraborate.
31. purposes according to claim 21 is characterized in that, the foamy cell diameter that described component (A) is obtained after the foam device foaming is 1.0-3.0mm.
32. purposes according to claim 21 is characterized in that, the foamy cell diameter that described component (A) is obtained after the foam device foaming is 1.0-2.5mm.
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| CA2865453C (en) * | 2012-04-04 | 2020-04-14 | Nalco Company | Chemical additives to inhibit the air oxidation and spontaneous combustion of coal |
| CN103602339B (en) * | 2013-11-15 | 2015-05-06 | 华电电力科学研究院 | High polymer-based stopping agent for inhibiting spontaneous combustion of brown coal dump and preparation method of high polymer-based stopping agent |
| CN103967512B (en) * | 2014-03-31 | 2016-08-17 | 中国矿业大学 | A kind of water base foam of mining preventing and treating spontaneous combustionof coal and preparation method thereof |
| CN108203518A (en) * | 2016-12-16 | 2018-06-26 | 北京林业大学 | A kind of preparation method of lignin enhancing PVA expanded materials |
| CN109899104A (en) * | 2019-01-21 | 2019-06-18 | 山东科技大学 | A kind of economic and environment-friendly type gel foam for preventing and treating spontaneous combustionof coal |
| CN109912911B (en) * | 2019-03-05 | 2021-10-29 | 中原工学院 | Preparation method of polymer micro-nanofiber reinforced polyvinyl alcohol foam material |
| CN109957434B (en) * | 2019-03-27 | 2021-08-10 | 中国矿业大学 | Inhibitor for inhibiting spontaneous combustion in upgraded lignite stacking and storing process and preparation and use methods thereof |
| CN115594877B (en) * | 2022-10-27 | 2023-09-19 | 华南理工大学 | Flame-retardant coating with self-repairing and recycling properties, and preparation method and application thereof |
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