CN104891835A - A graft modification method of flame-retardant fly ash - Google Patents
A graft modification method of flame-retardant fly ash Download PDFInfo
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- CN104891835A CN104891835A CN201510253924.7A CN201510253924A CN104891835A CN 104891835 A CN104891835 A CN 104891835A CN 201510253924 A CN201510253924 A CN 201510253924A CN 104891835 A CN104891835 A CN 104891835A
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- flyash
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- hour
- graft
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- 239000010881 fly ash Substances 0.000 title claims abstract description 81
- 238000002715 modification method Methods 0.000 title claims abstract description 25
- 239000003063 flame retardant Substances 0.000 title claims abstract description 20
- 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 title claims abstract description 19
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 32
- 239000010883 coal ash Substances 0.000 claims description 27
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 230000029936 alkylation Effects 0.000 claims description 10
- 238000005804 alkylation reaction Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 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
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 14
- 239000004567 concrete Substances 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000003245 coal Substances 0.000 description 8
- 239000011449 brick Substances 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 239000002956 ash Substances 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000876852 Scorias Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HHZLLMMKYBCNMW-UHFFFAOYSA-N [P].[Mg].[Ca].[Si].C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound [P].[Mg].[Ca].[Si].C(CC(O)(C(=O)O)CC(=O)O)(=O)O HHZLLMMKYBCNMW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- -1 flame-retardant compound Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Fireproofing Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A graft modification method of flame-retardant fly ash is disclosed. According to the method, the surface of a material mixture obtained from fly ash is subjected to silylanization by utilization of 3-aminopropyltriethoxysilane, and then butyl methacrylate is grafted to the silylanization surface of the material mixture, thus improving system stability, water resistance and adhesion force. A silicon-containing filtrate after the fly ash is dipped with sodium hydroxide is mixed with tetraethoxysilane to prepare a silicon emulsion, and then the silicon emulsion is mixed with high-boron calcium borate, decabromodiphenyl ether, and the like to form an efficient flame-retardant material mixture that is good in mechanical performance and improved in flame retardance and safety.
Description
Technical field
The present invention relates to a kind of method that flyash is recycled, particularly relate to a kind of graft-modification method of fireproof powder coal ash.
Background technology
Flyash, be receive to catch the thin ash got off from the flue gas after coal combustion, flyash is the primary solids refuse that coal-burning power plant discharges.The main oxides of power plants flyash consists of: SiO
2, Al
2o
3, FeO, Fe
2o
3, CaO, TiO
2deng.Flyash is one of industrial residue that the current discharge capacity of China is larger, and along with the development of power industry, the flyash quantity discharged of coal-burning power plant increases year by year.A large amount of flyash does not add process, will produce airborne dust, atmosphere pollution; River can be caused to silt up if enter water system, and toxic chemical substance wherein also can work the mischief to human body and biology.Flyash can be used as concrete adulterant in addition.
Shi Ge big coal country of China take coal as the basic fuel of electrical production.The energy industry stable development of China, power generation capacity annual growth is 7.3%, developing rapidly of power industry, bring the sharply increase of flyash quantity discharged, annual the discharged flyash total amount of Hazards in Power Plant increases year by year, nineteen ninety-five flyash quantity discharged reach 1.25 hundred million tons, within 2000, be about 1.5 hundred million tons, 300,000,000 tons will be reached by 2010, cause huge pressure to the development of the national economy of China and ecotope.On the other hand, China is again the limited country of a per capita resource reserve, the comprehensive utilization of flyash, turn waste into wealth, turn bane into boon, to become in China's economic construction an important techno-economic policy, solve China electrical production environmental pollution, the important means of contradiction between resource shortage, be also electrical production one of the task of facing solution.Through exploitation, flyash is widely used in all departments such as building work, building materials, water conservancy.
20 century 70s, worldwide energy dilemma, the exhaustion etc. of environmental pollution and mineral wealth excites the research and development of utilization of fly ash consumingly, and repeatedly hold international flyash meeting, research work is increasingly deep, and application aspect there has also been significant progress.Flyash becomes noticeable aboundresources on world market, cheap, and the emerging building materials raw material of bringing good to and remove all evil and the raw material of Chemicals, be subject to the favor of people.Mostly by theoretical investigation, applied research is turned to the research work of flyash, particularly important Resource analysis and exploitation.The product utilizing flyash to produce is in continuous increase, and technology is in continuous renewal.Domestic and international total utilization of PCA work, compared with in the past, there occurs great change, and main manifestations is: flyash administer guiding theory from the simple environment angle change in past be the comprehensive regulation, recycling; The approach of total utilization of PCA, with outside the application of the aspect such as roadbed, embankment, concrete admixture, soil remediation from the past, develops at advanced utilization ways such as cement raw material, cement mixture, Large Hydro-Junction engineering, pump concrete, mass concrete goods, senior fillers.
Flyash is the one seemingly pozzolana mixed material that coal dust is formed after high-temp combustion.It is the coal dust that coal is worn into less than 100 microns by the power station of coal combustion, sprays into burner hearth become suspended state to burn with preheated air, produces and mixes the high-temperature flue gas having a large amount of incombustible substance, just obtains flyash through particle collector trapping.The chemical constitution of flyash is similar to clayey, and main component is silicon-dioxide, aluminium sesquioxide, ferric oxide, calcium oxide and uncompleted burned carbon.Flyash is mainly used to produce pulverized fuel ash cement, flyash brick, fly ash silicate building block, powder ash air-entrained concrete and other material of construction, also can be used as agricultural fertilizer and soil improvement agent, reclaims industrial raw material and makes environmentally conscious materials.The application of flyash in Cement industry and concrete works: flyash replaces raw clay to produce cement; add the levigate hydraulic glue gel material made of proper amount of gypsum by Portland clinker and flyash, Cement industry employing flyash batching can utilize unburnt carbon wherein; Flyash makes cement mixture; Flyash produces low-temperature synthesizing water mud, and production principle is that first for admixtion vapor cure is generated hydrate, then forms cement minerals through dehydration and low-temperature solid phase reaction; Flyash makes clinker-free cement; comprise lime fly ash cement and pure fly ash cement; lime fly ash cement the flyash of drying is mixed the unslaked lime of 10%-30% or slaked lime and a small amount of gypsum combined grinding, or the hydraulic cementing materials evenly made of levigate rear remix respectively; Flyash makes mortar or concrete Additive, in concrete, adding coal ash replaces part of cement or fine aggregate, can not only reduce costs, and concrete workability can be improved, improve waterproof, gas, Sulphate-resistant property and chemistry-resistant characteristic, reduction hydration heat, improve concrete resistance to elevated temperatures, alleviate particle separation and bleed phenomenon, reduce concrete contraction and cracking and suppress stray current to the corrosion of reinforcement in concrete.The application of flyash in building product: steam flyash brick; with fly ash in electric power plant and unslaked lime or other alkali-activators for main raw material; also appropriate gypsum can be mixed; and add the aggregates such as a certain amount of cinder or water-granulated slag, a kind of materials for wall formed after processing, stirring, digestion, rolling, compression moulding, normal pressure or autoclave curing; Fired fly ash brick, with flyash, clay and other industrial wastes for raw material, makes brick through Raw material processing, stirring, shaping, dry, roast; Steam pressure produces foam powder coal ash insulating brick, is main raw material, adds a certain amount of lime and foaming agent with flyash, through a kind of novel insulating brick of prepare burden, stir, burn injection forming and steam pressure; Fly ash silicate building block, with flyash, lime, gypsum for gelling material, cinder, blast-furnace slag etc. are aggregate, the materials for wall of add water stirring, vibratory compaction, vapor cure; Powder ash air-entrained concrete, take flyash as raw material, adds unslaked lime, cement, gypsum and aluminium powder in right amount, adds water and stirs in slurry, inject a kind of porous light material of construction that mould is steam-cured; Lytag, is main raw material with flyash, mixes a small amount of binding agent and solid fuel, through mixing, balling-up, high temperature roast and a kind of artificial lightweight aggregate made; Coal ash light heat insulation brick, be carry out batching with flyash, scoria, soft soil and wood chip to form, have insulating efficiency high, refractoriness is done, thermal conductivity is little, can alleviate furnace wall thickness, shortens firing time, reduces fuel consumption, improves thermo-efficiency, reduce costs.Flyash makes agricultural fertilizer and soil improvement agent: flyash has good physicochemical property, can be widely used in transforming heavy clay, the immature soil, sour earth and saline-alkali soil, make up the defect that its sour thin plate is sticky, containing necessary nutritive elements of farm crop such as a large amount of solubility in citric acid silicon-calcium-magnesium phosphorus in flyash, therefore agricultural fertilizer can be used as.Reclaim industrial raw material: reclaiming coal resource, utilize flotation process to add flotation reagent in containing the grey pulp-water of coal powder coal ash, then adopt air flotation technology, make coal grain adhere to bubble floating and be separated with lime-ash; Containing Fe in Footwall drift material flyash
2o
3, Al
2o
3, and a large amount of rare metal; Sorting cenosphere, cenosphere has that quality is little, high strength, high temperature resistant and good insulating, may be used for the ideal filler of plastics, and for lightweight refractory and thermal insulation material, for petrochemical industry, for military industry field, tank brakes.Make environment-friendly materials: utilize flyash can manufacture the environment-friendly materials such as molecular sieve, flocculation agent and sorbing material; Flyash also can be used for process fluoride waste, electroplating wastewater and contains heavy metal example waste water and oily(waste)water, the Al contained in flyash
2o
3, CaO isoreactivity component, can title complex be produced with fluorine or produce colloid ion fluorine being had to throwing out, also containing zeolite, mullite, carbon granule and silica gel etc., there is mineral ion commutativity and adsorption and decoloration.
Summary of the invention
The object of the invention just there is provided a kind of graft-modification method of fireproof powder coal ash.
The present invention is achieved by the following technical solutions:
A graft-modification method for fireproof powder coal ash, is characterized in that comprising the following steps:
(1) flyash is pulverized, cross 200-300 mesh sieve, with the aqueous solution of the activator of its weight 3-5%, insulated and stirred 2-3 hour at 70-80 DEG C, oven dry dewaters, and calcines 1-2 hour at 800-900 DEG C, be cooled to normal temperature, join in the aqueous sodium hydroxide solution of concentration 10-16%, heat-insulation soaking 3-5 hour at 50-60 DEG C, filter, obtain filter residue and filtrate, filter residue is washed, dries, obtain flyash dry powder;
(2) PH regulating above-mentioned filtrate is 6-7, adds the tetraethoxy of its weight 7-10%, and raised temperature is 70-76 DEG C, adds the castor oil polyoxyethylene ether of batch mixing weight 0.1-0.2%, insulated and stirred 10-20 minute, obtains silicon emulsion;
(3) get high boron lime borate that weight ratio is 10-12:0.1-0.2:3-5:0.01-0.02, oxine, decabromodiphenyl oxide, dibasic lead phosphite mixing, ball milling is even, obtains flame retardant;
(4) by above-mentioned flyash dry powder, flame retardant, silicon emulsion mixing, 500-600 rev/min is stirred 10-20 minute, under normal temperature, ageing leaves standstill 2-3 hour, press filtration, vacuum-drying, ball milling is even, adds the APTES of ball milling material weight 50-60%, insulated and stirred 10-20 hour at 20-30 DEG C, obtains alkylation batch mixing;
(5) polyvinyl alcohol is got; join in its weight 20-30 times water, stir, add abovementioned alkyl batch mixing; adjustment temperature is 60-70 DEG C; under the protection of nitrogen, add butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate successively, stirring reaction 6-7 hour; reaction terminates rear ethanol, deionized water washs successively; press filtration, vacuum-drying, to obtain final product.
A graft-modification method for fireproof powder coal ash, the weight ratio of the flyash dry powder described in step (4), flame retardant is 100:6-10.
A graft-modification method for fireproof powder coal ash, the weight ratio of the polyvinyl alcohol described in step (5), butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate and alkylation batch mixing is 3-4:17-20:1-2:0.1-0.14:16-30.
A graft-modification method for fireproof powder coal ash, the aqueous solution of the activator described in step (1) is mixed by the raw material of following weight parts and forms: Sodium Silicofluoride 7-10 weight part, sodium-chlor 2-3 weight part, phytinic acid 0.2-0.4 weight part, deionized water 100 weight part.
Advantage of the present invention is:
The present invention utilizes APTES, make the mix surface silylation obtained by flyash, then butyl methacrylate is grafted on the silylation surface of compound, improve the stability of system, water resisting property and binding property, siliceous filtrate after flyash soaking with sodium hydroxide and tetraethoxy are mixed with silicon emulsion by the present invention, highly effective flame-retardant compound is mixed to form with high boron lime borate, decabromodiphenyl oxide etc., not only there is good mechanical property, also improve flame retardant resistance and security.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1:
A graft-modification method for fireproof powder coal ash, is characterized in that comprising the following steps:
(1) flyash is pulverized, cross 200 mesh sieves, with the aqueous solution of the activator of its weight 4%, insulated and stirred 2 hours at 70 DEG C, oven dry dewaters, and calcines 2 hours at 900 DEG C, be cooled to normal temperature, join in the aqueous sodium hydroxide solution of concentration 16%, heat-insulation soaking 3 hours at 60 DEG C, filter, obtain filter residue and filtrate, filter residue is washed, dries, obtain flyash dry powder;
(2) PH regulating above-mentioned filtrate is 7, adds the tetraethoxy of its weight 7-10%, and raised temperature is 76 DEG C, adds the castor oil polyoxyethylene ether of batch mixing weight 0.2%, and insulated and stirred 20 minutes, obtains silicon emulsion;
(3) get high boron lime borate that weight ratio is 12:0.2:3:0.02, oxine, decabromodiphenyl oxide, dibasic lead phosphite mixing, ball milling is even, obtains flame retardant;
(4) by above-mentioned flyash dry powder, flame retardant, silicon emulsion mixing, 500 revs/min are stirred 17 minutes, under normal temperature, ageing leaves standstill 2 hours, press filtration, vacuum-drying, ball milling is even, adds the APTES of ball milling material weight 50%, at 20 DEG C, insulated and stirred 18 hours, obtains alkylation batch mixing;
(5) polyvinyl alcohol is got; join in its weight 26 times of water, stir, add abovementioned alkyl batch mixing; temperature is regulated to be 70 DEG C; under the protection of nitrogen, add butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate successively, stirring reaction 6 hours; reaction terminates rear ethanol, deionized water washs successively; press filtration, vacuum-drying, to obtain final product.
A graft-modification method for fireproof powder coal ash, the weight ratio of the flyash dry powder described in step (4), flame retardant is 100:7.
A graft-modification method for fireproof powder coal ash, the weight ratio of the polyvinyl alcohol described in step (4), butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate and alkylation batch mixing is 3:20:1:0.14:30.
A graft-modification method for fireproof powder coal ash, the aqueous solution of the activator described in step (1) is mixed by the raw material of following weight parts and forms: Sodium Silicofluoride 9 weight part, sodium-chlor 2 weight part, phytinic acid 0.26 weight part, deionized water 100 weight part.
Embodiment 2
A graft-modification method for fireproof powder coal ash, is characterized in that comprising the following steps:
(1) flyash is pulverized, cross 300 mesh sieves, with the aqueous solution of the activator of its weight 4%, insulated and stirred 2 hours at 80 DEG C, oven dry dewaters, and calcines 1 hour at 900 DEG C, be cooled to normal temperature, join in the aqueous sodium hydroxide solution of concentration 10%, heat-insulation soaking 3 hours at 60 DEG C, filter, obtain filter residue and filtrate, filter residue is washed, dries, obtain flyash dry powder;
(2) PH regulating above-mentioned filtrate is 6, adds the tetraethoxy of its weight 10%, and raised temperature is 70 DEG C, adds the castor oil polyoxyethylene ether of batch mixing weight 0.17%, and insulated and stirred 18 minutes, obtains silicon emulsion;
(3) get the high boron lime borate of weight ratio 12:0.2:3:0.01, oxine, decabromodiphenyl oxide, dibasic lead phosphite mixing, ball milling is even, obtains flame retardant;
(4) by above-mentioned flyash dry powder, flame retardant, silicon emulsion mixing, 600 revs/min are stirred 20 minutes, under normal temperature, ageing leaves standstill 2 hours, press filtration, vacuum-drying, ball milling is even, adds the APTES of ball milling material weight 60%, at 27 DEG C, insulated and stirred 10 hours, obtains alkylation batch mixing;
(5) polyvinyl alcohol is got; join in its weight 28 times of water, stir, add abovementioned alkyl batch mixing; temperature is regulated to be 70 DEG C; under the protection of nitrogen, add butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate successively, stirring reaction 6 hours; reaction terminates rear ethanol, deionized water washs successively; press filtration, vacuum-drying, to obtain final product.
A graft-modification method for fireproof powder coal ash, the weight ratio of the flyash dry powder described in step (4), flame retardant is 10:1.
A graft-modification method for fireproof powder coal ash, the weight ratio of the polyvinyl alcohol described in step (5), butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate and alkylation batch mixing is 3:19:1:0.12:21.
A graft-modification method for fireproof powder coal ash, the aqueous solution of the activator described in step (1) is mixed by the raw material of following weight parts and forms: Sodium Silicofluoride 9 weight part, sodium-chlor 3 weight part, phytinic acid 0.4 weight part, deionized water 100 weight part.
Embodiment 3
A graft-modification method for fireproof powder coal ash, comprises the following steps:
(1) flyash is pulverized, cross 300 mesh sieves, with the aqueous solution of the activator of its weight 3%, insulated and stirred 2 hours at 80 DEG C, oven dry dewaters, and calcines 1 hour at 900 DEG C, be cooled to normal temperature, join in the aqueous sodium hydroxide solution of concentration 16%, heat-insulation soaking 3 hours at 60 DEG C, filter, obtain filter residue and filtrate, filter residue is washed, dries, obtain flyash dry powder;
(2) PH regulating above-mentioned filtrate is 6, adds the tetraethoxy of its weight 7-10%, and raised temperature is 76 DEG C, adds the castor oil polyoxyethylene ether of batch mixing weight 0.17%, and insulated and stirred 20 minutes, obtains silicon emulsion;
(3) get high boron lime borate that weight ratio is 10:0.17:3:0.01, oxine, decabromodiphenyl oxide, dibasic lead phosphite mixing, ball milling is even, obtains flame retardant;
(4) by above-mentioned flyash dry powder, flame retardant, silicon emulsion mixing, 560 revs/min are stirred 13 minutes, under normal temperature, ageing leaves standstill 2 hours, press filtration, vacuum-drying, ball milling is even, adds the APTES of ball milling material weight 51%, at 28 DEG C, insulated and stirred 18 hours, obtains alkylation batch mixing;
(5) polyvinyl alcohol is got; join in its weight 24 times of water, stir, add abovementioned alkyl batch mixing; temperature is regulated to be 68 DEG C; under the protection of nitrogen, add butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate successively, stirring reaction 6 hours; reaction terminates rear ethanol, deionized water washs successively; press filtration, vacuum-drying, to obtain final product.
A graft-modification method for fireproof powder coal ash, the weight ratio of the flyash dry powder described in step (4), flame retardant is 100:9.
A graft-modification method for fireproof powder coal ash, the weight ratio of the polyvinyl alcohol described in step (5), butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate and alkylation batch mixing is 3:20:1:0.1:17.
A graft-modification method for fireproof powder coal ash, the aqueous solution of the activator described in step (1) is mixed by the raw material of following weight parts and forms: Sodium Silicofluoride 9 weight part, sodium-chlor 2 weight part, phytinic acid 0.2 weight part, deionized water 100 weight part.
Claims (4)
1. a graft-modification method for fireproof powder coal ash, is characterized in that comprising the following steps:
(1) flyash is pulverized, cross 200-300 mesh sieve, with the aqueous solution of the activator of its weight 3-5%, insulated and stirred 2-3 hour at 70-80 DEG C, oven dry dewaters, and calcines 1-2 hour at 800-900 DEG C, be cooled to normal temperature, join in the aqueous sodium hydroxide solution of concentration 10-16%, heat-insulation soaking 3-5 hour at 50-60 DEG C, filter, obtain filter residue and filtrate, filter residue is washed, dries, obtain flyash dry powder;
(2) PH regulating above-mentioned filtrate is 6-7, adds the tetraethoxy of its weight 7-10%, and raised temperature is 70-76 DEG C, adds the castor oil polyoxyethylene ether of batch mixing weight 0.1-0.2%, insulated and stirred 10-20 minute, obtains silicon emulsion;
(3) get high boron lime borate that weight ratio is 10-12:0.1-0.2:3-5:0.01-0.02, oxine, decabromodiphenyl oxide, dibasic lead phosphite mixing, ball milling is even, obtains flame retardant;
(4) by above-mentioned flyash dry powder, flame retardant, silicon emulsion mixing, 500-600 rev/min is stirred 10-20 minute, under normal temperature, ageing leaves standstill 2-3 hour, press filtration, vacuum-drying, ball milling is even, adds the APTES of ball milling material weight 50-60%, insulated and stirred 10-20 hour at 20-30 DEG C, obtains alkylation batch mixing;
(5) polyvinyl alcohol is got; join in its weight 20-30 times water, stir, add abovementioned alkyl batch mixing; adjustment temperature is 60-70 DEG C; under the protection of nitrogen, add butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate successively, stirring reaction 6-7 hour; reaction terminates rear ethanol, deionized water washs successively; press filtration, vacuum-drying, to obtain final product.
2. the graft-modification method of a kind of fireproof powder coal ash according to claim 1, is characterized in that the flyash dry powder described in step (4), the weight ratio of flame retardant is 100:6-10.
3. the graft-modification method of a kind of fireproof powder coal ash according to claim 1, is characterized in that the weight ratio of the polyvinyl alcohol described in step (5), butyl methacrylate, divinylbenzene, Diisopropyl azodicarboxylate and alkylation batch mixing is 3-4:17-20:1-2:0.1-0.14:16-30.
4. the graft-modification method of a kind of fireproof powder coal ash according to claim 1, is characterized in that what the aqueous solution of the activator described in step (1) was made up of the raw material mixing of following weight parts: Sodium Silicofluoride 7-10 weight part, sodium-chlor 2-3 weight part, phytinic acid 0.2-0.4 weight part, deionized water 100 weight part.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264719A (en) * | 2000-03-31 | 2000-08-30 | 首都师范大学 | Process for preparing functional membrane material by modifying interface of powdered coal ash |
| CN103102545A (en) * | 2012-11-14 | 2013-05-15 | 安徽金桥电缆有限公司 | Cable sheath insulating material for computer and preparation method thereof |
| CN103172952A (en) * | 2013-04-08 | 2013-06-26 | 陕西理工学院 | Preparation method of coal ash-resin composite material suitable for extrusion molding |
| CN103880338A (en) * | 2014-01-22 | 2014-06-25 | 陕西理工学院 | Preparation method of coal ash thermal insulation-decoration integrated plate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264719A (en) * | 2000-03-31 | 2000-08-30 | 首都师范大学 | Process for preparing functional membrane material by modifying interface of powdered coal ash |
| CN103102545A (en) * | 2012-11-14 | 2013-05-15 | 安徽金桥电缆有限公司 | Cable sheath insulating material for computer and preparation method thereof |
| CN103172952A (en) * | 2013-04-08 | 2013-06-26 | 陕西理工学院 | Preparation method of coal ash-resin composite material suitable for extrusion molding |
| CN103880338A (en) * | 2014-01-22 | 2014-06-25 | 陕西理工学院 | Preparation method of coal ash thermal insulation-decoration integrated plate |
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