CN108910902B - Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash - Google Patents
Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash Download PDFInfo
- Publication number
- CN108910902B CN108910902B CN201810970502.5A CN201810970502A CN108910902B CN 108910902 B CN108910902 B CN 108910902B CN 201810970502 A CN201810970502 A CN 201810970502A CN 108910902 B CN108910902 B CN 108910902B
- Authority
- CN
- China
- Prior art keywords
- fly ash
- temperature
- tobermorite
- alumina
- alumina fly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010881 fly ash Substances 0.000 title claims abstract description 65
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 23
- 239000011810 insulating material Substances 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 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 claims abstract description 38
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 37
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000292 calcium oxide Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000004537 pulping Methods 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims 6
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000003245 coal Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002910 solid waste Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 240000006909 Tilia x europaea Species 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 241001092459 Rubus Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 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
- 230000002265 prevention Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a method for synthesizing tobermorite composite heat-insulating fireproof material by using high-alumina fly ash, belonging to the field of inorganic heat-insulating materials. The method comprises the steps of taking high-alumina fly ash as a main raw material, mixing the high-alumina fly ash with calcium oxide or calcium hydroxide, grinding the mixture, adding a trace amount of additive, uniformly mixing the two raw materials with water, pulping, performing dynamic hydrothermal synthesis reaction, and sequentially filtering and drying the mixture after the reaction to obtain the mullite and tobermorite composite heat-insulating fireproof material. The main raw material of the high-alumina fly ash is solid waste obtained after high-alumina coal is combusted in a pulverized coal furnace of a power plant; the invention greatly reduces the production cost of the composite material, has wide raw material sources, and meanwhile, the method for preparing the mullite and tobermorite composite heat-insulating fireproof material is simple, has short reaction time, can absorb solid wastes generated by a thermal power plant in a large scale, and is suitable for industrialized popularization.
Description
Technical Field
The invention relates to a method for synthesizing tobermorite composite heat-insulating material by using high-alumina fly ash, in particular to a method for hydrothermally synthesizing mullite and tobermorite type composite heat-insulating fireproof plate by using high-alumina fly ash, belonging to the field of inorganic heat-insulating materials. The fireproof door core board is mainly used in the fields of fireproof door core boards, ship compartment boards, steel structure heat preservation and fire prevention, building outer wall fireproof heat preservation, building inner flue air pipes, electrolytic bath heat preservation and insulation boards and the like.
Background
4 billions of tons of fly ash are discharged from thermal power plants in China every year, and the transportation and mass accumulation of high-alumina fly ash cause serious problems of land occupation and environmental pollution, easily cause dust pollution, cause the problem that heavy metal in underground water exceeds the standard, and the like. The high-alumina fly ash is generally rich in alumina, the alumina content of the fly ash after combustion in most coal fields in the inner Mongolia autonomous region is up to more than 40%, and particularly in the middle and western regions of the inner Mongolia, because of special geological background, several large coal fields in the region are rich in alumina. Taking a quasi-Geer coal field as an example, the coal storage capacity of the coal field is up to 260 hundred million tons, the average content of alumina in the fly ash formed after the coal is combusted is up to 48-52 percent, which is equivalent to the content of alumina in medium-grade bauxite, the coal ash is a fly ash type with the highest known alumina content in the world, and the potential storage capacity of the fly ash is up to 70-80 hundred million tons. The high-alumina fly ash has the characteristics of low density, high alumina content and abundant reserves. The Ore-Doss basin late ancient coal bed and gangue are rich in minerals such as boehmite, kaolinite and the like, the content of alumina in the fly ash generated after combustion is up to 50 percent, and the content of the alumina in the fly ash is equivalent to that in medium-grade bauxite, so the coal ash is a valuable alumina production raw material. According to statistics, the potential storage amount of the high-alumina fly ash in the midwest region of inner Mongolia is up to 150 hundred million tons. The comprehensive development and utilization of the aluminum silicon elements in the high-alumina fly ash resources are beneficial to the protection and development of the local environment, can improve the economic value of the high-alumina fly ash, and has a strategic and important circular economy industry.
The tobermorite is synthesized by generally needing a calcium raw material and a silicon raw material, and the heat preservation time is different from 4 hours to 28 days under the hydrothermal condition of 80-200 ℃. The calcareous raw materials mainly comprise lime or carbide slag, and the siliceous raw materials mainly comprise quartz, silica fume, silica gel, cement, kaolin, fly ash and the like. The main chemical reactions that take place are: 5CaO +6SiO2+5H2O→Ca5Si6O16(OH)2·4H2O。
Tobei mullite is the main mineral component of calcium silicate heat-insulating material, the use temperature of the heat-insulating material formed by the Tobei mullite can reach 650 ℃, and the Tobei mullite has the advantages of small volume weight, high-temperature thermal stability, low heat conductivity coefficient and the like, so the Tobei mullite is widely used as the main raw material of light heat-insulating fireproof material. At present, the preparation method of tobermorite is mainly a hydrothermal synthesis method, and the method is to use a calcareous raw material (mainly providing CaO) and a siliceous raw material (mainly providing SiO)2) Mixing the materials according to a certain proportion, placing the mixture into a high-pressure reaction kettle for reaction to obtain tobermorite, adding an additive and reinforcing fibers, and carrying out compression molding and drying to obtain the tobermorite type calcium silicate heat-insulating material. Most of siliceous raw materials adopted in the method are solid such as quartz sand with perfect crystallization or expensive white carbon black and the likeThe material, the time required by the reaction process is long, and the reaction temperature is high. Therefore, the method for producing tobermorite in the prior art has the defects of high production cost and long production time. How to find a siliceous raw material and a calcareous raw material which are low in cost and sufficient in market supply and can shorten the production time of tobermorite is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the problems of environmental pollution and resource waste of the existing high-alumina fly ash, and provides a method for synthesizing tobermorite composite heat-insulating material by using high-alumina fly ash.
The purpose of the invention is realized by the technical scheme.
A method for synthesizing tobermorite composite heat-insulating material by using high-alumina fly ash comprises the following steps:
step one, uniformly mixing high-alumina fly ash and a calcareous raw material, then adding a trace additive with the total mass not more than 3%, and grinding to be below 0.12mm to obtain a mixed raw material; the sum of the mass of the high-alumina fly ash and the calcium raw material is the total mass, and the mass of the high-alumina fly ash is 70-85% of the total mass; the mass of the calcareous raw material is 15-30% of the total mass;
and step two, mixing the mixed raw material obtained in the step one with water according to the liquid-solid mass ratio of 5-40, performing dynamic hydrothermal synthesis reaction after uniform pulping, and then sequentially performing filtration, washing and drying treatment to obtain the composite heat-insulating fireproof material with the main crystal phase of mullite and tobermorite.
The source of the raw material high-alumina fly ash used in the present invention is not limited, and may be, for example, solid waste obtained by burning high-alumina coal in a pulverized coal furnace of a power plant. In one embodiment, fly ash having an alumina content greater than 40% as described in the patent publication CN 102249253B is used; particularly, the mineral component of the high-alumina fly ash is mainly mullite (3 Al)2O3·2SiO2) The mass content is more than 50 percent, and in addition, the composition also comprisesWith a small amount of corundum (Al)2O3) Less than 10% of quartz (SiO)2) Less than 5%, and other mineral components and amorphous glass phase > 30%.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the high-alumina fly ash contains 40-50% of alumina, 35-45% of silicon oxide, 2-6% of calcium oxide, 1-4% of ferric oxide and less than 1% of sodium oxide.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the calcareous raw material can be one or more of quick lime, lime milk, chemically pure calcium oxide and chemically pure calcium hydroxide.
The inventor finds that the molar ratio of calcium oxide to silicon oxide in tobermorite is 5:6, the crystallization reaction temperature is 140-.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the trace additive has the function of standardizing the crystal growth direction in the crystal synthesis process so as to synthesize the qualified whiskers with the required long-jing ratio, and can be one or more of aluminum sulfate, sodium sulfate, barium sulfate, calcium sulfate, barium chloride, aluminum chloride and aluminum nitrate.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the dynamic hydrothermal synthesis reaction process in the control step 2) is to carry out multiple segmented temperature rise from room temperature, and finally the temperature is raised to 160-230 ℃, and the temperature is the final reaction temperature, and the final reaction time is 2-8 h.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the temperature rise in the reaction process in the step 2) is segmented temperature rise: if the final reaction temperature is not more than 180 ℃, keeping the temperature at 90-100 ℃ for 60min, keeping the temperature at 150 ℃ for 30min, and keeping the final reaction temperature for 2-8 h; if the final reaction temperature is higher than 180 ℃, keeping the temperature at 90-100 ℃ for 60min, keeping the temperature at 150 ℃ for 30min, keeping the temperature at 180 ℃ for 20min, and keeping the final reaction temperature for 2-8 h; wherein the stirring speed is 100-400rpm in the temperature rising process; the stirring speed during the heat preservation process is 100-.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the temperature rise rate of the sectional temperature rise is 1-3 ℃/min.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the reaction pressure in the dynamic hydrothermal synthesis reaction in the step 2) is controlled to be 0.61-2.80 MPa.
In the method for synthesizing the mullite and tobermorite composite heat-insulating fireproof material by using the high-alumina fly ash, the drying temperature in the step 2) is controlled to be 90-100 ℃, and the drying time is controlled to be 4-16 h.
Advantageous effects
1. High-alumina fly ash is used as a main raw material. Precious industrial resources such as high-grade limestone ore, quartz ore, bauxite and the like do not need to be consumed, and the raw materials are wide in source and low in price; on the other hand, the coal price of the high-alumina fly ash production place is lower than that of the bauxite production place; therefore, the production cost of independently synthesizing the mullite and the tobermorite can be reduced from the consideration of the raw material cost and the calcination cost.
2. In the traditional tobermorite synthesis process, as the raw material systems of quicklime, quartz sand and the like are adopted, the crystallization process is longer, the hydrothermal synthesis time in a high-pressure reaction kettle is longer, generally 8-16 hours are needed, and the synthesis method of the mullite and tobermorite composite material provided by the invention only needs 2-8 hours, so that the production efficiency can be greatly improved, and the unit production cost can be reduced.
3. The preparation method of the mullite and tobermorite composite material has the advantages of wide source of raw materials, low cost, simple preparation process, easy operation, low energy consumption, no three-waste discharge and good popularization and application prospect.
Drawings
FIG. 1 is an XRD spectrum of the mullite and tobermorite composite heat-insulating fireproof material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The high-alumina fly ash adopted in the embodiment is taken from a power plant in the area called and Haote in inner Mongolia, and the quick lime is taken from the clear river county in the city called and Haote in inner Mongolia, and the chemical compositions of the quick lime are shown in Table 1.
TABLE 1 chemical composition of high alumina fly ash and quicklime
The mullite and tobermorite type composite heat-insulating fireproof material of the embodiment is prepared by mixing 80kg of the high-alumina fly ash and 20kg of the quick lime, then 0.5kg of aluminum chloride, 0.3kg of aluminum sulfate and 0.7kg of barium chloride are added, the mixture is milled by a ball mill until all the particle sizes are less than 0.12mm, then 3045kg of water is added according to the liquid-solid ratio of 30 and is uniformly mixed, and then the mixture is put into a high-pressure reaction kettle, controlling the reaction temperature to be 200 ℃, the reaction pressure to be 1.58MPa, keeping the temperature of 90-100 ℃ for 60min, keeping the temperature of 150 ℃ for 30min, keeping the temperature of 180 ℃ for 20min, keeping the temperature of 200 ℃ for reaction for 5.0h, wherein the stirring speed in the temperature rise process is 300rpm, the stirring speed in the temperature rise process is 180rpm, the temperature rise rate is 3 ℃/min, cooling the product to 90 ℃ after the reaction is finished, and then filtering the reaction product, and drying the obtained filter cake at the temperature of 95 ℃ for 8.0h to obtain the mullite and tobermorite composite material.
The test shows that:
1) the water content of the obtained mullite and tobermorite composite material is 4.2 percent by mass, and the density of the obtained mullite and tobermorite composite material is 304kg/m3The thermal conductivity coefficient is 0.069W/(m.K), the compressive strength is 1.24MPa, and the flexural strength is 0.57 MPa.
2) As shown in fig. 1, we can know in the X-ray diffraction pattern that: the product obtained after drying is the mullite and tobermorite composite material.
Example 2
The high-alumina fly ash used in this example was obtained from a power plant of rubus, japan, shanxi province, and the quicklime was obtained from a lime plant of rubus, shanxi province, and the chemical composition thereof is shown in table 2.
TABLE 2 chemical compositions of high alumina fly ash and quicklime
The mullite and tobermorite type composite heat-insulating fireproof material of the embodiment is prepared by mixing 85kg of the high-alumina fly ash and 15kg of the quick lime, then 0.1kg of aluminum nitrate, 0.4kg of barium sulfate and 0.7kg of sodium sulfate are added, the mixture is milled by a ball mill until all the particle sizes are less than 0.08mm, then 1821.6kg of water is added according to the liquid-solid ratio of 18 and is evenly mixed and then is put into a high-pressure reaction kettle, controlling the reaction temperature to be 190 ℃, the reaction pressure to be 1.27MPa, keeping the temperature of 90-100 ℃ for 60min, keeping the temperature of 150 ℃ for 30min, keeping the temperature of 180 ℃ for 20min, keeping the temperature of 190 ℃ for 7.0h, wherein the stirring speed in the temperature rise process is 350rpm, the stirring speed in the temperature rise process is 150rpm, the temperature rise rate is 2 ℃/min, cooling the product to 90 ℃ after the reaction is finished, and then filtering the reaction product, and drying the obtained filter cake at the temperature of 95 ℃ for 12.0h to obtain the mullite and tobermorite composite material.
The test shows that:
the test shows that: the water content of the obtained mullite and tobermorite composite material is less than 3.4 percent by mass, and the density is 365kg/m3The thermal conductivity coefficient is 0.074W/(m.K), the compressive strength is 1.47MPa, and the flexural strength is 0.68 MPa.
The X-ray diffraction test was carried out thereon to obtain the same results as in example 1.
Example 3
The high-alumina fly ash used in this example was obtained from a power plant of Shuozhou, Shanxi province, and the chemically pure lime was obtained from a reagent factory of east China, Tianjin, and the chemical composition thereof is shown in Table 3.
TABLE 3 chemical composition of high alumina fly ash and quicklime
The mullite and tobermorite type composite heat-insulating fireproof material of the embodiment is prepared by mixing 89kg of the high-alumina fly ash and 11kg of the quick lime, then 0.8kg of barium chloride and 0.4kg of aluminum chloride are added, the mixture is milled by a ball mill until all the particle sizes are less than 0.10mm, then 2530kg of water is added according to the liquid-solid ratio of 25 and is uniformly mixed, and then the mixture is put into a high-pressure reaction kettle, controlling the reaction temperature to be 210 ℃, the reaction pressure to be 1.93MPa, keeping the temperature of 90-100 ℃ for 60min, keeping the temperature of 150 ℃ for 30min, keeping the temperature of 180 ℃ for 20min, keeping the temperature of 210 ℃ for 7.0h, wherein the stirring speed in the heating process is 320rpm, the stirring speed in the heat preservation process is 140rpm, the heating rate is 2 ℃/min, cooling the product to 90 ℃ after the reaction is finished, and then filtering the reaction product, and drying the obtained filter cake at the temperature of 95 ℃ for 16.0h to obtain the mullite and tobermorite composite material.
Tests show that:
the test shows that: the water content of the obtained mullite and tobermorite composite material is less than 2.8 percent by mass, and the density is 287kg/m3The thermal conductivity coefficient is 0.065W/(m.K), the compressive strength is 1.04MPa, and the flexural strength is 0.43MPa。
The X-ray diffraction test was carried out thereon to obtain the same results as in example 1.
Example 4
The high-alumina fly ash adopted in the embodiment is taken from a power plant in the area called and Haote in inner Mongolia, and the quick lime is taken from the clear river county in the city called and Haote in inner Mongolia, and the specific components are the same as those in the embodiment 1.
The mullite and tobermorite composite heat-insulating fireproof material of the embodiment is prepared by mixing 75kg of the high-alumina fly ash and 25kg of the quick lime, then 0.6kg of aluminum sulfate, 0.7kg of calcium sulfate and 0.4kg of barium chloride are added, the mixture is milled by a ball mill until all the particle sizes are less than 0.14mm, then 2440.8kg of water is added according to the liquid-solid ratio of 24 and is evenly mixed and then is put into a high-pressure reaction kettle, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.91MPa, keeping the temperature of 90-100 ℃ for 60min, keeping the temperature of 150 ℃ for 30min, keeping the temperature of 175 ℃ for reaction for 20.0h, wherein the stirring speed in the heating process is 300rpm, the stirring speed in the heat preservation process is 160rpm, the heating rate is 1 ℃/min, cooling the product to 90 ℃ after the reaction is finished, and then filtering the reaction product, and drying the obtained filter cake at the temperature of 95 ℃ for 10.0h to obtain the mullite and tobermorite composite material.
The test shows that:
1) the water content of the obtained mullite and tobermorite composite material is 4.3 percent by mass, and the density is 342kg/m3The thermal conductivity coefficient is 0.075W/(m.K), the compressive strength is 1.07MPa, and the flexural strength is 0.49 MPa.
2) As shown in fig. 1, we can know in the X-ray diffraction pattern: the product obtained after drying is the mullite and tobermorite composite material.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
The above detailed description is further intended to illustrate the objects, technical solutions and advantages of the present invention, and it should be understood that the above detailed description is only an example of the present invention and should not be used to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for synthesizing tobermorite composite heat-insulating material by using high-alumina fly ash is characterized by comprising the following steps: the method comprises the following steps:
step one, uniformly mixing high-alumina fly ash and a calcareous raw material, then adding a trace additive with the total mass not more than 3%, and grinding to be below 0.12mm to obtain a mixed raw material; the sum of the mass of the high-alumina fly ash and the mass of the calcareous raw materials is 70-85% of the total mass; the mass of the calcareous raw material is 15-30% of the total mass;
step two, mixing the mixed raw material obtained in the step one with water according to the liquid-solid mass ratio of 5-40, performing dynamic hydrothermal synthesis reaction after uniform pulping, and then sequentially performing filtration and drying treatment to obtain the composite heat-insulating fireproof material with the main crystal phase of mullite and tobermorite;
the micro additive is one or more of aluminum sulfate, sodium sulfate, barium sulfate, calcium sulfate, barium chloride, aluminum chloride and aluminum nitrate;
step two, the dynamic hydrothermal synthesis reaction process is as follows: heating from room temperature for multiple times in sections, and finally heating to 160-230 ℃, wherein the temperature is the final reaction temperature, and the final reaction time at the final reaction temperature is 2-8 h; the reaction pressure in the dynamic hydrothermal synthesis reaction is 0.61-2.80 MPa;
the high-alumina fly ash is fly ash with the content of alumina more than 40 percent.
2. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash as claimed in claim 1, is characterized in that: the calcareous raw material is one or more of quicklime, lime milk, chemically pure calcium oxide and chemically pure calcium hydroxide.
3. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash as claimed in claim 1, is characterized in that: the segmented temperature rise method comprises the following steps: if the final reaction temperature is not more than 180 ℃, preserving heat for 60min at 90-100 ℃, preserving heat for 30min at 150 ℃, and preserving heat for 2-8h at the final reaction temperature; if the final reaction temperature is higher than 180 ℃, keeping the temperature of 90-100 ℃ for 60min, keeping the temperature of 150 ℃ for 30min, keeping the temperature of 180 ℃ for 20min, and keeping the final reaction temperature for 2-8 h.
4. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash as claimed in claim 3, is characterized in that: the stirring speed is 100-400rpm in the temperature rising process; the stirring speed during the heat preservation process is 100-200 rpm.
5. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash according to claim 3 or 4, is characterized in that: the temperature rise rate of the sectional temperature rise is 1-3 ℃/min.
6. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash as claimed in claim 1, is characterized in that: and step two, drying, wherein the drying temperature is 90-100 ℃, and the drying time is 4-16 h.
7. The method for synthesizing tobermorite composite thermal insulation material by using high-alumina fly ash as claimed in claim 6, wherein: the content of alumina in the high-alumina fly ash is 40-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810970502.5A CN108910902B (en) | 2018-08-24 | 2018-08-24 | Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810970502.5A CN108910902B (en) | 2018-08-24 | 2018-08-24 | Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108910902A CN108910902A (en) | 2018-11-30 |
| CN108910902B true CN108910902B (en) | 2022-07-12 |
Family
ID=64406050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810970502.5A Active CN108910902B (en) | 2018-08-24 | 2018-08-24 | Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108910902B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645670B (en) * | 2020-12-29 | 2022-06-03 | 河南安筑新材料科技有限公司 | Floating bead fireproof heat insulation plate |
| CN113277794A (en) * | 2021-06-17 | 2021-08-20 | 内蒙古工业大学 | Tobo mullite type A-level wall thermal insulation material based on cooperation of carbide slag and silica fume and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828834A (en) * | 2014-02-12 | 2015-08-12 | 中国科学院过程工程研究所 | Method of preparing tobermorite from fly ash and application thereof |
| CN105692632A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院过程工程研究所 | Method for preparing tobermorite by use of silicon slag obtained after acid-process fly ash treatment for aluminium extraction |
| CN105780121A (en) * | 2016-04-18 | 2016-07-20 | 中南大学 | Method for synthesizing tobermorite whiskers with fly ash as raw material |
| CN106747205A (en) * | 2017-01-03 | 2017-05-31 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of method that utilization calcium silicate slag prepares eakleite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329409A (en) * | 1993-05-24 | 1994-11-29 | Asahi Chem Ind Co Ltd | Production of highly crystalline tobermorite |
-
2018
- 2018-08-24 CN CN201810970502.5A patent/CN108910902B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828834A (en) * | 2014-02-12 | 2015-08-12 | 中国科学院过程工程研究所 | Method of preparing tobermorite from fly ash and application thereof |
| CN105692632A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院过程工程研究所 | Method for preparing tobermorite by use of silicon slag obtained after acid-process fly ash treatment for aluminium extraction |
| CN105780121A (en) * | 2016-04-18 | 2016-07-20 | 中南大学 | Method for synthesizing tobermorite whiskers with fly ash as raw material |
| CN106747205A (en) * | 2017-01-03 | 2017-05-31 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of method that utilization calcium silicate slag prepares eakleite |
Non-Patent Citations (1)
| Title |
|---|
| 脱铝粉煤灰水热法合成1.1 nm 铝代托贝莫来石;杨敬杰等;《硅酸盐学报》;20171130;第45卷(第11期);第1700-1702页"2 实验"和"3.1 不同摩尔比的XRD分析" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108910902A (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108946748B (en) | Method for synthesizing xonotlite composite thermal insulation material from high-alumina fly ash | |
| CN111393047B (en) | A kind of high-speed iron belite cement and preparation method thereof | |
| CN102126866B (en) | A kind of high-purity silica refractory material and production technique thereof | |
| CN110606722B (en) | A kind of building wall panel and preparation method thereof | |
| CN113336516A (en) | Cementing material prepared from multi-element solid wastes and cooperative regulation and control method thereof | |
| CN111635152A (en) | High belite sulphoaluminate cement clinker and preparation method thereof | |
| CN107021654A (en) | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof | |
| CN108821686A (en) | A kind of preparation method and product of aluminium calcium carbonate composite gelled material | |
| CN108675657B (en) | Method for preparing silicate-sulphoaluminate composite system clinker by using waste residues | |
| CN104591563A (en) | Cementing material prepared from fly ash and preparation method thereof | |
| WO2019184637A1 (en) | Calcium magnesium silicate thermal insulation material, preparation method therefor and use thereof | |
| CN108910902B (en) | Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash | |
| CN108911691A (en) | A kind of method that red mud from sintering process prepares eakleite type heat preservation fireproofing material | |
| CN101607259B (en) | Method for activating fly ash at low temperature and application thereof | |
| CN106966402A (en) | The method that tobermorite is prepared using calcium silicate slag | |
| CN106673574A (en) | Non-calcined desulfurized gypsum hydraulic composite gel system | |
| CN109020397A (en) | A kind of phase-change energy-storage mortar and preparation method thereof | |
| CN109020459A (en) | A kind of method that red mud from sintering process prepares tobermorite type heat preservation fireproofing material | |
| Zhu et al. | Efflorescence of microwave-heated alkali-activated cement synthesized with ultrafine coal combustion ashes | |
| CN106242326B (en) | By SiO2Method for preparing ecological cement by using main raw materials | |
| CN104829261B (en) | Red sandstone aerated concrete and preparation method thereof | |
| Liu et al. | Environmentally friendly lime melting slag-GBFS-titanium gypsum cementitious material: Mechanical properties, hydration characteristics and microstructure | |
| CN115368034B (en) | A self-powdering carbon-cured gelling material prepared from solid waste and its preparation method | |
| CN111559896A (en) | Foaming phosphogypsum building block and preparation method thereof | |
| CN113060954B (en) | A method for preparing tobermullite-based inorganic cementitious material by using alkali-excited solid waste micropowder at room temperature and its product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |