CN114656251A - Mullite ceramic prepared from fluorite tailings and process method thereof - Google Patents
Mullite ceramic prepared from fluorite tailings and process method thereof Download PDFInfo
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- CN114656251A CN114656251A CN202210182120.2A CN202210182120A CN114656251A CN 114656251 A CN114656251 A CN 114656251A CN 202210182120 A CN202210182120 A CN 202210182120A CN 114656251 A CN114656251 A CN 114656251A
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- 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 title claims abstract description 79
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 76
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 239000000919 ceramic Substances 0.000 title claims abstract description 55
- 239000010436 fluorite Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000000280 densification Methods 0.000 abstract description 5
- 239000002920 hazardous waste Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 21
- 238000000498 ball milling Methods 0.000 description 18
- 229910052593 corundum Inorganic materials 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000010431 corundum Substances 0.000 description 14
- 229910010293 ceramic material Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 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 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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- 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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
The invention relates to a mullite ceramic prepared by fluorite tailings and a process method thereof, and relates to the technical field of solid waste treatment. The technological method of the mullite ceramic comprises the following steps of uniformly mixing fluorite tailings, alumina and secondary aluminum ash, and grinding to obtain a mixed concentrate; the mass ratio of the fluorite tailings to the alumina to the secondary aluminum ash is 10-13: 5-8: 1-3; and then the mixed concentrate is subjected to die filling and pressure application, and then sintering is carried out, so as to obtain the mullite ceramic. The process method provided by the invention has the advantages of short production period, no generation of any dangerous by-product, low preparation cost, high densification degree and high strength of the prepared mullite ceramic, solves the problem of serious environmental pollution caused by solid waste and hazardous waste which is difficult to repair, realizes efficient resource utilization of the solid waste and the hazardous waste, and opens up a new path for large-scale industrial utilization of the solid waste fluorite tailings.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to mullite ceramic prepared by fluorite tailings and a process method thereof.
Background
The fluorite tailings are waste of fluorite subjected to flotation treatment, namely fluorite ores with low fluorite content, and the main component of the fluorite tailings is SiO2The mass percentage of the catalyst is 70-80 wt% of the total mass percentage, and in addition, a small amount of CaF is contained2. In 2008, the basic reserve of fluorite ore reaches the peak, and then the exploitation of fluorite ore keeps the high-position operation state, and the current situation continues. At present, due to continuous high-level mining of fluorite ores for many years, the problem of stacking fluorite tailings is increasingly becoming a 'big and difficult' problem which cannot be ignored by people. A large amount of piles up not only occupies the land, hinders the traffic, influences resident's life and has the danger of mud-rock flow, and what is more serious is that harmful elements such as F in the fluorite tailing can infiltrate down through the rainwater erode and pollute the soil, pollute human drinking water source, cause crops to subtract output, cause serious destruction to the natural ecological environment that the people rely on to live. Therefore, the harmlessness and resource recycling of the fluorite tailings are very slow.
The aluminum ash is also called aluminum slag, is a solid waste slag generated in the aluminum industrial production, and mainly has two forms: primary aluminum ash and secondary aluminum ash. The secondary aluminum ash is solid waste containing metal aluminum and other components generated in the production, use and other processes of the industries such as electrolysis, cast aluminum and the like, the components of the secondary aluminum ash are relatively complex, the secondary aluminum ash usually contains 15% -30% of aluminum nitride, and a small amount of salt flux, oxide and the like, and the secondary aluminum ash can be subjected to hydrolysis reaction when meeting water, releases a large amount of ammonia gas and easily pollutes the environment. At present, the comprehensive resource utilization rate of secondary aluminum ash is still at a low level, a large amount of secondary aluminum ash is directly buried or accumulated near a production plant area, a series of environmental problems such as soil, air and the like are caused, and great pressure is formed on the environment.
Mullite (Mullite, 3 Al)2O3·2SiO2) Is a general name of a series of minerals generated by taking aluminosilicate as a starting material at high temperature, and is SiO2-Al2O3The compound stably existing in the binary system has high hardness, high melting point (1830 ℃), and low thermal expansion coefficient (4.5X 10)-6K-1) The mullite-containing refractory material has the advantages of small high-temperature creep value, high loaded softening point, good chemical corrosion resistance, good thermal shock resistance and the like, is an ideal refractory material, is widely applied to various fields of metallurgy, chemical industry, glass, ceramics, cement, national defense and the like, but naturally-formed mullite is rare in nature due to strict forming conditions of the mullite-containing refractory material, is generally artificially synthesized, and is usually prepared by an in-situ reaction sintering method, an electric melting method and the like. The method for preparing the mullite ceramic by using the solid wastes realizes the recycling and sustainable development utilization of the solid wastes, reduces the production cost of the mullite ceramic and enlarges the raw material production sources of the mullite ceramic. For example, in a method for preparing mullite from industrial waste residues, which is disclosed in Chinese patent CN107285774B, the used raw material is white mud which is residue left after aluminum extraction of an aluminum-containing mineral, so that the problem of recycling the aluminum-containing mineral aluminum extraction residue in the aluminum industry is solved, but the preparation process flow of the mullite in the method is more complicated, and the requirement on industrial utilization is higher; for example, in a method for preparing mullite ceramic by using alumina, silica and mullite seed crystals as raw materials, which is disclosed in chinese patent CN113754456A, the generated mullite ceramic material has good thermal shock resistance, long service life and high production efficiency, but the method requires a large number of initial synthesis raw materials, has a complicated process flow, and does not use large-scale industrial production. Also, as the method for preparing mullite by sintering natural kaolin mentioned in chinese patent CN109354032A, the mullite prepared at low temperature has uniform particle size, good dispersibility, good thermal stability, and effectively reduced energy consumption, but the method has the advantages of uniform particle size, good dispersibility, and good thermal stabilityIn the method, a large amount of organic acid such as oxalic acid or citric acid, fluorine-containing compounds such as sodium chloride or potassium fluoride and other additives are added, and the industrial requirement degree is high.
Therefore, the recycling and sustainable utilization of the solid waste are realized, and the method has important practical significance for solving the problem of random stacking and random placing of the solid waste at present.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of complicated process flow, more initial synthetic raw materials and high difficulty in industrial utilization in the mullite ceramic preparation process in the prior art.
In order to solve the technical problems, the invention provides mullite ceramic prepared by fluorite tailings and a process method thereof.
The first purpose of the invention is to provide a process for preparing mullite ceramic by using fluorite tailings, which comprises the following steps,
s1, uniformly mixing the fluorite tailings, the alumina and the secondary aluminum ash, and grinding to obtain a mixed concentrate; the mass ratio of the fluorite tailings to the alumina to the secondary aluminum ash is 10-13: 5-8: 1-3;
and S2, die-filling and pressing the mixed concentrate in the step S1, and sintering to obtain the mullite ceramic.
In one embodiment of the present invention, in the step S1, the fluorite tailings, the industrial alumina and the secondary aluminum ash all have a particle size of less than 200 mesh.
In one embodiment of the present invention, in step S1, the grinding medium is zirconia balls of 2-10 mm.
In one embodiment of the invention, the filling rate of the medium is 10-20%, the ball-to-material ratio is 3-4: 1.
in one embodiment of the present invention, in step S1, the rotation speed of the polishing is 300-400r/min, and the polishing time is 15-30 min.
In one embodiment of the present invention, in the step S2, the applied pressure of the die is 30 to 40 MPa.
In one embodiment of the present invention, in the step S2, the sintering is performed under the conditions of an oxygen partial pressure of 0.05-0.15MPa and an air flow rate of 140-160 mL/min.
In one embodiment of the present invention, in the step S2, the sintering is divided into 3 stages, namely, a preheating stage, a sintering stage and a cooling stage; the preheating section is heated to 850-900 ℃ at the heating rate of 5-10 ℃/min, and the temperature is kept for 1.5-2 h. The aluminum nitride and the metal aluminum in the secondary aluminum ash can be removed in the preheating section, so that the aluminum nitride and the metal aluminum are fully oxidized to generate aluminum oxide, the content of the aluminum oxide in the raw materials is improved, the higher aluminum-silicon ratio promotes the mullite reaction and the mullite phase at high temperature, and the strength and the thermal stability of the mullite-based ceramic are greatly improved.
In one embodiment of the present invention, the sintering section is heated to 1450-. The mullite-containing silicon dioxide can effectively promote the mullite reaction between the amorphous silicon dioxide and the crystalline silicon dioxide and the alumina in the sintering section, so that the mullite crystals grow rapidly and the columnar mullite crystals are increased remarkably. The liquid phase generated by the amorphous glass phase at high temperature greatly reduces the occurrence of closed air holes, and the existence of the glass phase is beneficial to the diffusion of aluminum ions and silicon ions related to mullite synthesis, so that the mullite reaction is more complete, and the densification degree of the ceramic material is further deepened.
In one embodiment of the invention, the cooling section is cooled to 20-35 ℃ at a cooling rate of 10-15 ℃/min.
The second purpose of the invention is to provide the mullite ceramic prepared by the method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the process method adopts two-step sintering to prepare the mullite ceramic, has short production period and can meet the requirement of large-scale industrial production. The main production raw material is solid waste fluorite tailings, and a small amount of hazardous waste secondary aluminum ash is also doped, so that the source is wide, no hazardous by-product is generated in the preparation process, the preparation cost is low, the prepared mullite ceramic is high in densification degree and high in strength, the application proportion of the fluorite tailings is more than five, the use space of the fluorite tailings is greatly expanded, the serious pollution of solid waste and hazardous waste to the environment, which is difficult to restore, is solved, the high-efficiency resource utilization of the solid waste and the hazardous waste is realized, and a new path is opened up for the large-scale industrial utilization of the solid waste fluorite tailings.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an X-ray diffraction pattern of a ceramic material in test example 2 of the present invention.
FIG. 2 is an SEM-EDS energy spectrum of mullite ceramic in test example 2 of the present invention; (ii) a Wherein, a, b, c and d are low-magnification SEM pictures of examples 1-4 respectively, and e, f, g and h are high-magnification SEM pictures of examples 1-4 respectively.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
A mullite ceramic prepared by fluorite tailings and a process method thereof specifically comprise the following steps:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing 65 parts of fluorite tailings, 25 parts of industrial alumina and 10 parts of secondary aluminum ash in proportion to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball material ratio is 3: 1, respectively weighing the components in a mass ratio of 5: 4: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 20%, and carrying out ball milling for 15min under the condition that the rotating speed is 300r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) the ground mixed concentrate is filled into a die and is pressed into a ceramic blank under the pressure of 30 MPa;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly raised to 850 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 90 min; then slowly raising the temperature to 1450 ℃ at the temperature rise rate of 2 ℃/min, and preserving the temperature for 2 h; and finally, cooling to room temperature at the cooling rate of 12 ℃/min to obtain the mullite ceramic.
Example 2
A mullite ceramic prepared by fluorite tailings and a process method thereof specifically comprise the following steps:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing according to the proportion of 60 parts of fluorite tailings, 30 parts of industrial alumina and 10 parts of secondary aluminum ash to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball-material ratio is 3: 1, respectively weighing the components in a mass ratio of 6: 3: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 15%, and carrying out ball milling for 20min under the condition that the rotating speed is 350r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) filling the ground mixed concentrate into a die, and pressing the die under 35MPa to prepare a ceramic blank;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly increased to 875 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 105 min; then slowly heating to 1500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 2.5 h; and finally, cooling to room temperature at the cooling rate of 12 ℃/min to obtain the mullite ceramic.
Example 3
A mullite ceramic prepared by fluorite tailings and a process method thereof specifically comprise the following steps:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing 55 parts of fluorite tailings, 35 parts of industrial alumina and 10 parts of secondary aluminum ash according to a proportion to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball-material ratio is 3: 1, respectively weighing the components in a mass ratio of 7: 2: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 10%, and carrying out ball milling for 25min under the condition that the rotating speed is 400r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) the ground mixed fine material is filled into a die and is pressed into a ceramic blank under 40 MPa;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly increased to 900 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120 min; then slowly heating to 1500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3 h; and finally, cooling to room temperature at the cooling rate of 12 ℃/min to obtain the mullite ceramic.
Example 4
A mullite ceramic prepared by fluorite tailings and a process method thereof specifically comprise the following steps:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing according to the proportion of 50 parts of fluorite tailings, 40 parts of industrial alumina and 10 parts of secondary aluminum ash to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball-material ratio is 3: 1, respectively weighing the components in a mass ratio of 7: 2: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 10%, and carrying out ball milling for 30min under the condition that the rotating speed is 400r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) the ground mixed fine material is filled into a die and is pressed into a ceramic blank under 40 MPa;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly increased to 900 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120 min; then slowly heating to 1550 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3 hours; and finally, cooling to room temperature at the cooling rate of 12 ℃/min to obtain the mullite ceramic.
Comparative example 1
Mainly using the secondary aluminum ash, and comprising the following steps:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing according to the proportion of 40 parts of fluorite tailings, 30 parts of industrial alumina and 30 parts of secondary aluminum ash to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball-material ratio is 3: 1, respectively weighing the components in a mass ratio of 7: 2: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 10%, and carrying out ball milling for 25min under the condition that the rotating speed is 400r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) the ground mixed fine material is filled into a die and is pressed into a ceramic blank under 40 MPa;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly increased to 900 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120 min; then slowly heating to 1500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3 h; and finally cooling to room temperature at the cooling rate of 12 ℃/min to obtain the ceramic material.
Comparative example 2
Mainly the dosage of fluorite tailings, and the specific steps are as follows:
(1) respectively drying and screening the fluorite tailings, the industrial alumina and the secondary aluminum ash to obtain particles with the particle size of less than 200 meshes;
(2) weighing the screened raw materials, and mixing according to the proportion of 70 parts of fluorite tailings, 20 parts of industrial alumina and 10 parts of secondary aluminum ash to obtain a mixture;
(3) injecting the mixture into a ball milling tank, wherein the ball-material ratio is 3: 1, respectively weighing the components in a mass ratio of 7: 2: 1, putting zirconia balls with the particle sizes of 2mm, 5mm and 10mm in a ball milling tank, wherein the filling rate is 10%, and carrying out ball milling for 25min under the condition that the rotating speed is 400r/min to obtain a mixed concentrate with the particle size of less than 200 meshes;
(4) the ground mixed fine material is filled into a die and is pressed into a ceramic blank under 40 MPa;
(5) and flatly paving the zirconia powder at the bottom of the corundum crucible, then placing the pressed ceramic blank above the zirconia powder, and sending the corundum crucible into a muffle furnace for heat treatment. The heat treatment was carried out in an air atmosphere having an oxygen partial pressure of 0.1MPa and an air flow rate of 150 mL/min. The heat treatment is that the temperature is rapidly increased to 900 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for 120 min; then slowly heating to 1500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3 h; and finally cooling to room temperature at the cooling rate of 12 ℃/min to obtain the ceramic material.
Test example 1
The ceramic materials prepared in the examples 1 to 4 and the comparative examples 1 to 2 are subjected to performance tests such as fracture toughness, bending strength and the like, and a universal material testing machine with the model of Instron 336 is used for testing; the fracture toughness adopts a single-side straight-through notched beam method, a sample with the size of 4mm multiplied by 6mm multiplied by 36mm is used, the notch depth is set to be 3mm, the span is set to be 20mm, and the loading rate is set to be 0.05 mm/min; the flexural strength is tested according to ISO14704-2000 standard, a test specimen with the size of 3mm multiplied by 4mm multiplied by 35mm is used, the set span is 30mm, the loading rate is 0.5mm/min, and the specific test results are shown in the following table 1.
Table 1 shows the relevant parameters of the finally measured mullite-based ceramic:
TABLE 1
| Test specimen | Fracture toughness (MPa. m)1/2) | Flexural strength (MPa) |
| Example 1 | 174.67 | 82 |
| Example 2 | 186.81 | 91 |
| Example 3 | 198.75 | 105 |
| Example 4 | 190.16 | 98 |
| Comparative example 1 | 167.49 | 77 |
| Comparative example 2 | 152.27 | 75 |
As can be seen from the data in Table 1, the mullite ceramic prepared by the invention has good mechanical properties. The examples are more advantageous than the comparative examples in terms of their properties, and the most prominent properties in the examples are the ceramic material samples prepared in example 3, which are excellent in fracture toughness and flexural strength.
Test example 2
(1) XRD analysis
XRD analysis tests were performed on the ceramic materials prepared in examples 1 to 4 and comparative examples 1 to 2, and X-ray diffraction patterns of the ceramic materials were measured using an X-ray diffractometer, with the results shown in FIG. 1. As can be seen from FIG. 1, the ceramic materials prepared by sintering the materials of examples 1-4 in different proportions are relatively similar in composition, mullite (3 Al)2O3·2SiO2，PDF#15-0776) were all the predominant crystalline phase and a small amount of corundum (Al) was detected2O3，PDF#43-1484) and no quartz phase was detected, indicating that all quartz phases in the sample were involved in the mullite reaction. In the examples 1 to 4, the intensity of the mullite phase diffraction peak is enhanced and then weakened, the intensity of the diffraction peak reaches the maximum in the example 3, the content of the mullite phase is at the highest level, the fracture toughness and the rupture strength of the sample also reach the highest values, and compared with other examples, the performance of the sample is obviously improved. While no significant diffraction peak of mullite phase was observed in any of comparative examples 1-2, the diffraction peak of mullite phase observed in comparative example 1 was relatively small in intensity because of Al in the raw material2O3The content is too high, so that the liquid phase amount is reduced, the generation amount of a mullite phase is correspondingly reduced, and meanwhile, the diffusivity of the liquid phase is weakened, so that the sintering compactness of a sample is poor, the fracture toughness and the breaking strength are relatively poor, and an expected product cannot be obtained; the diffraction peak intensity of the mullite phase observed in comparative example 2 is also relatively small because of α -Al in the raw material2O3In a smaller amount, resulting in a lower mullite phase content, resulting in a sampleThe fracture toughness and the breaking strength are relatively poor, and the expected mullite ceramic cannot be obtained.
(2) SEM-EDS analysis
Comparative example 1 and comparative example 2 were sintered at high temperature and cooled to obtain a glaze-like substance which spread in a corundum crucible and could not be shaped. The mullite ceramic materials prepared in examples 1 to 4 were subjected to SEM analysis and observed by a scanning electron microscope for the morphology and particle size of the ceramic material particles, and the results are shown in fig. 2. FIGS. 2a, 2b, 2c, and 2d are low-magnification SEM images of examples 1-4, respectively, and FIGS. 2e, 2f, 2g, and 2h are high-magnification SEM images of examples 1-4, respectively. As can be seen from the low-magnification SEM images 2a, 2b, 2c, and 2d, the number of pores on the surface of the ceramic sample decreased first and then increased, and the average pore diameter also tended to decrease first and then increase. In particular, in fig. 2c (i.e., example 3), the ceramic material had the least surface pores, the smallest average pore size, and the highest degree of densification. This is because the amorphous glass phase creates more liquid phase, the viscous flow mechanism facilitates the densification process, and the filling of the openings is done by capillary action. In high-magnification SEM figures 2e, 2f, 2g, 2h, 3 structures are shown, namely a: amorphous glass region, B: columnar mullite structure, C: a blocky mullite structure. With the increase of the ratio of aluminum to silicon, the amorphous glass phase region shows a trend of increasing after decreasing, the columnar mullite phase shows a trend of increasing after decreasing, and the massive mullite shows a trend of increasing. Combining with corresponding EDS analysis, as shown in Table 2, the mass percentage content of each element is shown in Table 2:
TABLE 2
| Point1 | Point2 | Point3 | Point4 | |
| Al | 9.7 | 34.6 | 27.1 | 25.8 |
| Si | 31.8 | 13.4 | 11.1 | 18.2 |
| O | 43 | 37.2 | 50.5 | 52.8 |
| Ca | 4.7 | 0.1 | 0.4 | 0.8 |
| K | 2.1 | 0.1 | 0.2 | 0.4 |
| Au | 1.2 | 4.3 | 1.4 | 0.8 |
| Na | 0.3 | 0.1 | 0.2 | 0.3 |
| Fe | 0.2 | 0.1 | 0.2 | 0.4 |
It can be seen that the spectrum contains predominantly Al, Si and O, consistent with the results of the XRD spectrum; the main component of the glass phase formed in the sample may be the Si-Al-O glass system; the columnar mullite phase and the blocky mullite phase both meet the requirement of the proportion of the mullite. Through analysis, the examples 1 to 4 have good performance, the higher degree of the example 3 accords with the ideal effect, and the test performance is best. The point scanning of 4 points selected in examples 1 to 4 revealed that small amounts of impurity elements such as K, Na, Ca, etc. were found in Al in addition to three elements of Al, Si, O in all the samples2O3-SiO2The system has the advantages of reducing the viscosity of a liquid phase formed by the glass phase at high temperature by the aid of a fluxing effect, accelerating the rapid flow of the liquid phase and promoting the generation of a mullite phase. By combining the performance analysis, the scheme of the invention is more suitable for preparing mullite ceramic, and the preparation method in the embodiment 3 is more excellent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A process method for preparing mullite ceramic by using fluorite tailings is characterized by comprising the following steps,
s1, mixing the fluorite tailings, the alumina and the secondary aluminum ash uniformly, and grinding to obtain a mixed concentrate; the mass ratio of the fluorite tailings to the aluminum oxide to the secondary aluminum ash is 10-13: 5-8: 1-3;
and S2, die-filling and pressing the mixed concentrate in the step S1, and sintering to obtain the mullite ceramic.
2. The process for preparing mullite ceramic from fluorite tailings according to claim 1, wherein in step S1, the fluorite tailings, the industrial alumina and the secondary aluminum ash all have a particle size of less than 200 meshes.
3. The process for preparing mullite ceramic from fluorite tailings as claimed in claim 1, wherein in step S1, the grinding medium is zirconia balls of 2-10 mm.
4. The process method for preparing mullite ceramic by using fluorite tailings according to claim 3, wherein the filling rate of the medium is 10-20%, and the ball-material ratio is 3-4: 1.
5. the process of claim 1, wherein in the step S1, the rotation speed of the grinding is 300-400r/min, and the grinding time is 15-30 min.
6. The process for preparing mullite ceramic from fluorite tailings as claimed in claim 1, wherein in the step of S2, the applied pressure of the die is 30-40 MPa.
7. The process of claim 1, wherein the sintering is performed under conditions of oxygen partial pressure of 0.05-0.15MPa and air flow rate of 140-160mL/min in S2 step.
8. The process for preparing mullite ceramic from fluorite tailings according to claim 1, wherein in the step of S2, the sintering is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage; the preheating section is heated to 850-900 ℃ at the heating rate of 5-10 ℃/min, and the temperature is kept for 1.5-2 h.
9. The process for preparing mullite ceramic from fluorite tailings as claimed in claim 8, wherein the sintering section is heated to 1450-.
10. The process method for preparing mullite ceramic from fluorite tailings according to claim 8, wherein the cooling section is used for cooling to 20-35 ℃ at a cooling rate of 10-15 ℃/min.
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