CN111470777B - CAS series iron tailing microcrystalline glass material and preparation method and application thereof - Google Patents
CAS series iron tailing microcrystalline glass material and preparation method and application thereof Download PDFInfo
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- CN111470777B CN111470777B CN202010229190.XA CN202010229190A CN111470777B CN 111470777 B CN111470777 B CN 111470777B CN 202010229190 A CN202010229190 A CN 202010229190A CN 111470777 B CN111470777 B CN 111470777B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 118
- 239000011521 glass Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 21
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004566 building material Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000013081 microcrystal Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 235000012255 calcium oxide Nutrition 0.000 description 16
- 238000002386 leaching Methods 0.000 description 16
- 229910001385 heavy metal Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical group [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 13
- 229910052661 anorthite Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001678 gehlenite Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
Abstract
The invention belongs to the field of harmless and comprehensive utilization of iron tailings, and discloses a CAS (CAS system iron tailing) microcrystalline glass material and a preparation method and application thereof. The microcrystalline glass material is prepared by ball-milling and mixing iron tailing powder, aluminum oxide, silicon oxide and calcium oxide powder, and then pressing the mixed powder into a sheet shape; sintering the sheet at 960-1460 ℃, and naturally cooling to normal temperature to obtain the material. The iron tailing microcrystalline glass material with excellent water absorption, elastic modulus, acid resistance and alkali resistance is obtained by implementing different raw material proportions, the water absorption is 0.3%, the elastic modulus is 733.6MPa, the acid resistance is 0.12%, and the alkali resistance is 0.01%, so that the national standard requirement is met. The method is simple, is easy for large-scale production, realizes harmless and resource utilization of the tailings, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of harmless and comprehensive utilization of solid waste tailings, and particularly relates to a CAS (CAS system iron tailing) microcrystalline glass material and a preparation method and application thereof.
Background
The tailings are solid waste generated in the beneficiation process, the content of the tailings discharged per year in China is up to more than 5 hundred million tons, and the discharge amount of the iron tailings is up to 1.5 hundred million tons. But the comprehensive utilization rate of tailings is low and is less than 10 percent. Therefore, the treatment and the reutilization of the tailings are the problems which should be paid extensive attention to in China at present. The treatment and disposal of the tailings are mainly carried out by an open-air stacking method for a long time, and the method occupies a large amount of land and causes pollution to air. And chemical elements in the iron tailings are very complex and are corroded in the open-air stacking process, and some metal elements in the iron tailings can migrate, so that the local soil and water are seriously polluted, and the human health is harmed. However, the tailings are also a potential resource, and chemical components such as alumina, silica, calcium oxide, magnesium oxide and the like contained in the tailings are common raw materials of building materials, so that the tailings can be reasonably developed and utilized to solve the environmental pollution and make up for the shortage of resources. In recent years, the treatment and utilization of tailings mainly focuses on the recovery of useful metal and non-metal minerals, as metallurgical raw materials, soil improvement agents, fertilizers, and the production of building materials. These treatment methods play a certain positive and important role, but the added value is low. The method for developing and producing the microcrystalline glass material by utilizing the tailings is a new effective way, and the microcrystalline glass has the basic properties of glass and the characteristics of ceramics, so that the microcrystalline glass has good properties, such as strong pressure resistance, good wear resistance, strong chemical corrosion resistance, small water absorption and the like, and is a product with high added value. Therefore, the microcrystalline glass prepared from the tailings can change waste into valuable, can meet the requirements of the current building materials, and has good economic and social benefits.
At present, researches on preparing microcrystalline glass by tailings are more and more, and a preparation method of the microcrystalline glass is disclosed in the patent. For example, patent CN200810306559.1 discloses a low expansion glass ceramics using spodumene tailings as main raw material and a manufacturing method thereof, which has the advantages of relatively high content of added spodumene, but more other components are added, and the sintering temperature is too high, and the temperature control process is complicated between 1550 ℃ and 1620 ℃. Patent CN201811015586.3 discloses a method for preparing glass ceramics by potassium feldspar tailings, which comprises the steps of performing high-pressure treatment on potassium feldspar particles before preparing the glass ceramics by the potassium feldspar tailings, and removing some titanium and iron in the potassium feldspar by combining a catching agent under the conditions of high pressure and weak acid formed by carbon dioxide, so that the content of the titanium and the iron is controlled within a certain range, and no nucleating agent is required to be added in the subsequent process. However, the heat treatment system of this method is complicated, and it is difficult to operate the method by water quenching. At present, methods for preparing CAS series microcrystalline glass materials by using iron tailings are few, and the methods do not pay attention to whether the leaching performance of heavy metals in the prepared products meets the national standard requirements or not. Therefore, the method for preparing the microcrystalline glass material with high performance, low cost, safety, environmental protection and simple operation from the iron tailings has important significance.
Disclosure of Invention
To overcome the above-mentioned disadvantages and drawbacks of the prior art, the present invention is primarily directed toProvides a CAS system (CaO-Al) 2 O 3 -SiO 2 ) Iron tailing microcrystalline glass material. The iron tailing microcrystalline glass material has good elastic modulus, acid resistance, alkali resistance and water absorption. The leaching concentration of heavy metals reaches the threshold value specified by the national standard GB5085.3-2007, and the environment-friendly requirement of the microcrystalline glass for building materials is met.
The invention also aims to provide a preparation method of the CAS series iron tailing microcrystalline glass material. The method is simple to operate, adopts a one-step heat treatment process for high-temperature sintering, and does not add a crystal nucleus agent. The technical problems of low resource utilization of the iron tailings, complex operation process and the like are solved.
The purpose of the invention is realized by the following technical scheme:
the CAS series iron tailing microcrystalline glass material is prepared by ball-milling and mixing iron tailing powder, aluminum oxide, silicon oxide and calcium oxide powder, then pressing the mixed powder into a sheet shape, sintering the sheet shape at 960-1460 ℃, and naturally cooling to the normal temperature.
Preferably, the mass ratio of the iron tailing powder to the alumina to the silica to the calcium oxide is (10-39): (22-33): (26-38): (13-19).
Preferably, the ball milling time is 0.5-2 h.
Preferably, the temperature rise rate of the sintering is 5-10 ℃/min.
Preferably, the sintering time is 1-3 h.
Preferably, the particle size of the iron tailing powder, the particle size of the aluminum oxide, the particle size of the silicon oxide and the particle size of the calcium oxide powder are 200-300 mu m.
Preferably, the diameter of the sheet is 25-30 mm, and the thickness is 2-4 mm.
Preferably, the pressing pressure is 20-30 MPa, and the pressing time is 1-2 min.
The preparation method of the CAS series iron tailing microcrystalline glass material comprises the following specific steps:
s1, drying iron tailings at 100-110 ℃, and grinding and sieving the iron tailings by using a ceramic mortar to obtain iron tailing powder;
s2, ball-milling and mixing iron tailing powder, aluminum oxide, silicon oxide and calcium oxide powder, and pressing the mixed powder into a sheet shape;
s4, placing the obtained sheet into an alumina crucible, then placing the crucible into a high-temperature resistance furnace for high-temperature sintering, and heating to 960-1460 ℃ for sintering; and naturally cooling to normal temperature to obtain the CAS series iron tailing microcrystalline glass material.
The CAS series iron tailing microcrystalline glass material is applied to the field of building materials.
The phases of alumina, silica and calcia used in the present invention are respectively γ -Al 2 O 3 Cristobalite and lime. The main phase of the CAS series iron tailing microcrystalline glass obtained by mixing, tabletting and sintering iron tailings, aluminum oxide, silicon oxide and calcium oxide is anorthite. When the temperature is lower than 950 ℃, the phase is mainly the phase of the raw material, namely cristobalite, quartz, lime, hematite and the like. The production of the anorthite begins at 1120 ℃, and a small amount of anorthite is produced at 1180 ℃. When the temperature was raised to 1260 ℃, the crystalline phase was completely transformed into anorthite. The reaction equation generated by the albite and the anorthite crystal phase is as follows:
3SiO 2 ·Al 2 O 3 +6CaO→3Ca 2 Al 2 SiO 7 (gehlenite) (1)
Ca 2 Al 2 SiO 7 +3SiO 2 +Al 2 O 3 →2CaAl 2 Si 2 O 8 (anorthite) (2)
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the iron tailings, the alumina, the silica and the calcium oxide powder are mixed in a specific raw material ratio, the problem of low aluminum and silicon contents in the iron tailings is solved through the synergistic effect of the components, the sintering is carried out after the mixing and tabletting, anorthite crystal phase is generated in the sintering process, and meanwhile, heavy metal is solidified in the iron tailing microcrystalline glass under the high-temperature sintering condition, so that the leaching performance of the heavy metal is obviously reduced.
2. The iron tailing microcrystalline glass material has excellent water absorption, elastic modulus, acid and alkali resistance, and meets the requirements of national standard JC/T872-2000.
3. The high-temperature sintering disclosed by the invention has a solidification effect on heavy metals in the iron tailings, the concentration of the heavy metals (Pb, Zn, Cu, Cr and Ni) in the leaching solution is far lower than the threshold value specified in GB5085.3-2007, and the harmless and resource utilization of the iron tailings is realized.
4. The preparation method is simple, large-scale production is easy, the obtained product is safe and environment-friendly, and the preparation method has good application prospect and can be applied to actual production as a building material.
Drawings
FIG. 1 is an X-ray diffraction pattern of a CAS series iron tailing microcrystalline glass material obtained by sintering at 1460 ℃ for 2 hours in examples 1-5.
FIG. 2 is a scanning electron microscope image of the CAS series iron tailing microcrystalline glass material obtained by sintering at 1460 ℃ for 2 hours in examples 1-5.
FIG. 3 is an X-ray diffraction pattern of the CAS series iron tailing microcrystalline glass material obtained by sintering the CAS series iron tailing microcrystalline glass material for 2 hours at 960-1460 ℃ in the example 6-10.
FIG. 4 is a scanning electron microscope image of the CAS series iron tailing microcrystalline glass material obtained by sintering the example 6-10 at 960-1460 ℃ for 2 h.
FIG. 5 is a schematic representation of the CAS series iron tailing microcrystalline glass materials obtained in examples 6-10.
FIG. 6 shows the water absorption, elastic modulus and acid and alkali resistance of the CAS series iron tailing glass ceramic materials obtained in examples 6-10.
Figure 7 is the heavy metal leaching performance of the CAS system iron tailing microcrystalline glass material obtained by sintering at 1460 ℃ for 2h in example 3 and the comparative example raw tailing powder and the sintered product of the raw tailing powder.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The chemical components of the iron tailings used in the embodiments 1 to 3 of the present invention are shown in table 1.
Table 1 chemical composition in iron tailings (%)
Example 1
The preparation method of the CAS series iron tailing microcrystalline glass material comprises the following steps:
1. drying the iron tailings in a drying oven at 105 ℃, and grinding and sieving by using a ceramic mortar to obtain iron tailings powder with the particle size of less than 200 mu m for later use;
2. mixing the components in a mass ratio of 10: 33: 38: 19, mixing the iron tailing powder with alumina, silica and calcium oxide by a ball mill;
3. pressing the mixed powder into a sheet with the diameter of 30mm and the thickness of 4mm at room temperature, wherein the pressure is 20MPa, and the pressing time is 2min, so as to ensure that the powder is tightly combined and facilitate the heat treatment reaction;
4. placing the obtained sheet into an alumina crucible, then placing the crucible into a high-temperature resistance furnace for high-temperature sintering, heating to 1460 ℃ at the heating rate of 5 ℃/min for sintering, and then preserving heat at 1460 ℃ for 2 h;
5. and after the alumina crucible and the high-temperature resistance furnace are naturally cooled to normal temperature, taking out the sample to obtain the CAS series iron tailing microcrystalline glass material which is marked as sample 1.
Example 2
The difference from example 1 is that: in the step 2, the mass ratio of the iron tailing powder to the aluminum oxide to the silicon oxide to the calcium oxide is 14: 28: 32: 16, the resulting CAS system iron tailing nucleated glass material, labeled sample 2.
Example 3
The difference from example 1 is that: in the step 2, the mass ratio of the iron tailing powder to the aluminum oxide to the silicon oxide to the calcium oxide is 30: 26: 29: 15, the resulting CAS system iron tailing microcrystalline glass material was labeled sample 3.
Example 4
The difference from example 1 is that: in the step 2, the mass ratio of the iron tailing powder to the aluminum oxide to the silicon oxide to the calcium oxide is 35: 24: 27: 14, the resulting CAS system iron tailing nucleated glass material, designated sample 4.
Example 5
The difference from example 1 is that: in the step 2, the mass ratio of the iron tailing powder to the aluminum oxide to the silicon oxide to the calcium oxide is 39: 22: 26: 13, the resulting CAS system iron tailing nucleated glass material, labeled sample 5.
Fig. 1 is an X-ray diffraction pattern of CAS-based microcrystalline glass materials (samples 1 to 5) obtained by sintering in examples 1 to 5 at 1460 ℃ for 2 hours, and it can be seen from fig. 1 that the main phase of the CAS-based microcrystalline glass materials is anorthite, and the strength of the anorthite is increased and then decreased along with the increase of the content of iron tailings, wherein the strength of the crystalline phase of the microcrystalline glass material (sample 4) obtained in example 4 is the highest. FIG. 2 is a scanning electron microscope image of a CAS series iron tailing microcrystalline glass material obtained by sintering at 1460 ℃ for 2h in examples 1-5, and it can be seen from FIG. 2 that as the weight percentage content of the tailings increases, the porosity of the sample becomes less and the compactness becomes better.
Example 6
The difference from example 3 is that: the sintering temperature of the iron tailing microcrystalline glass in the step 4 is 1260 ℃, and the obtained CAS series iron tailing microcrystalline glass material is marked as a sample 6.
Example 7
The difference from example 3 is that: the sintering temperature of the iron tailing microcrystalline glass in the step 4 is 1320 ℃, and the obtained CAS series iron tailing microcrystalline glass material is marked as a sample 7.
Example 8
The difference from example 3 is that: the sintering temperature of the iron tailing microcrystalline glass in the step 4 is 1360 ℃, and the obtained CAS series iron tailing microcrystalline glass material is marked as a sample 8.
Example 9
The difference from example 3 is that: the sintering temperature of the iron tailing microcrystalline glass in the step 4 is 1420 ℃, and the obtained CAS system iron tailing microcrystalline glass material is marked as a sample 9.
Example 10
The difference from example 3 is that: the sintering temperature of the iron tailing microcrystalline glass in the step 4 is 1460 ℃, and the obtained CAS series iron tailing microcrystalline glass material is marked as a sample 10.
FIG. 3 is an X-ray diffraction pattern of the CAS series iron tailing microcrystalline glass materials (samples 6-10) obtained by sintering the CAS series iron tailing microcrystalline glass materials for 2 hours in different temperatures in examples 6-10. The results show that: when the sintering temperature is 960 ℃, the main phases of the product are quartz, cristobalite, lime and hematite. Consistent with the addition of the starting materials, this indicates that no reaction has occurred between the starting materials. At 1120 c, gehlenite formation occurred in the product, and at this temperature, reaction between the starting materials began to occur. At 1180 ℃, a small amount of anorthite began to appear. When the temperature is increased to 1260 ℃, the gehlenite disappears, the peak of the gehlenite becomes more, and the strength is enhanced. As the temperature was increased up to 1460 ℃, the strength of anorthite was continuously increased.
FIG. 4 is a scanning electron microscope image of CAS series iron tailing microcrystalline glass materials (samples 6-10) obtained by sintering for 2h at different temperatures in examples 6-10, and it can be seen from FIG. 4 that along with the increase of the temperature, the pores of the samples become small, the microstructure compactness becomes good, and the volume of crystal particles attached to the surfaces of the samples becomes small and the number of the crystal particles becomes large. The above results indicate that low temperature does not allow sufficient contact of iron tailings, alumina, silica and calcia, so that the intermediate compound gehlenite is produced. And when the temperature is 1180-1460 ℃, stronger reaction is realized among the raw materials, and anorthite is formed.
FIG. 5 is a schematic representation of the CAS series iron tailing microcrystalline glass materials obtained in examples 6-10. As can be seen from fig. 5, as the temperature increases, the porosity of the sample surface decreases and the number of crystals increases. The temperature rise is shown to promote the growth of crystals and make the microstructure of the sample denser. FIG. 6 shows the water absorption, elastic modulus and acid and alkali resistance of the CAS series iron tailing glass ceramic materials obtained in examples 6-10. As can be seen from fig. 6, the water absorption, elastic modulus, acid resistance and alkali resistance of the obtained CAS system iron tailing microcrystalline glass material are all enhanced with the increase of temperature, which shows that the crystal content of the obtained CAS system iron tailing microcrystalline glass is increased and the density is increased by the temperature, so that the water absorption, elastic modulus, acid resistance and alkali resistance of the obtained CAS system iron tailing microcrystalline glass are enhanced.
The CAS series iron tailing microcrystalline glass materials in the examples 1-10 are subjected to performance tests, wherein the test methods of water absorption and elastic modulus refer to GB/T9966.3-2001, and the test method of acid and alkali resistance refers to JC/T872-2000. The water absorption, elastic modulus, acid and alkali resistance results of the iron tailing microcrystalline glass of the invention are shown in table 3.
TABLE 3 Properties of the CAS series iron tailing nucleated glass materials obtained in examples 1-10
Note: the national standard stipulates that the acid resistance and the alkali resistance, namely the mass loss rate, are not more than 0.2 percent and the appearance is unchanged.
Table 3 shows the properties of the CAS series iron tailing microcrystalline glass materials obtained in examples 1-10. The national standard of water absorption and elastic modulus refers to JC 205-92, and the acid and alkali resistance refers to the requirement of the national standard JC/T872-2000. As can be seen from the detection results in Table 3, the CAS-system iron tailing microcrystalline glass materials (sample 3 and sample 10) obtained in examples 3 and 10 have excellent water absorption, elastic modulus, acid and alkali resistance, the water absorption is 0.3%, the elastic modulus is 733.6MPa, the acid resistance is 0.12%, and the alkali resistance is 0.01%, so that the national standard requirements are met. In addition, with the increase of the temperature, various properties of the CAS series iron tailing microcrystalline glass are improved.
Leaching performance test is carried out on the CAS series iron tailing microcrystalline glass material obtained in the example 3, and the heavy metal leaching performance test method comprises the following steps:
(1) grinding the prepared CAS series iron tailing microcrystalline glass material into powder for later use;
(2) dissolving 5.7mL of acetic acid solution in deionized water, then using the deionized water to fix the volume to 500mL, adding 64.3mL of 1mol/L NaOH to fix the volume to 1L, and using 1mol/L HNO 3 Or 1mol/L NaOH to adjust the pH value of the solutionKeeping the temperature within the range of 4.93 +/-0.05 to prepare a leaching solution;
(3) each sample (1g of iron tailing microcrystalline glass powder is mixed with 20mL of leaching solution) is put into a centrifuge tube, the centrifuge tube is respectively placed on an overturning oscillator to vibrate for 0.25, 0.5, 1, 1.5, 2, 3, 7, 14 and 28 days, three parallel samples are arranged in each group of samples, and the corresponding samples are taken out after each period is finished.
(4) Centrifuging the sample, collecting supernatant, filtering with 0.45 μm filter head, and measuring heavy metal concentration in the supernatant.
Meanwhile, the comparison samples are respectively an iron tailing powder sintered product and iron tailing powder, namely the iron tailing powder is directly sintered under the condition that no reagent is added, the obtained product is ground into powder and then subjected to a leaching test, and the iron tailing powder is directly subjected to the leaching test. Figure 7 is the heavy metal leaching results of CAS system iron tailing microcrystalline glass material obtained by sintering at 1460 ℃ for 2h in example 3 and comparative example raw tailing powder and sintered product of raw tailing powder. Wherein o denotes raw tailings powder, o denotes raw tailings powder sintered product, and o denotes CAS-system microcrystalline glass; as can be seen from fig. 5, the leaching concentration of heavy metals Zn, Cu, Cr, and Ni in the raw tailing powder sintered product after high-temperature sintering is significantly reduced, but for Pb, the leaching concentration of the product obtained by sintering the iron tailing powder is increased. The heavy metal leaching concentration of the CAS series iron tailing microcrystalline glass material obtained by adding alumina, silica and calcium oxide into the iron tailing powder is lower than that of the other two groups. The results show that the iron tailing microcrystalline glass material prepared under the high-temperature sintering condition after mixing the iron tailing, the aluminum oxide, the silicon oxide and the calcium oxide powder can effectively solidify heavy metals in the product, the obtained material is safe and environment-friendly, and the recycling and harmless utilization of the iron tailing are realized.
Heavy metals in the iron tailing microcrystalline glass are solidified under the high-temperature sintering condition, the concentration of the heavy metals in the leaching solution is far lower than the specified threshold value, the GB5085.3-2007 requirement is met, and the recycling and harmless utilization of the iron tailings are realized. The preparation method of the CAS series iron tailing microcrystalline glass is simple to operate, the obtained product is safe and environment-friendly, large-scale production is easy to realize, and the CAS series iron tailing microcrystalline glass can be used as a building material to be applied to industrial production.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The CAS series iron tailing microcrystalline glass material is characterized in that iron tailing powder, aluminum oxide, silicon oxide and calcium oxide powder are subjected to ball milling for 0.5-2 hours and mixed, then the mixed powder is pressed for 1-2 minutes at the pressure of 20-30 MPa to form a sheet shape, the temperature of the sheet shape is raised to 960-1460 ℃ at the speed of 5-10 ℃/min, the sheet shape is sintered for 1-3 hours, and the material is naturally cooled to the normal temperature to obtain the CAS series iron tailing microcrystalline glass material; the mass ratio of the iron tailing powder to the aluminum oxide to the silicon oxide to the calcium oxide is (10-39): (22-33): (26-38): (13-19); the particle size of the iron tailing powder, the particle size of the aluminum oxide, the particle size of the silicon oxide and the particle size of the calcium oxide powder are 200-300 mu m.
2. The CAS system iron tailing microcrystalline glass material of claim 1, wherein the sheet shape has a diameter of 25-30 mm and a thickness of 2-4 mm.
3. The preparation method of the CAS system iron tailing microcrystalline glass material according to claim 1 or 2, characterized by comprising the following specific steps:
s1, drying iron tailings at 100-110 ℃, and grinding and sieving the iron tailings by using a ceramic mortar to obtain iron tailing powder;
s2, ball-milling and mixing iron tailing powder, aluminum oxide, silicon oxide and calcium oxide powder, and pressing the mixed powder into a sheet shape;
s4, placing the obtained sheet into an alumina crucible, then placing the crucible into a high-temperature resistance furnace for high-temperature sintering, and heating to 960-1460 ℃ for sintering; and naturally cooling to normal temperature to obtain the CAS series iron tailing microcrystal glass material.
4. The application of the CAS series iron tailing microcrystalline glass material as claimed in claim 1 or 2 in the field of building materials.
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