CN114959893B - Sintering method red mud carbonization recycling method and application of product thereof - Google Patents
Sintering method red mud carbonization recycling method and application of product thereof Download PDFInfo
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- CN114959893B CN114959893B CN202210474816.2A CN202210474816A CN114959893B CN 114959893 B CN114959893 B CN 114959893B CN 202210474816 A CN202210474816 A CN 202210474816A CN 114959893 B CN114959893 B CN 114959893B
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- 238000003763 carbonization Methods 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 84
- 238000005245 sintering Methods 0.000 title claims abstract description 65
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 136
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000002002 slurry Substances 0.000 claims abstract description 50
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 100
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 50
- 239000004568 cement Substances 0.000 claims description 39
- 238000005273 aeration Methods 0.000 claims description 17
- 230000008569 process Effects 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 10
- 238000010000 carbonizing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000000047 product Substances 0.000 description 70
- 239000007789 gas Substances 0.000 description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 24
- 238000012360 testing method Methods 0.000 description 19
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 16
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 12
- 235000019341 magnesium sulphate Nutrition 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000006703 hydration reaction Methods 0.000 description 9
- 230000036571 hydration Effects 0.000 description 8
- 229910021532 Calcite Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 239000003469 silicate cement Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical group [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/383—Whiskers
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention provides a carbonization recycling method of sintering red mud and application of a product thereof. The method comprises the following steps: preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution; step two, adding the sintering red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry; step three, introducing CO-containing slurry into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering slurry after the carbonization reaction is finished, and drying filter residues to obtain a product, wherein the product comprises calcium carbonate whiskers. The method can realize high value-added utilization of the sintering red mud, can prepare the calcium carbonate whisker with high value-added product with high efficiency and low cost, and can better solidify carbon dioxide gas.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a sintering method red mud carbonization recycling method and application of a product thereof.
Background
The synthetic aragonite type calcium carbonate whisker is a novel green environment-friendly material, has high cost performance, is widely applied to organic and inorganic composite materials as an excellent reinforcing and toughening filling material, and has wide application prospect and strong market competitiveness. At present, a relatively common method for synthesizing calcium carbonate whiskers at home and abroad is a carbonization method. However, in the existing methods for preparing calcium carbonate whiskers, the raw materials for preparing the calcium carbonate whiskers are mainly industrial ores such as marble, calcite, limestone and dolomite with high calcium content. The research of preparing the calcium carbonate whisker by utilizing the solid waste with high calcium content, household garbage and the like so as to realize the utilization of the solid waste with high added value also draws attention of a plurality of students. For example, some scholars extract calcium component crystal forms in steel slag based on ammonia water, and then the calcium carbonate whisker is prepared by regulating and controlling the pH value of a reaction system. Some scholars use phosphogypsum as a calcium source, and make calcium carbonate whisker by a carbonization method after refining through technologies such as HCl leaching, ammonia water impurity removal and the like. Still other scholars prepare calcium carbonate whiskers by a double decomposition method after acidizing carbide slag. And some students electrolyze and carbonize fly ash by using high-salt wastewater discharged from a traditional coal-fired power plant to prepare calcium carbonate whiskers. These are all high added value products prepared by utilizing solid wastes with high calcium content, but the process treatment before carbonization of the solid wastes is complex, such as grinding of steel slag and acidification and impurity removal of gypsum. The sintering red mud is liquid waste discharged by the sintering aluminum smelting process, is discharged and piled up in open air, pollutes underground water resources and environment, belongs to building materials which are difficult to be utilized in a large amount in solid waste due to high alkali content and low hydration activity, and can only realize low added value utilization of the sintering red mud at present.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a carbonization recycling method of sintering red mud and application of a product thereof, so as to solve the problem that the prior art can only realize low added value utilization of the sintering red mud.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for carbonizing and reutilizing red mud by a sintering method, which comprises the following steps:
preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution;
step two, adding the sintering red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry;
step three, introducing CO-containing slurry into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering slurry after the carbonization reaction is finished, and drying filter residues to obtain a product, wherein the product comprises calcium carbonate whiskers.
Optionally, in the first step, the concentration of the magnesium salt solution is 0.2-0.4mol/L; the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate.
Optionally, in step one, the magnesium salt solution is heated to a temperature of 60-80 ℃.
Optionally, in the second step, the mass ratio of the sintering red mud to the magnesium salt hot solution is 1:10-1:20.
Optionally, in the second step, the stirring speed is 300-500r/min.
Optionally, in step three, the CO-containing gas is a gas 2 The gas is industrial tail gas, and the CO contains 2 CO in gas 2 The volume concentration of (2) is 10-100%; the CO containing 2 The aeration rate of the gas is 0.1-0.5L/min/g.
Optionally, in the third step, the carbonization reaction time is 1-3 hours.
Optionally, in step three, the product further comprises a silica-alumina gel.
The invention also provides the calcium carbonate whisker produced by the sintering method red mud carbonization recycling method, and the length-diameter ratio of the calcium carbonate whisker is 5-6.
The invention also provides application of the product obtained by the sintering method red mud carbonization recycling method, which is characterized in that the product is applied to preparation of cement paste.
The beneficial effects are that:
the carbonization recycling method of the sintering red mud can realize high value-added utilization of the sintering red mud, can prepare the calcium carbonate whisker with high value-added product with high efficiency and low cost, and can better solidify carbon dioxide gas.
The method does not need a carbon dioxide sealing carbonization device, is easy for continuous production, does not depend on the concentration of carbon dioxide in carbonization effect, and can utilize carbon dioxide industrial waste gas with different concentrations to realize the recycling of the industrial waste gas.
The liquid form of the sintering method red mud is easier to carbonize by a wet method when the sintering method red mud is discharged, and the feasibility of industrial utilization is strong;
the method has simple process, the generated filtrate can be recycled, and the obtained product calcium carbonate whisker has the characteristic of short fibers.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Wherein:
FIG. 1 is a FT-IR spectrum of carbonized products of sintered process red mud at different magnesium chloride concentrations obtained in example 1 of the present invention;
FIG. 2 is an SEM image of carbonized red mud produced by sintering process at different magnesium chloride concentrations as obtained in example 1 of the present invention, wherein FIG. a shows a magnesium chloride concentration of 0.1mol/L, FIG. b shows a magnesium chloride concentration of 0.4mol/L, FIG. c shows a magnesium chloride concentration of 0.8mol/L, and FIG. d shows a magnesium chloride concentration of 1.2mol/L;
FIG. 3 is an XRD pattern of a carbonized product of sintered red mud at different carbonization temperatures under the condition that the concentration of magnesium chloride obtained in example 2 of the present invention is 0.4mol/L;
FIG. 4 is an XRD pattern of carbonized products of sintered process red mud at different carbonization times as obtained in example 3 of the present invention;
FIG. 5 is an SEM image of the carbonized product of the red mud sintered at different carbonization times according to example 3 of the present invention, wherein the graph a shows the carbonization time as 10min, the graph b shows the carbonization time as 30min, the graph c shows the carbonization time as 60min, the graph d shows the carbonization time as 120min, the graph e shows the carbonization time as 180min, and the graph f shows the carbonization time as 240min;
FIG. 6 is an SEM image of carbonized product of sintered red mud obtained in example 4 of the present invention;
FIG. 7 is a schematic view showing the influence of the carbonized product of the red mud obtained in the sintering method in example 4 of the present invention on the strength of cement paste;
FIG. 8 is an SEM image (left) and an EDS image (right) of hydration 3d of a cement slurry with an admixture of 5% of the carbonized product of the sintered red mud obtained in example 4;
FIG. 9 is an SEM image of the carbonized product of sintered red mud at different carbonization temperatures obtained in comparative example 1, wherein the graph a shows a carbonization temperature of 20℃and the graph b shows a carbonization temperature of 40℃and the graph c shows a carbonization temperature of 60℃and the graph d shows a carbonization temperature of 80 ℃.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention provides a carbonization recycling method of sintering red mud, which aims to realize high value-added utilization of the sintering red mud, can prepare and obtain a high value-added product calcium carbonate whisker with high efficiency and low cost, and can better solidify carbon dioxide gas.
In the embodiment of the invention, the carbonization and recycling method of the red mud by the sintering method comprises the following steps:
preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution.
In the specific embodiment of the present invention, in the first step, the concentration of the magnesium salt solution is 0.2-0.4mol/L (for example, 0.2mol/L, 0.3mol/L, 0.4mol/L and the interval value between any two end points), the magnesium salt solution with the concentration range is adopted, the finally produced calcium carbonate is aragonite calcium carbonate, and if the concentration of the magnesium salt solution is less than 0.2mol/L, the produced calcium carbonate is calcite type; if the concentration of the magnesium salt solution is more than 0.4mol/L, the morphology of the produced calcium carbonate whisker is destroyed, the whisker surface is rough, and cracks appear.
In a specific embodiment of the present invention, the magnesium salt is a soluble magnesium salt, and may be at least one of magnesium chloride, magnesium sulfate, and magnesium nitrate. Preferably, magnesium chloride, under the condition of equal magnesium-calcium ratio, the content of calcium carbonate whisker synthesized by adopting magnesium sulfate and magnesium nitrate as control agents is small, and chloride ions in the magnesium chloride can inhibit the growth of calcite type calcium carbonate and promote the generation of aragonite type calcium carbonate, so that the generation amount of calcium carbonate whisker can be increased by adopting the magnesium chloride.
In an embodiment of the invention, the magnesium salt solution is heated to a temperature of 60-80℃ (e.g., 60℃, 65℃, 70℃, 75℃,80℃, and any interval between two endpoints). Heating the magnesium salt solution to the range, so that the growth of the product calcium carbonate whisker along the length direction is facilitated; if the temperature is lower than 60 ℃, the calcium carbonate whisker is not easy to prepare; when the temperature is higher than 80 ℃, the local saturation of the system is higher, and the content of the product calcium carbonate whisker can be reduced.
And step two, adding the sintering red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry.
In the specific embodiment of the invention, the mass ratio of the sintering red mud to the magnesium salt hot solution is 1:10-1:20 (such as 1:10, 1:15, 1:20 and interval values between any two endpoint values). By selecting the mass ratio, the sintering red mud can be ensured to be fully dissolved in the solution, and the liquid form during industrial discharge is close to the liquid-solid ratio of 10, so that the next carbonization work is facilitated. If the mass ratio of the two is more than 1:10, the slurry is too thick, which is not beneficial to carbonization; if the mass ratio of the two is less than 1:20, the slurry is too thin, and the carbonization efficiency is reduced.
In the embodiment of the invention, the stirring speed is300-500r/min (e.g., 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, and interval values between any two endpoint values). The stirring speed range is selected for stirring and mixing, so that the slurry which is uniformly mixed can be obtained relatively quickly; if the stirring speed is less than 300r/min, CO may not be sufficiently dissolved and dispersed 2 Resulting in CO in aqueous solution 2 The dispersion is uneven, and the carbonization effect is not satisfied; if the stirring speed is more than 500r/min, CO will be caused 2 Not so much as to dissolve and escape as a result of the reaction. In order to achieve the best carbonization effect, the stirring speed should be equal to that of CO 2 The aeration rate and concentration are matched. That is, when the aeration rate is small, the stirring rate is small, and when the aeration rate is large, the stirring rate is large. The aeration rate is in turn related to the concentration of carbon dioxide in the industrial flue gas, the greater the concentration of carbon dioxide the less aeration rate is required.
Step three, introducing CO-containing slurry into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering slurry after the carbonization reaction is finished, and drying filter residues to obtain a product, wherein the product comprises calcium carbonate whiskers.
In a specific embodiment of the invention, the catalyst contains CO 2 The gas is industrial tail gas containing CO 2 CO in gas 2 The volume concentration of (a) is 10-100% (e.g., 10%, 20%, 30%, 50%, 70%, 100% and the interval between any two endpoints); the carbonization effect is independent of the concentration of carbon dioxide, and industrial waste gas of carbon dioxide with different concentrations can be utilized to realize the recycling of the industrial waste gas.
In a specific embodiment of the invention, the catalyst contains CO 2 The aeration rate of the gas is 0.1-0.5L/min/g (0.1L/min/g, 0.2L/min/g, 0.3L/min/g, 0.4L/min/g, 0.5L/min/g and interval value between any two end points), namely the CO content which is required to be satisfied by each gram of raw material (sintered red mud) 2 The ventilation rate of the gas is correspondingly improved along with the increase of the addition amount of the red mud in the sintering process, and the CO-containing gas is introduced into the method 2 The amount of the gas can meet the requirement of generating calcium carbonate whiskers by carbonization reaction, the product amount is reduced due to the too small rate, and waste is caused by the too large inlet amount.
In the specific embodiment of the invention, the carbonization reaction time is 1-3h (such as 1h, 2h, 3h and the interval value between any two endpoint values). Under the carbonization reaction time, a large amount of calcium carbonate whiskers can be generated in the slurry through carbonization reaction, the whisker surface appearance is smooth, and the length-diameter ratio is 5-6; if the carbonization time is less than 1h, the amount of calcium carbonate whisker generated in the slurry is less through carbonization reaction; if the carbonization time is more than 3 hours, the amount of calcium carbonate whiskers generated in the slurry is not increased through carbonization reaction.
Further, the obtained product also comprises aluminosilicate gel which has pozzolanic activity and can react with calcium hydroxide which is a cement hydration product to generate calcium aluminate hydrate and calcium silicate hydrate, and the content of the hydration product is increased, so that the strength of the cement paste is enhanced.
In the specific embodiment of the invention, the filtrate formed after the filtration in the step three can be recycled, and the filtrate is heated to 60-80 ℃, and then the step two and the step three are recycled to continuously prepare the calcium carbonate whisker, so that the production cost is saved, and the method has the advantages of environmental protection, high efficiency and economy.
The invention also provides the calcium carbonate whisker produced by the sintering method red mud carbonization recycling method, and the length-diameter ratio of the calcium carbonate whisker is 5-6.
The invention also provides application of the product obtained by the sintering method red mud carbonization recycling method, and the obtained product is applied to preparing cement paste. Specifically, the obtained product can replace part of cement to prepare cement paste, the replacement amount is 1-10% of the mass of cement, the cement ratio of the prepared cement paste is controlled to be 0.5, and the cement can be selected from one of silicate cement, ordinary silicate cement and sulphoaluminate cement.
The following describes the sintering process red mud carbonization recycling method and the application of the product thereof in detail by specific examples.
Example 1
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium chloride solutions with the concentration of 0, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.8mol/L and 1.2mol/L respectively, and heating the magnesium chloride solutions to 80 ℃ to obtain a magnesium chloride hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium chloride hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium chloride hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 400r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2h; and filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain carbonized products of the sintering red mud under different magnesium chloride concentrations.
FT-IR and SEM tests were performed on the carbonized product of sintered red mud at different magnesium chloride concentrations obtained in this example, and the test results are shown in FIG. 1 and FIG. 2, respectively, and it can be seen from FIG. 1 that the carbonized sintered red mud product mainly contains C-O groups and Si-O-Si groups, wherein 1417, 876 and 712cm -1 Is the vibration peak of calcite type calcium carbonate, and mainly exists in the red mud raw material of sintering method, 1480 and 855cm -1 Is the vibration peak of aragonite calcium carbonate; 562 and 1003cm -1 Is the vibration peak of silica gel with high polymerization degree. As can be seen, as the concentration of magnesium chloride increases, the calcite vibration peak disappears, aragonite calcium carbonate is generated, the intensity of the vibration peak gradually increases and then decreases, and 1480cm of the sample is obtained when the concentration of magnesium chloride is 0.4mol/L -1 The maximum area of the vibration peak of the aragonite type calcium carbonate shows that the aragonite production amount is the largest at the moment. When the solubility of magnesium chloride exceeds 0.4mol/L, 1621cm -1 A new vibration peak appears at the position corresponding to a magnesium chloride substance, which indicates that the magnesium chloride content is too high at the moment and is attached to a whisker product, and the corresponding aragonite vibration peak is weaker, which indicates that the whisker content is very small. In addition, as the concentration of magnesium chloride increases, the vibration peak of Si-O-Si groups is enhanced, which shows that the red mud carbonized product of the sintering method contains certain silica-alumina gel besides whiskers. The highly polymerized silica-alumina gel has better activity, can rapidly participate in cement hydration reaction, and increases the content of hydration products, thereby enhancing the strength of cement paste. As can be seen from FIG. 2, when chloridizingThe calcium carbonate crystal form is also calcite type when the magnesium concentration is 0.1mol/L, and a large amount of aragonite type calcium carbonate is generated when the magnesium chloride concentration is 0.2mol/L, and the rod-shaped aragonite grows radially around and loosely overlaps and fills the space, and the length-diameter ratio is about 5-6. When the magnesium chloride concentration exceeds 0.4mol/L, i.e., the concentration is 0.8mol/L and 1.2mol/L, it can be seen that the whisker morphology is destroyed, and especially in FIG. 2 (d), the whisker surface is roughened and cracks appear.
Example 2
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing a magnesium chloride solution with the concentration of 0.4mol/L, and heating the magnesium chloride solution to 20 ℃,40 ℃,60 ℃ and 80 ℃ respectively to obtain a magnesium chloride hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium chloride hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium chloride hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 400r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas is 0.1L/min/g, the carbonization time is 2h, the slurry after the carbonization reaction is finished is filtered, and the obtained filter residues are dried to obtain carbonized products of the sintering process red mud at different carbonization temperatures.
XRD test was performed on the carbonized product of the red mud obtained in this example at different carbonization temperatures, and the test results are shown in FIG. 3. As can be seen from fig. 3, no aragonite is generated at the carbonization temperature of 20 ℃, little aragonite is generated at the carbonization temperature of 40 ℃, and the carbonized product is magnesium calcium carbonate and whisker cannot be formed; at carbonization temperatures of 60℃and 80℃a large amount of aragonite appears in the carbonized product. The XRD spectrum is subjected to full spectrum fitting and simple quantitative analysis, and the result shows that the content of aragonite whisker increases with the increase of temperature, namely 0%, 10.8%, 52.6% and 60.5% respectively.
Example 3
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium chloride solutions with the concentration of 0.4mol/L respectively, and heating the magnesium chloride solutions to 80 ℃ to obtain magnesium chloride hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium chloride hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium chloride hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 400r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is respectively 10min, 30min, 60min, 120min, 180min and 240min; and filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain carbonized products of the sintering process red mud under different carbonization times.
XRD test and SEM test were performed on carbonized products of sintered red mud at different carbonization times obtained in this example, and the test results are shown in FIGS. 4 and 5. A simple quantitative analysis of the full spectrum fit of the XRD pattern in fig. 4 shows that as the carbonization time increases, the calcium carbonate whisker content in the crystal phase increases and then decreases. As can be seen from FIG. 5, as the carbonization time increases, whiskers are generated in large amounts, the surface morphology becomes smooth, the aspect ratio increases, but when the carbonization time is too long, the calcium carbonate whisker content does not increase. In general, when the carbonization time is 120min, the calcium carbonate whisker content is at most 60.2%, the whisker morphology is good, and the length-diameter ratio is about 6.
Example 4
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium chloride solutions with the concentration of 0.4mol/L respectively, and heating the magnesium chloride solutions to 80 ℃ to obtain magnesium chloride hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium chloride hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium chloride hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 400r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas was 0.1L/min/g, and the carbonization reaction time was 2h, performing H; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain a carbonized product of the sintering red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel;
(4) And (3) adding the carbonized product obtained in the step (III) into Portland cement to replace part of Portland cement, wherein the replacement amount is 0, 1%, 2%, 3% and 5% of the cement mass respectively, controlling the water cement ratio to be 0.5, uniformly mixing and stirring according to the proportion to obtain cement calcium carbide whisker mixed slurry, casting and molding the cement calcium carbide whisker mixed slurry by a mold, wherein the mold specification is 40X 40mm, demolding after one day, and then curing for 1 day, 3 days, 7 days and 28 days by water to obtain different groups of cement test blocks. The cement used in the embodiment is 42.5-grade silicate cement, and the performance index of the cement meets the requirements of national standard GB 8076-2008.
SEM test is carried out on carbonized products of the red mud obtained by the sintering method in the embodiment, and as shown in FIG. 6, it can be seen from FIG. 7 that rod-shaped whiskers on the surfaces of cluster particles radially grow to the periphery, and part of whisker inclusions are alternately distributed among the particles, and the cluster particles may be silica-alumina gel.
Meanwhile, compressive strength of different groups of cement test blocks is tested according to GB50081-2002 Standard for test method of mechanical Properties of ordinary concrete, and test results are shown in Table 1 and FIG. 7. As can be seen from table 1 and fig. 7, the addition of the obtained carbonized product enhanced the strength of silicate cement paste at each age, and when the amount of the carbonized product added was 5% of the cement mass, the compressive strength of the cured 28d was increased by 20.5% as compared with the blank group, and when the amount of the carbonized product added exceeded 5%, the strength increase tended to decrease although the strength was increased as compared with the blank group. It is possible that excessive whisker fiber aggregation tends to occur, resulting in a decrease in strength. When the mixing amount is more than 10% of the mass of the cement, the fluidity of the cement is affected, the water reducer is required to be added, the cost is increased, and the strength is not remarkably improved. So that the best effect can be achieved when the mass of the carbonized product instead of cement is 5%.
TABLE 1 compressive Strength (MPa) at different ages for cements with different amounts of carbonized product
| 0％ | 1％ | 2％ | 3％ | 5％ | 6％ | 8％ | 10％ | |
| 1d | 9.00 | 9.80 | 10.25 | 11.46 | 11.43 | 11.25 | 10.28 | 9.96 |
| 3d | 15.25 | 16.77 | 19.26 | 18.73 | 20.30 | 18.26 | 17.26 | 16.20 |
| 7d | 22.00 | 23.50 | 25.69 | 23.74 | 27.60 | 25.40 | 23.54 | 22.60 |
| 28d | 31.56 | 31.68 | 32.82 | 36.91 | 38.02 | 35.61 | 34.01 | 32.69 |
Further, SEM and EDS tests were performed on cement test pieces obtained by the sintering method of the present example, in which cement paste with an admixture of 5% was hydrated and oxidized for 3d, and the test results are shown in fig. 8, and it can be seen from fig. 8 that there was an obvious rod-like substance, and the calcium carbonate whisker was proved by the EDS test. Meanwhile, the whisker surface is wrapped by hydration products, the whisker is tightly connected with the cement matrix and the cement hydration products, and the cement matrix and the cement hydration products play roles of bonding and bridging, which is also the reason for the strength increase of the cement test block.
Example 5
(1) Preparing magnesium sulfate solutions with the concentration of 0.4mol/L respectively, and heating the magnesium sulfate solutions to 80 ℃ to obtain a magnesium sulfate hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium sulfate hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium sulfate hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 400r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain a carbonized product of the sintering red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel;
XRD testing was performed on the product of this example, with a whisker content of about 25.8%.
Example 6
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium chloride solutions with the concentration of 0.3mol/L respectively, and heating the magnesium chloride solutions to 80 ℃ to obtain magnesium chloride hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium chloride hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium chloride hot solution is 1:10, and stirring and mixing the mixture at the stirring rate of 500r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 30% by volume and contains CO 2 The aeration rate of the gas is 0.3L/min/g, and the carbonization reaction time is 2h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain a carbonized product of the sintering red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel; the whisker content was about 58.6% as measured by XRD.
Example 7
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium sulfate solutions with the concentration of 0.2mol/L respectively, and heating the magnesium sulfate solutions to 60 ℃ to obtain a magnesium sulfate hot solution;
(2) Adding the sintering red mud micropowder into the magnesium sulfate hot solution in the step (1), wherein the mass ratio of the two is 1:20, and stirring and mixing at the stirring rate of 300r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 10% by volume and contains CO 2 The aeration rate of the gas is 0.5L/min/g, and the carbonization reaction time is 1h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain a carbonized product of the sintering red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel; whisker content was about 10.6% by XRD.
Example 8
The carbonization and recycling method of the sintering method red mud comprises the following steps:
(1) Preparing magnesium nitrate solutions with the concentration of 0.2mol/L respectively, and heating the magnesium nitrate solutions to 75 ℃ to obtain a magnesium nitrate hot solution;
(2) Adding the red mud micropowder of the sintering method into the magnesium nitrate hot solution in the step (1), wherein the ratio of the red mud micropowder to the magnesium nitrate hot solution is 1:15, and stirring and mixing the red mud micropowder at the stirring rate of 300r/min to obtain slurry;
(3) Introducing CO-containing into the slurry 2 Gas, CO-containing 2 CO in gas 2 Is 50% by volume and contains CO 2 The aeration rate of the gas is 0.4L/min/g, and the carbonization reaction time is 1h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residues to obtain a carbonized product of the sintering red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel; whisker content was about 13.4% by XRD.
Comparative example 1
The present comparative example differs from example 2 in that the effect of different carbonization temperatures on the carbonized product was investigated with the magnesium chloride removed. The sintering method red mud carbonization recycling method of the comparative example comprises the following steps:
(1) Preparing red mud micropowder by a sintering method and an aqueous solution into 1:10, wherein the stirring speed of the slurry is 400r/min, the temperature is controlled at 20 ℃,40 ℃,60 ℃ and 80 ℃;
(2) Introducing CO into the slurry in the step (1) 2 Gas, CO-containing 2 CO in gas 2 Is 99.9% by volume and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2h;
(3) And (3) filtering the slurry after the reaction in the step (2), and drying the obtained filter residues to obtain carbonized products of the sintering process red mud at different carbonization temperatures.
SEM test is carried out on the carbonized products of the red mud sintered at different carbonization temperatures, the test result is shown in figure 9, and as can be seen from figure 9, the carbonized products have little change in morphology, the calcium carbonate is mainly calcite in block shape, and only a small amount of overlapped strip-shaped products, possibly calcium carbonate whiskers, appear at the carbonization temperature of 80 ℃. It can thus be seen that two important conditions for calcium carbonate whisker formation are carbonization temperature and the form controlling magnesium chloride.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The carbonization recycling method of the red mud by the sintering method is characterized by comprising the following steps of:
preparing a magnesium salt solution, and heating the magnesium salt solution to 80 ℃ to obtain a magnesium salt hot solution; the concentration of the magnesium salt solution is 0.4mol/L; the magnesium salt is magnesium chloride;
step two, adding the sintering red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry;
the mass ratio of the sintering red mud to the magnesium salt hot solution is 1:10;
step three, introducing CO-containing slurry into the slurry 2 Gas, carbonizing for 2 hours, filtering slurry after carbonizing, and drying filter residues to obtain a product, wherein the product comprises calcium carbonate whiskers; the length-diameter ratio of the calcium carbonate whisker is 5-6; the calcium carbonate whisker is aragonite type calcium carbonate, and the rod-shaped aragonite grows radially around and is loosely overlappedFilling the space.
2. The method for carbonizing and reutilizing sintered red mud according to claim 1, wherein in the second step, the stirring speed is 300-500r/min.
3. The method for carbonizing and reutilizing sintered red mud as set forth in claim 1, wherein in the third step, the carbon dioxide containing gas contains carbon dioxide 2 The gas is industrial tail gas, and the CO contains 2 CO in gas 2 The volume concentration of (2) is 10-100%; the CO containing 2 The aeration rate of the gas is 0.1-0.5L/min/g.
4. A process for the carbonisation of sintered red mud according to any of the claims 1 to 3, wherein in step three the product further comprises a silica alumina gel.
5. A calcium carbonate whisker produced by the carbonization and reuse method of sintered red mud according to any one of claims 1 to 3, wherein the calcium carbonate whisker has an aspect ratio of 5 to 6.
6. The use of the product obtained by the carbonization and reuse method of sintered red mud according to claim 4, wherein the product is used for preparing cement paste;
the product replaces part of cement to prepare cement paste, and the replacement amount is 5% of the mass of cement.
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