CN114959893A - 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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- CN114959893A CN114959893A CN202210474816.2A CN202210474816A CN114959893A CN 114959893 A CN114959893 A CN 114959893A CN 202210474816 A CN202210474816 A CN 202210474816A CN 114959893 A CN114959893 A CN 114959893A
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- 238000000034 method Methods 0.000 title claims abstract description 124
- 238000003763 carbonization Methods 0.000 title claims abstract description 93
- 238000005245 sintering Methods 0.000 title claims abstract description 80
- 238000004064 recycling Methods 0.000 title claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 129
- 239000000243 solution Substances 0.000 claims abstract description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 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
- 238000001035 drying Methods 0.000 claims abstract description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 112
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 56
- 239000004568 cement Substances 0.000 claims description 34
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 32
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 20
- 238000005273 aeration Methods 0.000 claims description 19
- 238000010000 carbonizing Methods 0.000 claims description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 16
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000004939 coking Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 70
- 239000007789 gas Substances 0.000 description 52
- 239000000843 powder Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 17
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- 230000035484 reaction time Effects 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 9
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- 229910021532 Calcite Inorganic materials 0.000 description 7
- 239000011398 Portland cement 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
- 239000011575 calcium Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 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
- 238000003723 Smelting Methods 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
- 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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 1
- 238000010998 test method Methods 0.000 description 1
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Images
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)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention provides a sintering red mud carbonization recycling method and application of a product thereof. The method comprises the following steps: step one, preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution; adding the sintering process red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry; step three, introducing CO into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a product, wherein the product comprises calcium carbonate whiskers. The method of the invention can realize the butt firingThe high value-added utilization of the coking red mud can efficiently prepare the calcium carbonate crystal whisker with high value-added products at 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 synthesized aragonite type calcium carbonate crystal 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, the carbonization method is the most common method for synthesizing calcium carbonate whiskers at home and abroad. However, in these conventional methods for producing calcium carbonate whiskers, the raw materials for producing calcium carbonate whiskers are mainly industrial ores having a high calcium content, such as marble, calcite, limestone, and dolomite. The research of preparing calcium carbonate whiskers by utilizing solid wastes with high calcium content, household garbage and the like so as to realize the high value-added utilization of the solid wastes also draws attention of a plurality of scholars. For example, some scholars extract calcium component crystal form in steel slag based on ammonia water, and then prepare calcium carbonate whisker by regulating and controlling the pH value of a reaction system. Some scholars use phosphogypsum as a calcium source, refine the phosphogypsum by processes of HCl leaching, ammonia water impurity removal and the like, and then prepare calcium carbonate whiskers by a carbonization method. Some researchers have prepared calcium carbonate whiskers by a double decomposition method after acidifying the calcium carbonate slag. And some scholars use high-salinity wastewater discharged by a traditional coal-fired power plant to electrolyze and carbonize the fly ash to prepare the calcium carbonate whiskers. The solid wastes with high calcium content are used for preparing high value-added products, but the process treatment before the carbonization of the solid wastes is more complicated, such as the grinding of steel slag and the acidification and impurity removal of gypsum. The sintering process red mud is liquid waste discharged by a sintering process aluminum smelting process, is discharged and stacked in the open air, pollutes underground water resources and environment, belongs to building materials difficult to utilize in 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 process red mud at present.
Therefore, 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 sintering process red mud carbonization recycling method and application of products thereof, so as to solve the problem that only low value-added utilization of sintering process red mud can be realized in the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a sintering method red mud carbonization recycling method comprises the following steps:
step one, preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution;
adding the sintering process red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry;
step three, introducing CO into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a product, wherein the product comprises calcium carbonate whiskers.
Optionally, in the first step, the concentration of the magnesium salt solution is 0.2-0.4 mol/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 process red mud to the magnesium salt hot solution is 1:10-1: 20.
Optionally, in the second step, the stirring speed is 300-500 r/min.
Optionally, in step three, the CO is contained 2 The gas is industrial tail gas containing CO 2 CO in gas 2 The volume concentration of (A) is 10-100%; said CO-containing 2 The aeration rate of the gas is 0.1-0.5L/min/g.
Optionally, in step three, the carbonization reaction time is 1-3 h.
Optionally, in step three, the product further comprises a silica-alumina gel.
The invention also provides calcium carbonate whiskers produced by the sintering method red mud carbonization recycling method, wherein the length-diameter ratio of the calcium carbonate whiskers 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 preparing cement slurry.
Has the advantages that:
the method for carbonizing and recycling the red mud by the sintering method can realize high value-added utilization of the red mud by the sintering method, can efficiently prepare the calcium carbonate crystal whisker with high value-added product at 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, has carbonization effect independent of the concentration of carbon dioxide, and can utilize carbon dioxide industrial waste gas with different concentrations to realize resource utilization of the industrial waste gas.
The liquid form of the sintering red mud is easier to be carbonized by a wet method when being discharged, and the industrial utilization feasibility 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 fiber.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention. Wherein:
FIG. 1 is a FT-IR spectrum of carbonized products of sintering red mud obtained in example 1 of the present invention at different concentrations of magnesium chloride;
FIG. 2 is an SEM image of the carbonized product of the red mud of the sintering process at different concentrations of magnesium chloride obtained in example 1 of the present invention, wherein a shows that the concentration of magnesium chloride is 0.1mol/L, b shows that the concentration of magnesium chloride is 0.4mol/L, c shows that the concentration of magnesium chloride is 0.8mol/L, and d shows that the concentration of magnesium chloride is 1.2 mol/L;
FIG. 3 is an XRD (X-ray diffraction) diagram of the carbonized product of the red mud of the sintering method at different carbonization temperatures under the condition that the concentration of magnesium chloride obtained in example 2 of the invention is 0.4 mol/L;
FIG. 4 is an XRD diagram of the carbonized product of the sintering red mud obtained in example 3 of the present invention at different carbonization times;
FIG. 5 is an SEM photograph of a carbonized product of a red mud by a sintering process at different carbonization times obtained in example 3 of the present invention, wherein a shows that the carbonization time is 10min, b shows that the carbonization time is 30min, c shows that the carbonization time is 60min, d shows that the carbonization time is 120min, e shows that the carbonization time is 180min, and f shows that the carbonization time is 240 min;
FIG. 6 is an SEM image of a carbonized product of the red mud of the sintering process obtained in example 4 of the present invention;
FIG. 7 is a schematic diagram showing the effect of the carbonization product of red mud of the sintering process obtained in example 4 of the present invention on the strength of cement paste when used for preparing cement paste;
FIG. 8 is an SEM image (left image) and an EDS image (right image) of hydration 3d of a cement slurry with a carbonization product addition amount of 5% in the red mud of the sintering method obtained in example 4;
FIG. 9 is an SEM photograph of the carbonized product of the red mud of the sintering process at different carbonization temperatures obtained in comparative example 1 of the present invention, wherein a is a photograph showing that the carbonization temperature is 20 ℃, b is a photograph showing that the carbonization temperature is 40 ℃, c is a photograph showing that the carbonization temperature is 60 ℃, and d is a photograph showing that the carbonization temperature is 80 ℃.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The sintering method red mud has high calcium oxide content and good carbonization activity, and the invention provides a sintering method red mud carbonization recycling method based on the method, aiming at realizing high value-added utilization of the sintering method red mud, and the method can be used for preparing high value-added product calcium carbonate whiskers with high efficiency and low cost and better solidifying carbon dioxide gas.
In the embodiment of the invention, the method for carbonizing and recycling red mud by a sintering method comprises the following steps:
step one, preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution.
In the specific embodiment of the 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 between any two endpoints), the calcium carbonate finally generated is aragonite calcium carbonate by using the magnesium salt solution with the concentration range, and if the concentration of the magnesium salt solution is less than 0.2mol/L, the generated calcium carbonate is calcite; if the concentration of the magnesium salt solution is more than 0.4mol/L, the appearance of the generated calcium carbonate whisker is damaged, the surface of the whisker is rough, and cracks appear.
In an embodiment of the present invention, the magnesium salt is a soluble magnesium salt, and is selected from at least one of magnesium chloride, magnesium sulfate and magnesium nitrate. Preferably, magnesium chloride is used, and the content of calcium carbonate whiskers synthesized by using magnesium sulfate and magnesium nitrate as control agents is low under the condition of the same magnesium-calcium ratio, and the 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 the calcium carbonate whiskers can be increased by using the magnesium chloride.
In an embodiment of the invention, the magnesium salt solution is heated to a temperature of 60-80 ℃ (such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and any interval between the two endpoints). Heating the magnesium salt solution to the above range, which is beneficial to the growth of the calcium carbonate crystal whisker along the length direction; if the temperature is lower than 60 ℃, the calcium carbonate crystal whisker is not easy to prepare; when the temperature is higher than 80 ℃, the local saturation of the system is higher, which causes the content of calcium carbonate crystal whiskers of the product to be reduced.
And step two, adding the sintering process 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 red mud of the sintering method to the hot solution of the magnesium salt is 1:10-1:20 (such as 1:10, 1:15, 1:20 and the interval value between any two endpoint values). The mass ratio is selected, so that the red mud obtained by the sintering method can be fully dissolved in the solution, and the liquid form during industrial discharge is close to the liquid-solid ratio of 10, thereby being beneficial to the next carbonization work. If the mass ratio of the two is more than 1:10, the slurry is too thick and 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 is 300-500r/min (such as 300r/min, 350r/min, 400r/min, 450r/min, 500r/min and the interval value between any two end values). The stirring speed range is selected for stirring and mixing, so that slurry which is uniformly mixed can be quickly obtained; if the stirring speed is less than 300r/min, the dispersed CO cannot be dissolved sufficiently 2 Resulting in CO in aqueous solution 2 The dispersion is not uniform, and the carbonization effect cannot be met; if the stirring speed is more than 500r/min, CO will be generated 2 It does not have time to dissolve and react and escape. It should be noted that in order to achieve the best carbonization effect, the stirring rate should be in addition to the CO 2 The aeration rate and concentration are matched. That is, when the aeration rate is small, the stirring rate is correspondingly small, and when the aeration rate is large, the stirring rate is correspondingly increased. 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 smaller the aeration rate required.
Step three, introducing CO into the slurry 2 Gas and carbonization reaction for a period of time, filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a product, wherein the product is prepared byThe product comprises calcium carbonate whiskers.
In the specific embodiment of the present invention, the catalyst contains CO 2 The gas is industrial tail gas containing CO 2 CO in gas 2 Is 10-100% (e.g., 10%, 20%, 30%, 50%, 70%, 100%, and the interval between any two endpoints); the carbonization effect does not depend on the concentration of carbon dioxide, and the resource utilization of the industrial waste gas can be realized by utilizing the carbon dioxide industrial waste gas with different concentrations.
In the specific embodiment of the present 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 the interval value between any two endpoint values), namely the CO content required to be met by each gram of raw material (sintering red mud) 2 The aeration rate of the gas is increased along with the increase of the addition of the red mud in the sintering method, the numerical value of the aeration rate is correspondingly improved, and the CO is introduced into the invention 2 The amount of the gas can meet the requirement of generating calcium carbonate whiskers by a carbonization reaction, the product amount is reduced due to too low speed, and the waste is caused due to too large introduction amount.
In the embodiment of the present invention, the carbonization time is 1-3h (e.g., 1h, 2h, 3h, and the interval between any two endpoints). Under the carbonization reaction time, a large amount of calcium carbonate whiskers can be generated in the slurry through carbonization reaction, the surface appearance of the whiskers is smooth, and the length-diameter ratio is 5-6; if the carbonization time is less than 1h, the amount of calcium carbonate whiskers generated in the slurry is less through carbonization reaction; if the carbonization time is more than 3h, the amount of calcium carbonate whiskers generated in the slurry is not increased through the carbonization reaction.
Furthermore, the obtained product also comprises aluminosilico-alumina gel which has pozzolanic activity and can react with calcium hydroxide serving as a cement hydration product to generate hydrated calcium aluminate and hydrated calcium silicate, so that the content of the hydration product is increased, and the strength of cement slurry is enhanced.
In the specific embodiment of the invention, the filtrate formed after the filtration in the third step can be recycled, and after the filtrate is heated to 60-80 ℃, the second step and the third step are circulated to continuously prepare the calcium carbonate whiskers, so that the production cost is saved, and the method has the advantages of environmental protection, high efficiency and economy.
The invention also provides calcium carbonate whiskers produced by the sintering method red mud carbonization recycling method, wherein the length-diameter ratio of the calcium carbonate whiskers 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 replacing amount is 1-10% of the mass of the cement, the water cement ratio of the prepared cement paste is controlled to be 0.5, and the cement can be selected from one of Portland cement, ordinary Portland cement and sulphoaluminate cement.
The method for carbonizing and recycling red mud by sintering method and the application of the product thereof of the present invention will be described in detail by specific examples.
Example 1
The method for carbonizing and recycling red mud by the sintering method comprises the following steps:
(1) preparing magnesium chloride solutions with the concentrations 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 red mud micro powder obtained by a sintering method into the hot magnesium chloride solution obtained in the step (1), wherein the ratio of the red mud micro powder to the hot magnesium chloride solution is 1:10, and stirring and mixing the red mud micro powder and the hot magnesium chloride solution at the stirring speed of 400r/min to obtain slurry;
(3) introducing CO into the slurry 2 Gas, containing CO 2 CO in gas 2 Has a volume concentration of 99.9% and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2 h; and filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain the carbonized product of the red mud of the sintering method under different magnesium chloride concentrations.
FT-IR test and SEM test were performed on the carbonized product of the red mud of the sintering process obtained in this example at different concentrations of magnesium chloride, and the results are shown in FIGS. 1 and 2, and it can be seen from FIG. 1 that the carbonized red mud of the sintering process mainly contains C-O groups and Si-O-Si groups, of which 1417, 876 and 712cm -1 Is the vibration peak of calcite type calcium carbonate, mainly existsIn the sintering process red mud raw material, 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, with the increase of the concentration of magnesium chloride, the calcite vibration peak disappears, aragonite calcium carbonate is generated, the intensity of the vibration peak is gradually increased and then weakened, and when the concentration of magnesium chloride is 0.4mol/L, 1480cm in the sample -1 The maximum vibration peak area of the aragonite-type calcium carbonate indicates that the maximum aragonite is generated at the moment. 1621cm when the solubility of magnesium chloride exceeds 0.4mol/L -1 And a new vibration peak appears at the position corresponding to the magnesium chloride substance, which shows that the magnesium chloride content is too high at the moment and is attached to the whisker product, and the corresponding aragonite vibration peak is weaker, which shows that the whisker content is less. In addition, with the increase of the concentration of magnesium chloride, the vibration peak of Si-O-Si groups is enhanced, which shows that the carbonized product of the red mud in the sintering method contains certain silicon-aluminum gel besides whiskers. The highly polymerized silica-alumina gel has better activity, can rapidly participate in the hydration reaction of cement, increases the content of hydration products, and further enhances the strength of cement paste. As can be seen from FIG. 2, the crystal form of calcium carbonate is still calcite type when the concentration of magnesium chloride is 0.1mol/L, and a large amount of aragonite type calcium carbonate appears when the concentration of magnesium chloride is 0.2mol/L, the rod-shaped aragonite grows radially around and loosely overlaps and fills the space, and the aspect ratio is about 5-6. When the magnesium chloride concentration exceeds 0.4mol/L, that is, the concentration is 0.8mol/L and 1.2mol/L, it can be seen that the morphology of the whisker is deteriorated, and particularly in FIG. 2(d), the surface of the whisker is rough and cracks appear.
Example 2
The method for carbonizing and recycling red mud by the sintering method comprises the following steps:
(1) preparing magnesium chloride solution with the concentration of 0.4mol/L, and respectively heating the magnesium chloride solution to 20 ℃, 40 ℃, 60 ℃ and 80 ℃ to obtain magnesium chloride hot solution;
(2) adding red mud micro powder obtained by a sintering method into the hot magnesium chloride solution obtained in the step (1), wherein the ratio of the red mud micro powder to the hot magnesium chloride solution is 1:10, and stirring and mixing the red mud micro powder and the hot magnesium chloride solution at the stirring speed of 400r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 Gas (es)Middle CO 2 Has a volume concentration of 99.9% 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 filtered, and the obtained filter residue is dried to obtain the carbonized product of the red mud of the sintering method at different carbonization temperatures.
XRD tests were carried out on the carbonized products of the red mud obtained in this example by sintering at different carbonization temperatures, and the results are shown in FIG. 3. As can be seen from fig. 3, no aragonite is formed at the carbonization temperature of 20 ℃, few aragonite is formed at the carbonization temperature of 40 ℃, and the carbonized product is calcium magnesium carbonate, which cannot form whiskers; at the carbonization temperatures of 60 ℃ and 80 ℃, a great amount of aragonite appears in the carbonized product. The XRD pattern is subjected to full spectrum fitting for simple quantitative analysis, and the result shows that the aragonite whisker content is increased with the increase of temperature, and is respectively 0%, 10.8%, 52.6% and 60.5%.
Example 3
The method for carbonizing and recycling red mud by the sintering method comprises the following steps of:
(1) preparing magnesium chloride solutions with the concentration of 0.4mol/L respectively, and heating the magnesium chloride solutions to 80 ℃ to obtain hot magnesium chloride solutions;
(2) adding red mud micro powder obtained by a sintering method into the hot magnesium chloride solution obtained in the step (1), wherein the ratio of the red mud micro powder to the hot magnesium chloride solution is 1:10, and stirring and mixing the red mud micro powder and the hot magnesium chloride solution at the stirring speed of 400r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 99.9% and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 10min, 30min, 60min, 120min, 180min and 240min respectively; and filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain the carbonized product of the red mud of the sintering method under different carbonization time.
XRD test and SEM test were performed on the carbonized products of the sintering red mud obtained in this example at different carbonization times, and the test results are shown in fig. 4 and 5. By performing a simple quantitative analysis of the XRD pattern in fig. 4 by full spectrum fitting, it can be concluded that the content of calcium carbonate whiskers in the crystal phase increases first and then decreases with the increase of the carbonization time. As can be seen from FIG. 5, as the carbonization time increased, a large amount of whiskers were formed, the surface morphology became smooth, and the aspect ratio increased, but when the carbonization time was too long, the calcium carbonate whisker content did not increase. In general, when the carbonization time is 120min, the content of calcium carbonate whiskers is 60.2 percent at most, the whiskers have good appearance, and the length-diameter ratio is about 6.
Example 4
The method for carbonizing and recycling red mud by the sintering method 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 hot magnesium chloride solutions;
(2) adding red mud micro powder obtained by a sintering method into the hot magnesium chloride solution obtained in the step (1), wherein the ratio of the red mud micro powder to the hot magnesium chloride solution is 1:10, and stirring and mixing the red mud micro powder and the hot magnesium chloride solution at the stirring speed of 400r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 99.9% and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2 h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a carbonized product of the sintering-process red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel;
(4) and (3) doping the carbonized product obtained in the step (three) into portland cement to replace partial portland cement, wherein the replacing amount is 0, 1%, 2%, 3% and 5% of the mass of the cement respectively, the water cement ratio is controlled to be 0.5, then uniformly mixing and stirring the mixture according to the proportion to prepare cement calcium carbide whisker mixed slurry, adopting a mold to perform casting molding, the specification of the mold is 40 multiplied by 40mm, demolding the mixture after one day, and then performing water curing for 1 day, 3 days, 7 days and 28 days to obtain different groups of cement test blocks. The cement used in the embodiment is 42.5-grade portland cement, and the performance index of the cement meets the requirements of national standard GB 8076-.
SEM tests were performed on the carbonized product of the red mud obtained in this example by the sintering method, and as shown in fig. 6, it can be seen from fig. 7 that the rod-like whiskers on the surface of the cluster particles grow radially to the periphery, and some whiskers are interspersed among the particles, and the cluster particles may be silicon-aluminum gel.
Meanwhile, the compression strength of different groups of cement test blocks is tested according to GB50081-2002 standard on mechanical property test method of common concrete, and the 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 enhances the strength of portland cement slurries of various ages, and when the amount of the carbonized product is 5% by mass of the cement, the compressive strength for curing 28d is increased by 20.5% compared to the blank set, and when the amount of the carbonized product exceeds 5%, although the strength is increased, the strength increase tends to be decreased compared to the blank set. It is likely that too much whisker fiber will tend to agglomerate, 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, a water reducing agent needs to be added, the cost is increased, and the strength is not obviously improved. Therefore, when the mass of the carbonized product replacing the cement is 5 percent, the best effect can be achieved.
TABLE 1 compressive strengths (MPa) of cement at different ages for different admixtures of carbonation products
| 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 |
Furthermore, SEM and EDS tests were performed on the cement test block obtained by hydration and oxidation of a cement slurry containing 5% of carbonized product of the red mud obtained in this example for 3d, and the test results are shown in fig. 8, and it can be seen from fig. 8 that there are obvious rod-like substances, and the calcium carbonate whiskers are proved by the EDS test. Meanwhile, the surfaces of the whiskers are wrapped by hydration products, and the whiskers are tightly connected with the cement matrix and the cement hydration products to play a role in bonding and bridging, which is also a reason for increasing the strength 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 magnesium sulfate hot solutions;
(2) adding red mud micro powder obtained by a sintering method into the magnesium sulfate hot solution obtained in the step (1), wherein the ratio of the red mud micro powder to the magnesium sulfate hot solution is 1:10, and stirring and mixing the red mud micro powder and the magnesium sulfate hot solution at the stirring speed of 400r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 99.9% and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2 h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a carbonized product of the sintering-process red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel;
XRD was performed on the product of this example and the whisker content was about 25.8%.
Example 6
The method for carbonizing and recycling red mud by the sintering method 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 hot magnesium chloride solutions;
(2) adding red mud micro powder obtained by a sintering method into the hot magnesium chloride solution obtained in the step (1), wherein the ratio of the red mud micro powder to the hot magnesium chloride solution is 1:10, and stirring and mixing the red mud micro powder and the hot magnesium chloride solution at a stirring speed of 500r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 30% and contains CO 2 The aeration rate of the gas is 0.3L/min/g, and the carbonization reaction time is 2 h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue 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% by XRD.
Example 7
The method for carbonizing and recycling red mud by the sintering method 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 magnesium sulfate hot solutions;
(2) adding red mud micro powder obtained by a sintering method into the magnesium sulfate hot solution obtained in the step (1), wherein the mass ratio of the red mud micro powder to the magnesium sulfate hot solution is 1:20, and stirring and mixing the red mud micro powder and the magnesium sulfate hot solution at the stirring speed of 300r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Is 10% by volume, contains CO 2 The aeration rate of the gas is 0.5L/min/g, and the carbonization reaction time is 1 h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a carbonized product of the sintering-process red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel; the whisker content was about 10.6% by XRD.
Example 8
The method for carbonizing and recycling red mud by the sintering method comprises the following steps:
(1) preparing magnesium nitrate solutions with the concentrations of 0.2mol/L respectively, and heating the magnesium nitrate solutions to 75 ℃ to obtain magnesium nitrate hot solutions;
(2) adding the red mud micro powder obtained by the sintering method into the magnesium nitrate hot solution obtained in the step (1), wherein the ratio of the red mud micro powder to the magnesium nitrate hot solution is 1:15, and stirring and mixing the red mud micro powder and the magnesium nitrate hot solution at the stirring speed of 300r/min to obtain slurry;
(3) introducing CO-containing gas into the slurry 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 50% and contains CO 2 The aeration rate of the gas is 0.4L/min/g, and the carbonization reaction time is 1 h; filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a carbonized product of the sintering-process red mud, wherein the carbonized product is calcium carbonate whisker containing silica-alumina gel; the whisker content was about 13.4% by XRD.
Comparative example 1
This comparative example differs from example 2 in that the effect of different carbonization temperatures on the carbonized product was investigated in the absence of magnesium chloride. The sintering method red mud carbonization recycling method of the comparative example comprises the following steps:
(1) preparing red mud micro powder and aqueous solution by a sintering method into a mixture of 1:10, stirring at the speed of 400r/min, and controlling the temperature at 20 ℃, 40 ℃, 60 ℃ and 80 ℃;
(2) introducing CO-containing into the slurry obtained in the step (1) 2 Gas containing CO 2 CO in gas 2 Has a volume concentration of 99.9% and contains CO 2 The aeration rate of the gas is 0.1L/min/g, and the carbonization reaction time is 2 h;
(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 red mud of the sintering method at different carbonization temperatures.
The SEM test of the carbonized product of the red mud obtained by the sintering method with different carbonization temperatures in this example is performed, and the test result is shown in fig. 9, and it can be seen from fig. 9 that the morphology of the carbonized product is not greatly changed by the carbonization temperature, and calcium carbonate is mainly massive calcite, and only a small amount of overlapped strip-shaped products, possibly calcium carbonate whiskers, appear at the carbonization temperature of 80 ℃. Thus, it can be seen that two important conditions for calcium carbonate whisker formation are the carbonization temperature and the crystal form control agent magnesium chloride.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A sintering method red mud carbonization recycling method is characterized by comprising the following steps:
step one, preparing a magnesium salt solution, and heating the magnesium salt solution to obtain a magnesium salt hot solution;
adding the sintering process red mud into the magnesium salt hot solution, and stirring and mixing to obtain slurry;
step three, introducing CO into the slurry 2 And (3) carrying out gas carbonization reaction for a period of time, filtering the slurry after the carbonization reaction is finished, and drying the obtained filter residue to obtain a product, wherein the product comprises calcium carbonate whiskers.
2. The method for carbonizing and recycling red mud produced by a sintering method according to claim 1, wherein in the first step, the concentration of the magnesium salt solution is 0.2 to 0.4 mol/L;
the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate.
3. The method for carbonizing and recycling red mud from a sintering process according to claim 1, wherein in the first step, the magnesium salt solution is heated to a temperature of 60 to 80 ℃.
4. The method for carbonizing and recycling sintering process red mud according to claim 1, wherein in the second step, the mass ratio of the sintering process red mud to the magnesium salt hot solution is 1:10-1: 20.
5. The method for carbonizing and recycling red mud from a sintering method according to claim 1, wherein in the second step, the stirring speed is 300-500 r/min.
6. The method for carbonizing and recycling sintering process red mud of claim 1, wherein in step three, the CO-containing material 2 The gas is industrial tail gas containing CO 2 CO in gas 2 The volume concentration of (A) is 10-100%;
said CO-containing 2 The aeration rate of the gas is 0.1-0.5L/min/g.
7. The method for carbonizing and recycling red mud from a sintering process according to claim 1, wherein in the third step, the time of the carbonization reaction is 1 to 3 hours.
8. The method for carbonizing and recycling sintering process red mud according to any of claims 1 to 7, wherein in step three, the product further comprises silica alumina gel.
9. Calcium carbonate whiskers produced by the method for carbonizing and recycling sintering process red mud of any one of claims 1 to 7, wherein the aspect ratio of the calcium carbonate whiskers is 5 to 6.
10. Use of the product of the red mud carbonizing and recycling method according to claim 8, wherein the product is used for preparing cement paste.
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| CN116477861A (en) * | 2023-04-27 | 2023-07-25 | 镇江建科建设科技有限公司 | CaCO (CaCO) generated in carbonized steel slag slurry 3 Crystal form regulating and controlling method |
| CN116835899A (en) * | 2023-05-19 | 2023-10-03 | 盐城工学院 | Wet magnesium carbide slag fiber reinforced material and preparation method and application thereof |
| WO2024109477A1 (en) * | 2022-11-21 | 2024-05-30 | 湖南大学 | Metal smelting waste residue-derived material, preparation method therefor and application thereof |
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| CN1641077A (en) * | 2004-01-13 | 2005-07-20 | 中国人民解放军国防科学技术大学 | Method for preparing aragonite type calcium carbonate whisker |
| CN113800792A (en) * | 2021-09-13 | 2021-12-17 | 河南理工大学 | Method for activating sintering-process red mud by in-situ wet carbonization at room temperature, activated red mud and application thereof |
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| CN1641077A (en) * | 2004-01-13 | 2005-07-20 | 中国人民解放军国防科学技术大学 | Method for preparing aragonite type calcium carbonate whisker |
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| CN116477861A (en) * | 2023-04-27 | 2023-07-25 | 镇江建科建设科技有限公司 | CaCO (CaCO) generated in carbonized steel slag slurry 3 Crystal form regulating and controlling method |
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