CN110183124B - Micro-expansion sulphoaluminate cement clinker and preparation method thereof - Google Patents
Micro-expansion sulphoaluminate cement clinker and preparation method thereof Download PDFInfo
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- CN110183124B CN110183124B CN201910396111.1A CN201910396111A CN110183124B CN 110183124 B CN110183124 B CN 110183124B CN 201910396111 A CN201910396111 A CN 201910396111A CN 110183124 B CN110183124 B CN 110183124B
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- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention provides a micro-expansion sulphoaluminate cement clinker and a preparation method thereof, belonging to the technical field of cement clinker. The micro-expansion sulphoaluminate cement clinker is prepared from the following raw materials in percentage by weight: 45-52 wt.% of MgO-containing waste rock; 30-36 wt.% of aluminum slag; 14-20 wt.% of desulfurized gypsum; 0-1.5 wt.% of fly ash; in chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%. The invention completely adopts industrial waste as raw materials, fully utilizes the properties and mutual matching of the industrial waste and elements contained in the industrial waste, and calcines the micro-expansion sulphoaluminate cement clinker with the physical strength far higher than that of the common silicate cement clinker, wherein the 3d compressive strength can reach more than 78.0MPa, and the 28d compressive strength can reach more than 84.0 MPa.
Description
Technical Field
The invention relates to the technical field of cement clinker, in particular to micro-expansion sulphoaluminate cement clinker and a preparation method thereof.
Background
Compared with the common Portland cement clinker, the production of the sulphoaluminate cement clinker can save energy consumption and reduce the emission of carbon dioxide by more than 20 percent, and simultaneously can be comparable with the common Portland cement clinker in performance, thereby being a hotspot for researching novel low-carbon and energy-saving cement in recent years.
The patent with publication number CN102249576A discloses a preparation method and application of low-energy-consumption and low-emission cement, limestone, bauxite, clay or sandstone and natural gypsum are used as raw materials, and are fired into novel cement mainly comprising belite and anhydrous calcium sulphoaluminate minerals, wherein the 3d strength of the cement can reach 33MPa, and the 28d strength can reach 55 MPa.
The patent with the application number of 201210022401.8 discloses an active belite sulphoaluminate cement clinker and a preparation method thereof, the used raw materials mainly comprise limestone, high-alumina powder, coal ash and natural gypsum, the 3d strength of the prepared clinker reaches 30-50 MPa, the 28d strength reaches 60-70 MPa, and the water demand and the setting characteristics are close to those of common silicic acid cement clinker.
The method for calcining the sulphoaluminate cement clinker at least uses a natural mineral as a raw material. In fact, China generates a large amount of various industrial solid wastes every year, the components and the properties of the industrial solid wastes are close to those of some natural minerals, if the industrial solid wastes can be well utilized, the use problem of industrial waste residues can be solved, various complex impurity ions in the industrial solid wastes can be fully utilized, materials with special properties are formed, and products with high added values are generated.
Disclosure of Invention
The invention aims to provide a micro-expansion sulphoaluminate cement clinker and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a micro-expansion sulphoaluminate cement clinker which is prepared from the following raw materials in percentage by weight:
45-52 wt.% of MgO-containing waste rock;
30-36 wt.% of aluminum slag;
14-20 wt.% of desulfurized gypsum;
0-1.5 wt.% of fly ash;
in chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%.
Preferably, in terms of chemical composition, Al in the aluminum slag2O3The content of (B) is more than or equal to 70 wt.%.
Preferably, in terms of chemical composition, SO in the desulfurized gypsum3The content of (A) is more than or equal to 40 wt.%.
Preferably, the micro-expanded sulphoaluminate cement clinker comprises 60.0-62.0 wt.% C in terms of mineral composition4A3S, 21.0-25.0 wt.% C2S, 3.2-3.5 wt.% of C4AF and other minerals.
The invention also provides a preparation method of the micro-expansion sulphoaluminate cement clinker in the technical scheme, which comprises the following steps:
mixing the raw materials and then grinding to obtain powdery raw materials;
and calcining the powdery raw material to obtain the micro-expansion sulphoaluminate cement clinker.
Preferably, the calcining temperature is 1300-1400 ℃.
Preferably, the atmosphere of the calcination is a weakly oxidizing atmosphere.
Preferably, the screen allowance of the powdery raw material at 0.045mm is less than or equal to 10 percent.
Preferably, the calcining further comprises cooling the calcined product.
Preferably, the equipment used for cooling is a grate cooler.
The invention provides a micro-expansion sulphoaluminate cement clinker which is prepared from the following raw materials in percentage by weight: 45-52 wt.% of MgO-containing waste rock; 30-36 wt.% of aluminum slag; 14-20 wt.% of desulfurized gypsum; 0-1.5 wt.% of fly ash; in chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%. The invention fully adopts industrial wastes as raw materials, fully utilizes the properties and mutual matching of the industrial wastes and elements contained in the industrial wastes, particularly the peculiar micro-expansion performance of MgO in MgO-containing waste stones, after calcination, MgO in the MgO-containing waste stones is partially and fixedly dissolved in various clinker minerals, and the rest exists among the clinker minerals in the form of periclase crystals, the periclase is hydrated to form brucite, and the brucite is hydrated with sulphoaluminate cement to form ettringite, thereby having multiple functions of improving the strength and providing double expansion sources. The raw materials are matched with each other, the micro-expansion sulphoaluminate cement clinker with the physical strength far higher than that of the common silicate cement clinker is calcined, the physical strength of the micro-expansion sulphoaluminate cement clinker can be comparable with that of various sulphoaluminate cement clinkers calcined by adopting natural mineral raw materials, the 3d compressive strength can reach more than 78.0MPa, and the 28d compressive strength can reach more than 84.0 MPa.
Detailed Description
The invention provides a micro-expansion sulphoaluminate cement clinker which is prepared from the following raw materials in percentage by weight:
45-52 wt.% of MgO-containing waste rock;
30-36 wt.% of aluminum slag;
14-20 wt.% of desulfurized gypsum;
0-1.5 wt.% of fly ash;
in chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%.
The raw material for preparing the micro-expansion sulphoaluminate cement clinker comprises 45-52 wt.% of MgO-containing waste stone, and the preferable raw material is 47-52%. In terms of chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%, preferably 48-55 wt%. The invention has no special requirement on the source of the waste MgO-containing stone and can meet the requirements of the chemical components. In a specific embodiment of the present invention, the MgO-containing waste rock is preferably MgO-containing mining waste rock. The particle size of the MgO-containing waste rock is preferably less than or equal to 30 mm. The MgO in the MgO-containing waste rock has micro-expansion performance, and can be used for calcining micro-expansion sulphoaluminate cement clinker with the physical strength far higher than that of common silicate cement clinker by matching with other raw materials, and the physical strength of the micro-expansion sulphoaluminate cement clinker can be comparable with that of various sulphoaluminate cement clinkers calcined by adopting natural mineral raw materials.
The raw material for preparing the micro-expansion sulphoaluminate cement clinker comprises 30-36 wt.% of aluminum slag, and more preferably 32-35 wt.%. In chemical composition, Al in the aluminum slag of the invention2O3The content of (B) is preferably not less than 70wt.%, more preferably not less than 80 wt.%. The source of the aluminum slag is not particularly required, and the aluminum slag with the source known by the technicians in the field can be adopted. In a specific embodiment of the present invention, the aluminum dross is preferably electrolytic aluminum dross.
The preparation raw material of the micro-expansion sulphoaluminate cement clinker provided by the invention comprises 15-20 wt.% of desulfurized gypsum, and more preferably 15-19 wt.%. In terms of chemical composition, SO in the desulfurized gypsum of the invention3The content of (b) is preferably not less than 40wt.%, more preferably 40 to 43 wt.%. The source of the desulfurized gypsum is not particularly required in the invention, and the desulfurized gypsum from which the source is well known to those skilled in the art can be used.
The raw material for preparing the micro-expansion sulphoaluminate cement clinker comprises 0-1.5 wt.% of fly ash, and more preferably 0.5-1.5 wt.%. The source of the fly ash is not particularly required in the invention, and the fly ash with the source well known to those skilled in the art can be adopted.
The invention fully uses industrial waste as raw material, fully utilizes the property and mutual matching of the industrial waste and the elements contained in the industrial waste, and all the raw materials are mutually matched to calcine the micro-expansion sulphoaluminate cement clinker with the physical strength far higher than that of the common silicate cement clinker, and the physical strength of the micro-expansion sulphoaluminate cement clinker can be comparable with that of various sulphoaluminate cement clinkers calcined by adopting natural mineral raw materials.
According to the invention, the raw materials are mixed according to the proportion, the MgO content of the obtained micro-expansion sulphoaluminate cement clinker is 3.5-4.5% in chemical composition, and the micro-expansion sulphoaluminate cement clinker comprises 60.0-62.0 wt.% of C in mineral composition4A3S, 21.0-25.0 wt.% C2S, 3.2-3.5 wt.% of C4AF and small amounts of other minerals. The invention has no special requirements on the types of other minerals, and specifically comprises the following steps: periclase, free gypsum, and the like.
The invention also provides a preparation method of the micro-expansion sulphoaluminate cement clinker in the technical scheme, which comprises the following steps:
mixing the raw materials and then grinding to obtain powdery raw materials;
and calcining the powdery raw material to obtain the micro-expansion sulphoaluminate cement clinker.
The invention mixes all the raw materials and grinds them to obtain the powdery raw material. The mixing mode of the raw materials is not particularly required, and the mixing mode known by the person skilled in the art can be adopted. The invention has no special requirement on the grinding mode, and the grinding mode known by the technicians in the field can be adopted. In the present invention, the amount of the powdery raw material remaining on a 0.045mm sieve is preferably 10% or less.
After the powdery raw material is obtained, the powdery raw material is calcined to obtain the micro-expansion sulphoaluminate cement clinker.
Before calcination, the present invention preferably performs homogenization treatment on the powdery raw material to obtain a homogenized raw material. The mode of the homogenization treatment is not particularly required in the present invention, and a homogenization treatment mode known to those skilled in the art can be adopted. The homogenization treatment of the invention can ensure the stability of the quality of the raw materials entering the kiln.
After obtaining the homogenized raw meal, the invention calcines the homogenized raw meal. In the invention, the calcination temperature is preferably 1300-1400 ℃. The invention has no special requirement on the calcining time until the cement clinker minerals are completely formed. The invention preferably judges whether all cement clinker minerals are formed according to the clinker detection result. In the invention, the calcining atmosphere is preferably a weak oxidizing atmosphere, the weak oxidizing atmosphere is preferably realized by controlling the negative pressure of the kiln head, and the value of the negative pressure of the kiln head is preferably-20 to-50 Pa. The equipment adopted by the calcination of the invention is preferably a novel dry kiln with a five-stage preheater and an external decomposing furnace. In the calcining process, MgO in the MgO-containing waste stone is partially and fixedly dissolved in each clinker mineral, the rest exists among the clinker minerals in the form of periclase crystals, the periclase is hydrated to form brucite, and the hydrated product of the brucite and sulphoaluminate cement, namely ettringite, has multiple functions of improving strength and providing double expansion sources.
After calcination, the present invention preferably further comprises cooling the calcined product to obtain a micro-expanded sulphoaluminate cement clinker. In the invention, the equipment used for cooling is preferably a grate cooler.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not to be construed as being limited thereto.
The raw materials are subjected to component analysis and classification and are sent into a special storage, and the components of the raw materials are shown in a table 1:
TABLE 1 chemical composition of industrial residues
Example 1
1) The weight percentages are as follows: MgO-rich mining MgO-containing waste stone 51.5%, electrolytic aluminum slag 33.2%, desulfurized gypsum 14.0%, and fly ash 1.3%, and metering by using a metering device to form a mixed material.
2) Feeding the mixed material obtained in the step 1) into a pulverizer or a vertical mill for pulverizing, wherein the fineness of the pulverized raw material is controlled to be less than or equal to 10 percent with the screen residue of 0.045mm, and thus obtaining the fine powdery raw material.
3) And (3) feeding the raw material obtained in the step 2) into a novel dry kiln, calcining at the temperature of 1300-1400 ℃ in a weak oxidation atmosphere until the minerals of the cement clinker are completely formed, and cooling by a grate cooler to obtain the cement clinker. The chemical composition and the main mineral composition are shown in table 2.
Example 2
1) The weight percentages are as follows: the MgO-rich mining material comprises 50% of MgO waste rock, 33.6% of electrolytic aluminum slag, 15.2% of desulfurized gypsum and 1.2% of fly ash, and is metered by utilizing a metering device to form a mixed material.
2) Feeding the mixed material obtained in the step 1) into a pulverizer or a vertical mill for pulverizing, wherein the fineness of the pulverized raw material is controlled to be less than or equal to 10 percent with the screen residue of 0.045mm, and thus obtaining the fine powdery raw material.
3) And (3) feeding the raw material obtained in the step 2) into a novel dry kiln, calcining at the temperature of 1300-1400 ℃ in a weak oxidation atmosphere until the minerals of the cement clinker are completely formed, and cooling by a grate cooler to obtain the cement clinker. The chemical composition and the main mineral composition are shown in table 2.
Example 3
1) The weight percentages are as follows: the MgO-rich mining material comprises 49.0% of MgO-containing waste rock, 33.8% of electrolytic aluminum slag, 16.6% of desulfurized gypsum and 0.6% of fly ash, and the mixed material is formed by metering by utilizing metering equipment.
2) Feeding the mixed material obtained in the step 1) into a pulverizer or a vertical mill for pulverizing, wherein the fineness of the pulverized raw material is controlled to be less than or equal to 10 percent with the screen residue of 0.045mm, and thus obtaining the fine powdery raw material.
3) And (3) feeding the raw material obtained in the step 2) into a novel dry kiln, calcining at the temperature of 1300-1400 ℃ in a weak oxidation atmosphere until the minerals of the cement clinker are completely formed, and cooling by a grate cooler to obtain the cement clinker. The chemical composition and the main mineral composition are shown in table 2.
Example 4
1) The weight percentages are as follows: the MgO-rich mining material comprises 47% of MgO waste rock, 34.7% of electrolytic aluminum slag and 18.3% of desulfurized gypsum, and the mixed material is formed by metering by utilizing metering equipment.
2) Feeding the mixed material obtained in the step 1) into a pulverizer or a vertical mill for pulverizing, wherein the fineness of the pulverized raw material is controlled to be less than or equal to 10 percent with the screen residue of 0.045mm, and thus obtaining the fine powdery raw material.
3) And (3) feeding the raw material obtained in the step 2) into a novel dry kiln, calcining at the temperature of 1300-1400 ℃ in a weak oxidation atmosphere until the minerals of the cement clinker are completely formed, and cooling by a grate cooler to obtain the cement clinker. The chemical composition and the main mineral composition are shown in table 2.
TABLE 2 chemical composition and main mineral composition of cement clinker prepared in examples 1 to 4
The cement clinker obtained in examples 1 to 4 was ground to 370 to 420m according to the national standard method2After/kg, the physical properties such as strength, water consumption for standard consistency, free swell ratio and setting time were measured and the results are shown in Table 3.
TABLE 3 physical Properties of Cement Clinkers prepared in examples 1 to 4
The results in Table 3 show that the cement clinker of the present invention has a compressive strength of 78.1MPa or more in 3d and a compressive strength of 84.1MPa or more in 28d, and has excellent physical strength.
The embodiments above show that the cement clinker is prepared by using industrial wastes as raw materials, the physical strength of the cement clinker is far higher than that of ordinary silicate cement clinker, the physical strength of the cement clinker can be comparable to that of various sulphoaluminate cement clinkers calcined by using natural mineral raw materials, the 3d compressive strength can reach more than 78.0MPa, and the 28d compressive strength can reach more than 84.0 MPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The micro-expansion sulphoaluminate cement clinker is prepared from the following raw materials in percentage by weight:
45-52 wt.% of MgO-containing waste rock;
30-36 wt.% of aluminum slag;
15.2-20 wt.% of desulfurized gypsum;
0-1.5 wt.% of fly ash;
in chemical composition, the content of MgO in the MgO-containing waste rock is less than or equal to 7 wt%, and the content of CaO is more than or equal to 48 wt%;
al in the aluminum slag2 O3 The content of (A) is more than or equal to 70 wt.%; SO in the desulfurized gypsum3 The content of (A) is more than or equal to 40 wt.%;
the micro-expansion sulphoaluminate cement clinker comprises 60.0-62.0 wt.% of C in terms of mineral composition4 A3 S, 21.0-25.0 wt.% C2 S, 3.2-3.5 wt.% of C4 AF and other minerals.
2. A process for the preparation of a micro-expanded sulphoaluminate cement clinker according to claim 1, comprising the steps of:
mixing the raw materials and then grinding to obtain powdery raw materials;
and calcining the powdery raw material to obtain the micro-expansion sulphoaluminate cement clinker.
3. The method according to claim 2, wherein the calcination is carried out at a temperature of 1300 to 1400 ℃.
4. The production method according to claim 2 or 3, characterized in that the atmosphere of the calcination is a weakly oxidizing atmosphere.
5. The method of claim 2, wherein the powdery raw material has a screen residue of 10% or less at 0.045 mm.
6. The method of claim 2, wherein the calcining further comprises cooling the calcined product.
7. The preparation method according to claim 6, wherein the equipment for cooling is a grate cooler.
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