CN111925140B - Production method and application of calcium aluminate cement clinker and alumina cement clinker - Google Patents
Production method and application of calcium aluminate cement clinker and alumina cement clinker Download PDFInfo
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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
- C04B7/32—Aluminous cements
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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
- C04B7/36—Manufacture of hydraulic cements in general
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/40—Dehydrating; Forming, e.g. granulating
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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
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- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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Abstract
The invention belongs to the technical field of preparation of calcium aluminate cement clinker or aluminate binding agent, and particularly relates to a production method and application of calcium aluminate cement clinker and alumina cement clinker. The production method comprises the following steps: the wet pulping and extruding process to obtain green material, and sintering in one or two stage rotary kiln; wherein the length of the formed body along the diameter direction of the rotary kiln cylinder is 1-80 mm; the uniformity of the formed body is that the difference value of the water content per cubic centimeter is less than 0.5 percent; the temperature field of the rotary kiln is as follows: the temperature of the feed preheating section is 100-450 ℃, the temperature of the middle soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1250-1700 ℃. The production process of the invention can obtain high-quality cement products with uniform and stable mineral phases, and the cement products have the advantages of finer fineness, higher bulk density, less water demand, shorter time interval between initial setting and final setting and higher breaking strength after application.
Description
Technical Field
The invention belongs to the technical field of preparation of calcium aluminate cement clinker or aluminate binding agent, and particularly relates to a production method and application of calcium aluminate cement clinker and alumina cement clinker.
Background
The castable consists of two parts of aggregate and matrix powder binder, and the CA-80 calcium aluminate cement clinker is one of the common powder binders. At present, the preparation process of the CA-80 calcium aluminate cement clinker mainly comprises three processes: firstly, an electric melting method; secondly, a rotary kiln powder burning method; thirdly, a brick burning method for a tunnel kiln; among them, the rotary kiln powder burning method is the most common industrial production process.
The rotary kiln powder firing method is to mix and grind industrial alumina and calcium oxide or calcium carbonate according to a proportion and fire the mixture by a rotary kiln to obtain the calcium aluminate cement. However, in actual production, the obtained calcium aluminate cement has nonuniform and stable mineral phase and poor quality.
Disclosure of Invention
The first object of the present invention is to provide a novel method for producing a calcium aluminate cement clinker and an alumina cement clinker.
The production method comprises the following steps: the wet pulping and extruding process to obtain green material, and sintering in one or two stage rotary kiln; wherein the length of the formed body along the diameter direction of the rotary kiln cylinder is 1-80 mm; the uniformity of the formed body is that the difference of the water content per cubic centimeter is less than 0.5 percent;
and the temperature field of the rotary kiln is as follows: the temperature of the feed preheating section is 100-450 ℃, the temperature of the middle soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1250-1700 ℃.
The invention adopts wet pulping and extrusion combined technology to prepare the green compact, reasonably controls the matching relationship among the size and the uniformity of the green compact and the temperature field distribution of the rotary kiln, effectively reduces the fluctuation of the sintering process through the crystal nucleus effect formed by the synergistic reaction of the three, avoids the successive precipitation of different melting point substances, realizes the continuous and stable production, and ensures the stable and uniform crystallization conditions, thereby improving the number of formed crystal nuclei, ensuring the synchronization of the crystal nucleus formation, further ensuring the complete crystal growth, and finally obtaining the cement products with uniform mineral phases, high quality and different brands.
Compared with the existing cement of the same type, the CA-70/80 series calcium aluminate cement clinker obtained by the method has the advantages of finer granularity, higher bulk density, higher flexural strength and less water demand, and the time interval between initial setting and final setting is shorter, so that the relatively long initial setting time and the relatively high early strength are considered, and the use problem that the enough construction time and the quick development strength cannot be considered is solved. Compared with the similar products, the obtained CA-50 series alumina cement clinker also has the advantages of finer granularity and shorter time interval between initial setting and final setting.
Aiming at different grades of cement products, the temperature zones in the rotary kiln are as follows:
for CA-80 series calcium aluminate cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1400-1700 ℃;
specifically, the temperature of the middle soaking section is 700-800 ℃, and the temperature of the outlet firing section is 1550-1650 ℃; or the temperature of the middle soaking section is 600-700 ℃, and the temperature of the outlet sintering section is 1450-1550 ℃; or the temperature of the middle soaking section is 500-600 ℃, and the temperature of the outlet firing section is 1400-1500 ℃.
For CA-70 series calcium aluminate cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, the temperature of the outlet sintering section is 1400-1650 ℃, and 1500-1650 ℃ is preferred.
For CA-50 series alumina cement clinker, the temperature of the middle soaking section is 500-800 ℃, the temperature of the outlet sintering section is 1250-1500 ℃, and 1450-1500 ℃ is preferred.
Tests show that the temperature difference between each temperature zone is reasonably controlled according to raw material components, the fluctuation of the sintering process can be reduced to the maximum extent, so that high-quality calcium aluminate cement or alumina cement clinker with more uniform and stable mineral phases is obtained, and the application performance is better.
In addition, in order to further improve the yield and the quality of cement clinker products, the two-section rotary kilns are connected in series, the first rotary kiln executes a feeding preheating section and a middle soaking section, and the second rotary kiln executes an outlet burning section.
The conveying conditions of the materials in the rotary kiln are not particularly limited, and the conventional conveying process conditions of the rotary kiln in the field are adopted.
Generally, the smaller the size of the formed body, the more favorable the reaction, but at the same time, the more difficult the extrusion process, and the length (diameter) of the formed body of the present invention in the direction of the cylinder diameter of the rotary kiln is preferably 7 to 9mm, in view of the combination.
The shape of the molded body may be various shapes such as a square shape, a cylindrical shape, a diamond shape, etc., as long as the volume size of the molded body meets the requirement of the space in the rotary kiln, and the invention is not particularly limited thereto. As a specific embodiment, the molded article of the present invention is preferably a cylindrical article having a diameter of 7 to 9mm and a length of 15 to 20 mm.
Preferably, the water content of the formed body is controlled to be 8-12%, preferably 10-12%, which is not only more beneficial to the sufficient combustion of the formed body, but also beneficial to improving the binding force of cement and reducing the water demand.
Further research shows that the reasonable control of the density of the formed body is helpful for improving the sintering effect and further improving the binding force of the cement,the water demand is reduced. For this purpose, the density of the shaped bodies is controlled to be 1.2 to 2.2g/cm3Preferably 1.7 to 2.0g/cm3。
As one embodiment of the present invention, the molded article has a diameter of 7 to 9mm, a length of 15 to 20mm, a water content of 10 to 12% and a difference in water content per cubic centimeter of less than 0.5%, and a density of 1.7 to 2.0g/cm3The sintering reaction in the rotary kiln is more sufficient, and the obtained cement product has more uniform and stable mineral phase and crystalline phase.
In order to increase the efficiency of the extrusion, the pulp must be subjected to homogenization, dewatering and densification (pugging) before the extrusion.
In order to ensure the continuous and stable operation and the extrusion forming effect of each process, the water content and the uniformity of the materials in each treatment stage need to be strictly controlled, and the method specifically comprises the following steps:
controlling the water content of the homogenized slurry to be 40-50%, and controlling the uniformity to reach that the difference value of the water content per cubic centimeter is less than 5%;
controlling the water content of the slurry after the dehydration treatment to be 15-20%, wherein the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 1%.
Controlling the density of the densified material to be 1.2-1.5g/cm3Preferably 1.4 to 1.5g/cm3And the uniformity index reaches the difference value of the water content per cubic centimeter less than 0.5 percent, and the requirement of extrusion forming on materials is met.
The solid content in the slurry is controlled to be 70-80%, and the solid content in the slurry is preferably 78-80%, so that the subsequent homogenization treatment is facilitated.
For CA-80 series calcium aluminate cement clinker, the mass ratio of alumina, calcium oxide or calcium carbonate in the slurry is (78-80): (20-22).
For CA-70 series calcium aluminate cement clinker, the mass ratio of alumina, calcium oxide or calcium carbonate in the slurry is (69-70): (30-31).
For CA-50 series alumina cement clinker, the mass ratio of bauxite to limestone in the slurry is (48-50): (50-52).
The second purpose of the invention is to provide the cement clinker product obtained by the production process. The cement clinker product is CA-70/80 calcium aluminate cement clinker or CA-50 alumina cement clinker.
The cement product prepared by the method has small particle size and narrow distribution range; the microstructure shows that the crystal growth in the clinker is completely consistent, the homogeneity is good, the mineral phase is uniform and stable, and the clinker belongs to high-quality CA-70/80 series calcium aluminate cement clinker or CA-50 series alumina cement clinker.
A third object of the present invention is to provide the use of the above cement clinker product in an aluminate binder or a refractory castable material.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In one embodiment of the present invention, the method for producing the calcium aluminate cement clinker and the alumina cement clinker comprises the steps of:
(1) wet ball milling slurry:
preparation of slurry for CA-80 series calcium aluminate cement clinker: adding water into industrial alumina, calcium oxide or calcium carbonate, mixing and grinding to obtain slurry with the particle size of 200-400 meshes and the solid content of 70-80%.
Wherein the mass ratio of the alumina, the calcium oxide or the calcium carbonate to the water is (78-80): (20-22): (90-100); the grinding time is 8-24 h.
Preparation of slurry for CA-70 series calcium aluminate cement clinker: adding water into industrial alumina, calcium oxide or calcium carbonate, mixing and grinding to obtain slurry with the particle size of 200-400 meshes and the solid content of 70-80%.
Wherein the mass ratio of the alumina, the calcium oxide or the calcium carbonate to the water is (69-70): (30-31): (90-100); the grinding time is 8-24 h.
Preparation of slurry for CA-50 alumina Cement clinker: adding water into high-quality bauxite and limestone, mixing and grinding to obtain slurry with the particle size of 200-400 meshes and the solid content of 70-80%.
Wherein the mass ratio of the bauxite to the limestone to the water is (48-50): (50-52): (90-100); the grinding time is 8-24 h.
(2) Homogenizing:
inputting the obtained slurry into a slurry tank, filtering, and then homogenizing, wherein the homogenizing treatment specifically comprises the following steps: storing and filtering the slurry by using a plurality of slurry pools, synchronously conveying the filtered slurry to a cloth filter through a plunger pump, and uniformly mixing the slurry while conveying;
wherein, the water content of the homogenized slurry is controlled to be 40-50%, and the uniformity reaches that the difference value of the water content per cubic centimeter is less than 5%;
wherein, the pressure fluctuation of the plunger pump is controlled to be less than 1 percent so as to ensure continuous and stable conveying and continuous and stable production.
(3) And (3) dehydration treatment:
continuously conveying the slurry to a filter cloth machine for dehydration treatment;
wherein, the water content of the slurry after the dehydration treatment is controlled to be 15-20%, and the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 1%.
(4) And (3) densification treatment:
the slurry is continuously conveyed to a pug kneading machine for further pug refining, so that the homogenization of the materials is further improved, and the density is increased;
wherein the density of the material after densification treatment is controlled to be 1.2-1.5g/cm3And the uniformity index reaches the difference value of the water content per cubic centimeter less than 0.5 percent, and the requirement of extrusion forming on materials is met.
(5) Extrusion molding:
carrying out extrusion forming on the obtained materials to obtain a formed body: diameter of 7-9mm, water content of 10-12%, water content difference per cubic centimeter of less than 0.5%, and density of 1.7-2.0g/cm3A cylinder of (a).
(6) Firing:
when the length of the cylinder reaches 15-20mm, the cylinder is automatically cut off and is continuously conveyed to a drying kiln, the cylinder is dried, screened and then conveyed to a rotary kiln for burning, and cement clinker is obtained after cooling;
the temperature field of the rotary kiln is as follows: the temperature of a feed preheating section is 100-450 ℃, the temperature of a middle soaking section is 500-800 ℃, and the temperature of an outlet firing section is 1250-1700 ℃; the residence time of each stage is 6-8 h.
Further, for CA-80 series calcium aluminate cement clinker, the temperature of an outlet firing section is 1450-1700 ℃;
for CA-70 series calcium aluminate cement clinker, the temperature of an outlet firing section is 1400-1650 ℃;
for CA-50 series alumina cement clinker, the temperature of an outlet firing section is 1250-1500 ℃.
And finely grinding the high-quality cement clinker obtained by calcining to obtain cement products with different quality grade brands.
EXAMPLE 1 CA-80 series calcium aluminate Cement Clinker
The embodiment provides a production method of CA-80 series calcium aluminate cement, which comprises the following steps:
(1) wet ball milling slurry:
adding 80kg of alumina, 20kg of calcium oxide and 100kg of water into a wet ball mill, and grinding for 15h to obtain slurry with the particle size of 200-400 meshes and the solid content of 78-80%.
(2) Homogenizing:
inputting the obtained slurry into a slurry tank, filtering, and then homogenizing, wherein the homogenizing treatment specifically comprises the following steps: storing and filtering the slurry by using a plurality of slurry pools, synchronously conveying the filtered slurry to a cloth filter through a plunger pump, and uniformly mixing the slurry while conveying;
the water content of the homogenized slurry is controlled to be about 45 percent, and the uniformity reaches that the difference value of the water content per cubic centimeter is less than 5 percent;
wherein, the pressure fluctuation of the plunger pump is controlled to be less than 1 percent so as to ensure continuous and stable conveying and continuous and stable production.
(3) And (3) dehydration treatment:
and (3) continuously conveying the slurry to a filter cloth machine for dehydration treatment, controlling the water content in the slurry to be about 16%, and controlling the uniformity index to reach that the difference value of the water content per cubic centimeter is less than 1%.
(4) And (3) densification treatment:
and continuously conveying the slurry to a pug kneading machine for further pugging so as to further improve the homogenization of the materials and increase the density.
At this time, the density of the obtained material reaches 1.4-1.5g/cm3And the uniformity index reaches the difference value of the water content per cubic centimeter less than 0.5 percent, and the requirement of extrusion forming on materials is met.
(5) Extrusion molding:
carrying out extrusion forming on the obtained materials to obtain a formed body: diameter of 7-9mm, water content of about 10%, water content difference per cubic centimeter of less than 0.5%, and density of 1.8-2.0g/cm3A cylinder of (a).
(6) Firing:
when the length of the cylinder obtained by extrusion molding reaches 20mm, the cylinder can be automatically cut off and is continuously conveyed to a drying kiln, and after drying, the cylinder is screened and then conveyed to a rotary kiln, fired and cooled to obtain cement clinker;
the temperature field of the rotary kiln is as follows: the temperature of a feed preheating section is 100-200 ℃, the temperature of a middle soaking section is 700-800 ℃, and the temperature of an outlet firing section is 1550-1650 ℃; the residence time of each stage is 6-8 h.
The indexes of the CA-80 calcium aluminate cement obtained by detection are shown in tables 1 and 2.
EXAMPLE 2 CA-80 series calcium aluminate Cement Clinker
The embodiment provides a production method of CA-80 series calcium aluminate cement, which comprises the following steps:
(1) wet ball milling slurry:
78kg of alumina, 20kg of calcium oxide and 90kg of water are added into a wet ball mill and ground for 16h to obtain slurry with 200-400 meshes and 75% of solid content.
(2) Homogenizing:
inputting the obtained slurry into a slurry tank for filtration homogenization treatment, and specifically comprising the following steps: storing and filtering the slurry by using a plurality of slurry pools, synchronously conveying the filtered slurry to a cloth filter through a plunger pump, and uniformly mixing the slurry while conveying;
the water content of the homogenized slurry is controlled to be about 45 percent, and the uniformity reaches that the difference value of the water content per cubic centimeter is less than 5 percent;
wherein, the pressure fluctuation of the plunger pump is controlled to be less than 1 percent so as to ensure continuous and stable conveying and continuous and stable production.
(3) And (3) dehydration treatment:
and (3) continuously conveying the slurry to a filter cloth machine for dehydration treatment, controlling the water content in the slurry to be about 20%, and controlling the uniformity index to reach that the difference value of the water content per cubic centimeter is less than 1%.
(4) And (3) densification treatment:
and continuously conveying the slurry to a pug kneading machine for further pugging so as to further improve the homogenization of the materials and increase the density.
At this time, the density of the obtained material reaches 1.3-1.4g/cm3And the uniformity index reaches the difference value of the water content per cubic centimeter less than 0.5 percent, and the requirement of extrusion forming on materials is met.
(5) Extrusion molding:
carrying out extrusion forming on the obtained materials to obtain a formed body: diameter of 7-9mm, water content of about 12%, water content difference per cubic centimeter of less than 0.5%, and density of 1.7-1.9g/cm3A cylinder of (a).
(6) Firing:
when the length of the cylinder obtained by extrusion molding reaches 20mm, the cylinder can be automatically cut off and is continuously conveyed to a drying kiln, and after drying, the cylinder is screened and then conveyed to a rotary kiln for firing and cooling to obtain cement clinker;
the temperature field of the rotary kiln is as follows: the temperature of a feed preheating section is 100-150 ℃, the temperature of a middle soaking section is 600-700 ℃, and the temperature of an outlet sintering section is 1450-1550 ℃; the residence time of each stage is 6-8 h.
The indexes of the CA-80 calcium aluminate cement obtained by detection are shown in tables 1 and 2.
EXAMPLE 3 CA-80 series calcium aluminate Cement Clinker
The embodiment provides a production method of CA-80 series calcium aluminate cement, which comprises the following steps:
(1) wet ball milling slurry:
79kg of alumina, 20kg of calcium oxide and 90kg of water are added into a wet ball mill and ground for 24 hours to obtain slurry with the solid content of about 70 percent and the size of 200-400 meshes.
(2) Homogenizing:
inputting the obtained slurry into a slurry tank for filtration homogenization treatment, and specifically comprising the following steps: storing and filtering the slurry by using a plurality of slurry pools, synchronously conveying the filtered slurry to a cloth filter through a plunger pump, and uniformly mixing the slurry while conveying;
the water content of the homogenized slurry is controlled to be about 45 percent, and the uniformity reaches that the difference value of the water content per cubic centimeter is less than 5 percent;
wherein, the pressure fluctuation of the plunger pump is controlled to be less than 1 percent so as to ensure continuous and stable conveying and continuous and stable production.
(3) And (3) dehydration treatment:
and (3) continuously conveying the slurry to a filter cloth machine for dehydration treatment, controlling the water content in the slurry to be about 20%, and controlling the uniformity index to reach that the difference value of the water content per cubic centimeter is less than 1%.
(4) And (3) densification treatment:
and continuously conveying the slurry to a pug kneading machine for further pugging so as to further improve the homogenization of the materials and increase the density.
At this time, the density of the obtained material reaches 1.2-1.3g/cm3And the uniformity index reaches the difference value of the water content per cubic centimeter less than 0.5 percent, and the requirement of extrusion forming on materials is met.
(5) Extrusion molding:
carrying out extrusion forming on the obtained materials to obtain a formed body: diameter of 7-9mm, water content of about 11%, water content difference per cubic centimeter of less than 0.5%, and density of 1.8-1.9g/cm3A cylinder of (a).
(4) Firing:
when the length of the cylinder obtained by extrusion molding reaches 20mm, the cylinder can be automatically cut off and is continuously conveyed to a drying kiln, the cylinder is dried, screened and then conveyed to the rotary kiln for burning, and cement clinker is obtained after cooling;
the temperature field of the rotary kiln is as follows: the temperature of a feed preheating section is 100-200 ℃, the temperature of a middle soaking section is 500-600 ℃, and the temperature of an outlet firing section is 1400-1500 ℃; the residence time of each stage is 6-8 h.
The indexes of the CA-80 calcium aluminate cement obtained by detection are shown in tables 1 and 2.
Effect verification 1
Calcium aluminate cement samples from the examples and comparative examples were tested using a commercially available dry powder fired CA-80 type calcium aluminate cement as a comparative example.
The test criteria are as follows:
GB/T205-2000 aluminate cement chemical analysis method.
GB/T1345-1991 cement fineness test method.
GB/T1346-1989 method for testing water consumption, setting time and stability of standard consistency of cement.
GB/T8074- -1987 cement specific surface area determination method.
GB/T12573-1990 method for sampling cement.
The test results were as follows:
TABLE 1
As can be seen from Table 1, the CA-80 calcium aluminate cement clinker of the present invention has the following characteristics:
chemical components: in mass percent, Al2O3Content (wt.)>78%, CaO content between 20 and 21%, SiO2Content (wt.)<0.3％，Fe2O3Content (wt.)<0.15%, MgO content<0.4％。
Compared with the existing CA-80 type calcium aluminate cement clinker, the CA-80 calcium aluminate cement clinker prepared by the method has high mineral purity, finer fineness and larger volume specific surface area.
Meanwhile, the microstructure of the calcium aluminate cement clinker obtained in the examples 1-3 and the microstructure of the calcium aluminate cement clinker obtained in the comparative example 1 are observed, and the calcium aluminate cement clinker obtained in the examples 1-3 has the advantages of very consistent crystal development, good uniformity and uniform and stable mineral phase, and belongs to high-quality CA-80 calcium aluminate cement clinker. The mineral phase of comparative example 1 was not uniform and stable, and the quality was poor.
TABLE 2
As can be seen from Table 2, the calcium aluminate cement clinker prepared by the invention has higher flexural strength (more than 6.5MPa) and larger bulk density (more than 1.18 g/cm)3) The water demand is smaller (less than 22%) in practical application, and the time interval between initial setting and final setting is shorter.
Example 4 CA-70 series calcium aluminate Cement Clinker
This example provides a process for the production of a CA-70 series calcium aluminate cement clinker, similar to that of example 1, with the main differences:
(1) preparing slurry: 70kg of alumina, 30kg of calcium oxide and 100kg of water are added into a wet ball mill and ground for 15h to obtain slurry with the particle size of 200-400 meshes and the solid content of 78-80%.
(2) The temperature of the outlet firing section is 1450-1650 ℃.
Effect verification 2
Samples of the calcium aluminate cement clinker obtained in example 4 and comparative example 2 were tested using a commercially available dry powder fired CA-70 type calcium aluminate cement clinker as comparative example 2.
The test results were as follows:
TABLE 3
As can be seen from Table 3, the CA-70 calcium aluminate cement clinker of the present invention has the following characteristics:
chemical components: in mass percent, Al2O3The content of the CaO is between 26 and 27 percent, and the SiO is between 72 and 73 percent2Content (wt.)<0.3％，Fe2O3Content (wt.)<0.15%, MgO content<0.4％。
Compared with the existing CA-70 type calcium aluminate cement clinker, the CA-70 series calcium aluminate cement clinker prepared by the method has high mineral purity, finer fineness and larger volume specific surface area.
Meanwhile, the microstructure of the calcium aluminate cement clinker obtained in the example 4 and the microstructure of the calcium aluminate cement clinker obtained in the comparative example 2 are observed, and the calcium aluminate cement clinker obtained in the example 4 is very consistent in crystal growth, good in uniformity and uniform and stable in mineral phase, and belongs to high-quality CA-70 calcium aluminate cement clinker. The mineral phase of comparative example 2 was not uniform and stable, and the quality was poor.
TABLE 4
As can be seen from Table 4, the CA-70 series calcium aluminate cement clinker prepared by the method of the present invention has higher flexural strength (more than 6.8MPa) and higher bulk density (more than 1.2 g/cm)3) The water demand is smaller (less than 20%) in practical application, and the time interval between initial setting and final setting is shorter.
EXAMPLE 5 CA-50 SERIES ALUMINA CEMENT CLINKER
This example provides a method for producing a CA-50 series aluminous cement clinker, similar to example 1, with the main differences:
(1) preparing slurry: 49kg of bauxite, 51kg of limestone and 100kg of water are added into a wet ball mill and ground for 15h to obtain slurry with the particle size of 200-400 meshes and the solid content of 78-80%.
(2) The temperature of the outlet firing section is 1450-1500 ℃.
Effect verification 3
Samples of the alumina cement clinker obtained in example 4 and comparative example 3 were tested using a commercially available dry powder-fired CA-50 type alumina cement clinker as comparative example 3.
The test results were as follows:
TABLE 5
As is clear from Table 5, the CA-50 alumina cement clinker of the present invention has the following characteristics:
chemical components: in mass percent, Al2O350% of SiO2Content (wt.)<4％，Fe2O3Content (wt.)<1.5%, R2O content<0.3%, S content<0.01％。
Compared with the existing CA-50 type alumina cement clinker, the CA-50 type alumina cement clinker prepared by the method has high mineral purity, finer fineness and larger volume specific surface area.
Meanwhile, the microstructure of the alumina cement clinker obtained in the example 5 and the microstructure of the alumina cement clinker obtained in the comparative example 3 are observed, and the alumina cement clinker obtained in the example 5 has the advantages of very consistent crystal development, good uniformity and uniform and stable mineral phase, and belongs to high-quality CA-50 alumina cement clinker. The mineral phase of comparative example 3 was not uniform and stable, and the quality was poor.
TABLE 6
As can be seen from Table 6, the CA-50 aluminous cement clinker obtained by the process of the present invention has a higher flexural strength (greater than 13MPa) and a shorter time interval between initial setting and final setting.
Although the invention has been described in detail herein with reference to specific embodiments and general illustrations, it is to be understood that modifications or improvements may be made thereto based on the invention, including changes in names such as calcium aluminate binders or aluminate binders; as will be apparent to those skilled in the art. Therefore, it is intended to claim any modification or improvement made without departing from the spirit of the present invention, whether it is dry milling or wet milling, if it is extrusion (mechanical) molded, the size of the molded article is in the range of 1 to 80mm, the shape includes various shapes such as cube, sphere, cylinder, rhombohedron, etc., and it is fired in a rotary kiln or two-stage firing in a rotary kiln.
Claims (12)
1. A method for producing calcium aluminate cement clinker and alumina cement clinker is characterized by comprising the following steps: the wet pulping and extruding process to obtain green material, and sintering in one or two stage rotary kiln; the two-section rotary kiln is formed by connecting two rotary kilns in series, wherein the first rotary kiln executes a feeding preheating section and a middle soaking section, and the second rotary kiln executes an outlet burning section;
wherein the content of the first and second substances,
the slurry for producing the calcium aluminate cement clinker comprises alumina, calcium oxide or calcium carbonate;
the slurry for producing the alumina cement clinker comprises bauxite and limestone;
the length range of the forming body along the diameter direction of the rotary kiln cylinder is 1-80 mm;
the uniformity of the formed body is that the difference of the water content per cubic centimeter is less than 0.5 percent;
the temperature field of the rotary kiln is as follows: the temperature of the feed preheating section is 100-450 ℃, the temperature of the middle soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1250-1700 ℃.
2. A method as claimed in claim 1, wherein the temperature field of the rotary kiln is as follows for different grades of cement clinker products:
for CA-80 series calcium aluminate cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1400-1700 ℃;
for CA-70 series calcium aluminate cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1400-1650 ℃;
for CA-50 series alumina cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1250-1500 ℃.
3. The production method according to claim 2, wherein for CA-70 series calcium aluminate cement clinker, the temperature of the intermediate soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1500-1650 ℃;
for CA-50 series alumina cement clinker, the temperature of the middle soaking section is 500-800 ℃, and the temperature of the outlet firing section is 1450-1500 ℃.
4. The production method according to claim 1, wherein the length of the molded body in the direction of the diameter of the cylinder of the rotary kiln is 7 to 9 mm.
5. The production method according to claim 4, wherein the molded body has a cylindrical shape with a length of 15 to 20 mm.
6. The production method according to claim 1, characterized in that the water content of the molded body is controlled to 8-12%;
and/or controlling the density of the formed body to be 1.2-2.2g/cm for carrying out thin film planting.
7. The production method according to claim 6, characterized in that the water content of the molded body is controlled to 10-12%; controlling the density of the formed body to be 1.7-2.0g/cm thin shoots.
8. The production method according to claim 1, wherein the molded body is a cylindrical shape produced by carrying out thin film cultivation with a diameter of 7-9mm, a length of 15-20mm, a water content of 10-12% and a difference in water content per cubic centimeter of less than 0.5%, and a density of 1.7-2.0 g/cm.
9. The production method according to any one of claims 1 to 8, wherein the slurry is subjected to homogenization, dehydration and densification prior to the extrusion;
controlling the water content of the homogenized slurry to be 40-50%, and controlling the uniformity to reach that the difference value of the water content per cubic centimeter is less than 5%;
and/or controlling the water content of the slurry after the dehydration treatment to be 15-20%, wherein the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 1%;
and/or controlling the density of the densified material to be 1.2-1.5g/cm for carrying out the high-speed dry-mass cultivation, wherein the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 0.5%.
10. The production method according to claim 1, characterized by comprising the steps of:
(1) wet ball milling slurry:
preparation of slurry for CA-80 series calcium aluminate cement clinker: adding water into industrial alumina, calcium oxide or calcium carbonate for grinding to obtain slurry with the particle size of 200-400 meshes and the solid content of 70-80 percent;
wherein the mass ratio of the industrial alumina, the calcium oxide or the calcium carbonate to the water is (78-80): (20-22): (90-100); grinding for 8-24 h;
(2) homogenizing:
inputting the obtained slurry into a slurry tank, filtering, and then homogenizing: storing and filtering the slurry by using a plurality of slurry pools, synchronously conveying the filtered slurry to a cloth filter through a plunger pump, and uniformly mixing the slurry while conveying;
wherein, the water content of the homogenized slurry is controlled to be 40-50%, and the uniformity reaches that the difference value of the water content per cubic centimeter is less than 5%;
wherein, the pressure fluctuation of the plunger pump is controlled to be less than 1 percent;
(3) and (3) dehydration treatment:
continuously conveying the slurry to a filter cloth machine for dehydration treatment;
wherein, the water content of the slurry after the dehydration treatment is controlled to be 15-20%, and the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 1%;
(4) and (3) densification treatment:
the slurry is continuously conveyed to a pug kneading machine for further pug refining, so that the homogenization of the materials is further improved, and the density is increased;
wherein, controlling the density of the material after densification treatment to be 1.2-1.5g/cm for carrying out the cultivation, and the uniformity index reaches that the difference value of the water content per cubic centimeter is less than 0.5%;
(5) extrusion molding:
carrying out extrusion forming on the obtained materials to obtain a formed body: a cylinder having a diameter of 7-9mm, a water content of 10-12%, a difference in water content per cubic centimeter of less than 0.5%, and a density of 1.7-2.0g/cm for carrying out a thin film strip;
(6) firing:
when the length of the cylinder reaches 15-20mm, the cylinder is automatically cut off and is continuously conveyed to a drying kiln, the cylinder is dried, screened and then conveyed to a rotary kiln for burning, and cement clinker is obtained after cooling;
the temperature field of the rotary kiln is as follows: the temperature of a feed preheating section is 100-200 ℃, the temperature of a middle soaking section is 500-800 ℃, and the temperature of an outlet firing section is 1450-1700 ℃; the residence time of each stage is 6-8 h.
11. A cement clinker product obtained by the production method as recited in any one of claims 1 to 10, said cement clinker product being a CA-70/80 series calcium aluminate cement clinker or a CA-50 series aluminous cement clinker.
12. Use of the cement clinker product according to claim 11 in an aluminate binder or a refractory castable material.
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