CN111943533A - Red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material, cement clinker, cement and preparation method thereof - Google Patents
Red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material, cement clinker, cement and preparation method thereof Download PDFInfo
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- CN111943533A CN111943533A CN202010914232.3A CN202010914232A CN111943533A CN 111943533 A CN111943533 A CN 111943533A CN 202010914232 A CN202010914232 A CN 202010914232A CN 111943533 A CN111943533 A CN 111943533A
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B7/00—Hydraulic cements
- C04B7/22—Iron ore cements ; Iron rich cements, e.g. Ferrari cements, Kühl cements
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- 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
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Abstract
The invention relates to the technical field of cement, in particular to a red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material, cement clinker, cement and a preparation method thereof, wherein the raw material composition of the cement raw material comprises the following components in parts by weight: 30-50 parts of calcareous raw material, 20-50 parts of red mud, 10-25 parts of barium-containing and/or strontium-containing raw material, 20-30 parts of aluminum raw material and 5-20 parts of gypsum. The invention not only burns the cement clinker with high content of calcium aluminoferrite at low temperature, avoids the phenomena of cement kiln skinning and even blockage caused by cement clinker fusion, but also obviously improves the hydration activity of the calcium aluminoferrite. The detection shows that the calcium aluminoferrite in the cement clinker reaches 25-60%, the 28-day hydration degree of the calcium aluminoferrite in the cement clinker is more than or equal to 70%, the 28-day hydration degree of calcium sulfosilicate is more than or equal to 25%, and the radioactivity of the cement clinker meets the requirement IRaLess than or equal to 1.0 and Ir≤1.0。
Description
Technical Field
The invention relates to the technical field of cement, in particular to a red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material, cement clinker, cement and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The preparation process of the cement mainly comprises the following steps: crushing and pre-homogenizing → preparation of raw materials → homogenizing of raw materials → pre-heating decomposition → burning of clinker → cement grinding, and finally obtaining the main mineral composition: cement clinker of tricalcium silicate, dicalcium silicate, tricalcium aluminate, calcium aluminoferrite and calcium sulfate; the content of calcium aluminoferrite is increased, the chloride ion curing capacity and the wear-resisting and scouring-resisting performance of the cement can be improved, and therefore the high-iron cement is particularly suitable for marine engineering and road engineering.
In the common portland cement and sulphoaluminate cement, the clinker calcination temperature is 1450 ℃ and 1350 ℃, respectively, calcium aluminoferrite is melted into liquid phase after the calcination temperature exceeds 1200 ℃, which easily causes the cement clinker to block the cement kiln, so the designed content of the calcium aluminoferrite in the portland cement clinker and the sulphoaluminate cement clinker is always lower than 15 wt.%.
In conclusion, the present inventors believe that the current high-iron cement preparation method still has the following disadvantages: (1) the sintering temperature of the cement clinker needs to be reduced, and the calcium aluminoferrite is prevented from being fused, so that the content of the calcium aluminoferrite in the cement clinker is increased. (2) The hydration activity of the calcium aluminoferrite is lower than that of the main mineral alite of portland cement and the main mineral calcium aluminoferrite of sulphoaluminate cement, and the hydration activity needs to be further improved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material, a cement clinker, cement and a preparation method thereof. In order to achieve the above object, the technical solution of the present invention is specifically as follows:
in the first aspect of the invention, the red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material comprises the following components in parts by weight: 30-50 parts of calcareous raw material, 20-50 parts of red mud, 5-20 parts of barium-containing and/or strontium-containing raw material, 20-30 parts of aluminum raw material and 10-20 parts of gypsum.
Further, the calcium raw material comprises at least one of limestone, carbide slag and the like, and the aluminum raw material is Al2O3Low grade alumina or aluminum ash with a content of less than 50%. Calcium, iron, aluminum and sulfur elements are provided by calcareous raw materials, red mud, aluminum raw materials and gypsum to form calcium sulpho-iron aluminate, calcium sulpho-calcium silicate, calcium aluminoferrite and belite in the subsequent process of preparing cement clinker.
The present invention replaces most of belite mineral calcium sulfosilicate minerals in the cement clinker with sufficient gypsum to satisfy the sufficient formation of calcium sulfoaluminate and calcium sulfosilicate minerals by adding sufficient gypsum in the cement raw materials.
Further, the barium-and/or strontium-containing raw material comprises at least one of barium slag and/or strontium slag and the like. In the invention, the mineralization of calcium sulphoaluminate minerals by a large amount of alkali metal potassium and sodium contained in the red mud is utilized, and the formation temperature of the calcium sulphoaluminate can be obviously reduced under the condition that barium and/or strontium exist, so that the calcium sulphoaluminate can be further promoted to be formed in a large amount within the range of 1050-. In addition, barium and strontium contained in the barium slag or the strontium slag can absorb the rays released by potassium-40, radium-226 and thorium-232 in the red mud, so that the radioactivity of the cement is obviously reduced.
Further, the aluminum raw material comprises at least one of aluminum ash, bauxite tailings and the like. In the invention, the formation temperature of each component (calcium aluminoferrite, calcium sulfosilicate, calcium aluminoferrite and dicalcium silicate) in the clinker of the aged cement can be unified to 1050-1180 ℃ by reducing the formation temperature of the calcium aluminoferrite, so that a large amount of calcium aluminoferrite can be designed and generated in the clinker of the cement, and the calcium aluminoferrite can not be melted in the temperature range, thereby avoiding the problem of furnace skinning and even blockage.
Further, the gypsum includes at least one of natural gypsum, industrial waste gypsum, and the like.
Furthermore, each raw material in the red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material is divided into powder so as to be mixed fully and contact and react fully in the subsequent clinker preparation process.
In a second aspect of the present invention, a cement clinker is provided, which comprises the following components by mass: 25-60% of calcium aluminoferrite, 25-45% of calcium sulfosilicate, 15-30% of calcium sulfoaluminoferrite and 0-2% of dicalcium silicate.
Further, the calcium aluminoferrite comprises C2F、C6AF2、C4AF、C6A2F.
In a third aspect of the present invention, there is provided a method for producing the cement clinker, comprising the steps of:
(1) uniformly mixing the calcareous raw material, the red mud, the barium-and/or strontium-containing raw material, the aluminum raw material and the gypsum in proportion to obtain cement raw materials;
(2) and (2) calcining the cement raw material obtained in the step (1), and then quenching in air to obtain the cement.
Further, in the step (1), the raw materials are mixed, ground and sieved by a 100-mesh sieve to prepare the cement raw material.
Further, in the step (2), the cement raw material is pressed into cakes or balls and dried, and then the obtained raw material cakes or raw material balls are calcined for 5-30min at 1050-.
In a fourth aspect of the present invention, there is provided a calcium sulfosilicate-calcium aluminoferrite cement, comprising the following components in parts by weight: 5-15 parts of limestone, 5-10 parts of silica fume and 80-100 parts of the cement clinker.
In the process of calcining cement clinker, sodium and potassium contained in the red mud are dissolved in the cement clinker minerals in a solid solution manner, but are released in the cement hydration process, and under the condition of gypsum, alkali metals are converted into sodium sulfate and potassium sulfate to cause cement to be saltpetering, and the compactness of a cement-based material and the chemical reaction of silica fume and alkali are improved by introducing part of stone powder and silica fume, so that the saltpetering phenomenon is avoided.
In addition, compared with the traditional portland cement clinker and the like, the calcium sulfosilicate-calcium ferroaluminate cement does not contain gypsum, wherein the calcium sulfoferroaluminate forms U phase or AFm after post hydration. Under the condition of introducing gypsum, the calcium sulphoaluminate hydrates to form AFt, and compared with the AFt, the solid solution capacity of the calcium sulphoaluminate and the AFt to alkali metal potassium and sodium is obviously enhanced, so that the solidification capacity of cement to alkali metal is improved without introducing the gypsum, and the efflorescence phenomenon is avoided.
Compared with the prior art, the technical scheme provided by the invention at least has the following beneficial effects:
(1) the red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker has the calcination temperature of 1050-1180 ℃, is obviously reduced compared with the calcination temperatures of silicate cement clinker and sulphoaluminate cement clinker (1450 ℃ and 1350 ℃ respectively), has the content of calcium aluminoferrite in the cement clinker up to 25-60 percent, is obviously improved compared with the content of calcium aluminoferrite in the silicate cement clinker and the sulphoaluminate cement clinker which is not more than 15 percent, does not melt the cement clinker, and has no skin formation and blockage phenomenon in a kiln.
(2) The hydration activity of calcium aluminoferrite and calcium sulfosilicate can be improved by alkali in the red mud, the activity of calcium aluminoferrite and calcium sulfosilicate in the red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker is effectively improved, and through detection, the hydration degree of calcium aluminoferrite in the cement clinker sintered by the embodiment of the invention is more than or equal to 70% in 28 days, and the hydration degree of calcium sulfosilicate is more than or equal to 25% in 28 days, so that the mechanical property of the cement is obviously improved. In addition, because the content of iron phase in the cement is higher, the red mud-based calcium sulfosilicate-iron aluminate cement has good chloride ion corrosion resistance, sulfate corrosion resistance, wear resistance and scouring resistance.
(3) The invention absorbs the rays released by potassium-40, radium-226 and thorium-232 in the red mud through the barium slag or the strontium slag, obviously reduces the radioactivity of the cement, and eliminates the defect that the radioactivity exceeds the standard when the polluting solid waste of the red mud is used as the cement raw material; through detection, the radioactivity of the cement clinker prepared by the embodiment of the invention simultaneously meets the I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) The hydration activity of calcium aluminoferrite is low, and the hydration activity of calcium sulfosilicate is very low, however, in the invention, part of alkali metal and barium and/or strontium are dissolved in the cement clinker in a solid solution manner in the calcination process, so that the crystal structure defects of calcium aluminoferrite and calcium sulfosilicate are increased, and the hydration activity of the calcium aluminoferrite and calcium sulfosilicate is improved. In addition, the hydration activity of calcium sulfosilicate is further activated in the presence of calcium aluminoferrite and calcium sulfoaluminate.
(5) Although the red mud for preparing the cement clinker contains a large amount of alkali metals, the red mud-based calcium sulfosilicate-calcium aluminoferrite cement prepared by the invention does not need gypsum, and simultaneously introduces part of stone powder and silica fume, so that sodium and potassium in a cement hydration product are effectively solidified, and the phenomenon of efflorescence is avoided.
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 incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is an XRD pattern of red mud-based calcium sulfosilicate-ferric aluminate cement clinker prepared by the first example of the present invention.
Fig. 2 is a graph showing the results of testing the erosion resistance of the red mud-based calcium sulfosilicate-ferrous aluminate cement prepared according to the first embodiment of the present invention.
Fig. 3 is a graph showing the results of the compressive strength test of the red mud-based calcium sulfosilicate-ferrous aluminate cement prepared according to the first embodiment of the present invention.
Fig. 4 shows the hydration degree of calcium aluminoferrite and calcium sulfosilicate in the red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker prepared by the second embodiment of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
In the following examples, the carbide slag was purchased from Shandong Hengtong chemical Co., Ltd. The carbide slag is waste slag which is generated after acetylene gas is obtained by hydrolyzing calcium carbide and takes calcium oxide as a main component, and in addition, the carbide slag also comprises magnesium oxide, aluminum oxide, ferric oxide, silicon dioxide and other components.
In the following examples, the red mud is bayer process red mud available from trust group ltd. The red mud is alkaline waste residue discharged in the process of extracting aluminum oxide in the aluminum production industry, and the main component of the red mud comprises SiO2、CaO、Fe2O3、Al2O3、Na2O、K2O、TiO2MgO, and the like.
In the following examples, the barium residue was purchased from Hebei Xin Ji chemical group, LLC. The barium slag is solid waste generated in the process of producing barium carbonate by using barite, and the main components of the barium slag comprise acid-soluble barium and water-soluble barium.
In the following examples, the strontium slag was purchased from the chemical group, llc of north oceanic collection, hebei. The strontium slag is a mixture of unreacted ore and coal after leaching in the process of producing strontium carbonate by a leaching process, and contains water-soluble barium.
In the following examples, the aluminum ash was purchased from Shandong Wei Qiaoqiao Chuangyage group, Inc. The aluminum ash is generated in the process of melting all aluminum, and the main component of the aluminum ash is aluminum oxide, and part of aluminum metal and other impurities are included.
In the following examples, the bauxite tailings were obtained from the spring of the river. Bauxite tailings are an aluminum-containing waste produced during the mining of bauxite ores.
In the following examples, the silica fume is available from Shandong Liufu Silicones, Inc. The silicon ash is volatile SiO generated when ferroalloy is used for smelting ferrosilicon and industrial silicon2And Si gas and air are quickly oxidized, condensed and precipitated to form.
First embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) 45 parts of limestone, 20 parts of red mud, 10 parts of barium slag, 30 parts of aluminum ash and 20 parts of fluorgypsum are uniformly mixed in parts by weight, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw meal obtained in the step (1), pressing the cement raw meal into cakes in a mould, drying the obtained raw meal cakes, calcining the raw meal cakes at 1125 ℃ for 5min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis and the mineral composition of the cement clinker was measured by Rietveld quantitative analysis, referring to fig. 1, which shows that the main mineral composition was 25% by mass of calcium aluminoferrite, 45% by mass of calcium sulfosilicate, 30% by mass of calcium sulfoaluminoferrite, and 0% by mass of dicalcium silicate.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.05、IrLess than or equal to 0.04, and is obviously lower than I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 15 parts by weight of limestone, 5 parts by weight of silica fume and 100 parts by weight of the cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.30, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and reach 71.29% and 26.0% respectively.
(5) The red mud-based calcium sulfosilicate-iron aluminate cement sample prepared in (4) above was tested for erosion resistance, and the results are shown in fig. 2, and it can be seen that the cement of this example has better resistance to chloride ion erosion and sulfate erosion than the conventional sulfate cement and sulphoaluminate cement.
(6) As shown in fig. 3, it can be seen that the compressive strength of the cement sample of the present example in the 28-day hydration period reaches 85MPa or more, so that the red mud based calcium sulfosilicate-iron aluminate cement of the present example has excellent wear resistance and scouring resistance.
Second embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) by weight, 50 parts of carbide slag, 30 parts of red mud, 15 parts of strontium slag, 20 parts of bauxite tailings and 20 parts of boron gypsum are uniformly mixed, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water to the cement raw material obtained in the step (1), uniformly stirring, pressing into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1100 ℃ for 20min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker, whose main mineral composition was 47% by mass of calcium aluminoferrite, 25% by mass of calcium sulfosilicate, 30% by mass of calcium aluminothiosilicate, and 2% by mass of dicalcium silicate, was measured by Rietveld quantitative analysis.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.08、Ira0.07, significantly lower than I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 10 parts by weight of limestone, 10 parts by weight of silica fume and 80 parts by weight of the cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.30, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and reach 73.4% and 26.7% respectively (refer to fig. 4).
Third embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) 45 parts of limestone, 35 parts of red mud, 15 parts of barium slag, 25 parts of bauxite tailings and 15 parts of boron gypsum are uniformly mixed in parts by weight, and the mixture is ground and sieved by a 100-mesh sieve to obtain cement raw materials.
(2) And (2) sprinkling water to the cement raw material obtained in the step (1), uniformly stirring, pressing into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1150 ℃ for 20min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker, whose main mineral composition was 60% by mass of calcium aluminoferrite, 19% by mass of calcium sulfosilicate, 20% by mass of calcium aluminothiosilicate, and 1% by mass of dicalcium silicate, was measured by Rietveld quantitative analysis.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.10、IrLess than or equal to 0.09, is obviously lower than the I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 15 parts by weight of limestone, 5 parts by weight of silica fume and 80 parts by weight of the cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.31, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and respectively reach 79.7% and 30.48%.
Fourth embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) 30 parts of limestone, 50 parts of red mud, 20 parts of barium slag, 30 parts of bauxite tailings and 10 parts of phosphogypsum are uniformly mixed in parts by weight, and the mixture is ground and sieved by a 100-mesh sieve to obtain cement raw materials.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the cement raw material into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1050 ℃ for 30min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker, whose main mineral composition was 60% by mass of calcium aluminoferrite, 24% by mass of calcium sulfosilicate, 15% by mass of calcium aluminothiosilicate, and 1% by mass of dicalcium silicate, was tested by Rietveld quantitative analysis.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.14、IrLess than or equal to 0.12, is obviously lower than the I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 5 parts by weight of limestone, 10 parts by weight of silica fume and 85 parts by weight of cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.30, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and reach 80.20% and 26.89% respectively.
Fifth embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) by weight, 40 parts of limestone, 20 parts of red mud, 10 parts of barium slag, 27 parts of aluminum ash and 10 parts of natural gypsum are uniformly mixed, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the water in a mould to form a cake, drying the obtained raw material cake, calcining the raw material cake at 1180 ℃ for 5min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker was tested by Rietveld quantitative analysis, which was composed of the following main minerals: 28 mass% of calcium aluminoferrite, 40 mass% of calcium sulfosilicate, 30 mass% of calcium sulfoaluminoferrite, and 2 mass% of dicalcium silicate.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.07、IrLess than or equal to 0.05 and is obviously lower than I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 10 parts by weight of limestone, 7 parts by weight of silica fume and 100 parts by weight of cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.30, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and reach 71.2% and 25.5% respectively.
Sixth embodiment
A preparation method of red mud-based calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following steps:
(1) 30 parts of limestone, 20 parts of red mud, 5 parts of strontium slag, 25 parts of aluminum ash and 20 parts of natural gypsum are uniformly mixed in parts by weight, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the cement raw material into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1120 ℃ for 15min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
(1) The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker was tested by Rietveld quantitative analysis, which was composed of the following main minerals: 28 mass% of calcium aluminoferrite, 40 mass% of calcium sulfosilicate, 30 mass% of calcium sulfoaluminoferrite, and 2 mass% of dicalcium silicate.
(2) In the preparation process, the cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝0.07、Ir0.05, which is significantly lower than I required in the national standardRaLess than or equal to 1.0 and Ir≤1.0。
(4) 8 parts by weight of limestone, 10 parts by weight of silica fume and 85 parts by weight of cement clinker prepared in the embodiment are mixed to obtain calcium silicate sulfate-calcium aluminoferrite cement, the calcium silicate sulfate-calcium aluminoferrite cement is prepared into slurry according to the water-cement ratio of 0.30, the slurry is poured into a grinding tool for forming and then is naturally cured for 28 days, the sample is free from the phenomenon of whiskering, and the detection result shows that the 28-day hydration degrees of calcium aluminoferrite and calcium silicate sulfate are remarkably improved and reach 71.2% and 25.5% respectively.
Comparative test example 1
A preparation method of cement clinker comprises the following steps:
(1) by weight, 50 parts of carbide slag, 30 parts of iron ore, 20 parts of bauxite tailings and 5 parts of boron gypsum are uniformly mixed, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the cement raw material into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1300 ℃ for 20min, and then quenching the obtained product in air to obtain the cement clinker.
In the test example, when the composition of the cement clinker minerals is designed, strontium slag is not added, and the red mud is replaced by iron ore, so that calcium sulfosilicate is completely replaced by belite; in addition, the addition amount of gypsum was reduced to comparatively study the influence of the amount of gypsum in the raw meal on the low-temperature sufficient formation of calcium sulfoferrite aluminate.
The cement clinker prepared in this example was subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker was tested by Rietveld quantitative analysis, which was composed of the following main minerals: 25% by mass of calcium aluminoferrite, 17% by mass of calcium sulfosilicate, 21% by mass of calcium sulfoaluminoferrite, 29% by mass of dicalcium silicate and 8% by mass of calcium aluminate.
It can be seen that belite reacts with gypsum to form calcium sulfosilicate, and the gypsum required for forming calcium sulfoferrite aluminate is insufficient, so that cement clinker minerals cannot be fully formed, and therefore, the design of calcium sulfosilicate minerals for cement clinker and the reduction of belite minerals are very important for the medium formation of the cement clinker minerals.
Comparative test example 2
A preparation method of cement clinker comprises the following steps:
(1) by weight, 50 parts of carbide slag, 30 parts of iron ore, 20 parts of bauxite tailings and 20 parts of boron gypsum are uniformly mixed, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the water in a mould to form a cake, drying the obtained raw material cake, calcining the raw material cake at 1150 ℃ for 20min and 90min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
In this test example, the red mud was replaced with iron ore to provide Fe for cement clinker mineral formation2O3Comparison of the formation of cement clinker under alkali-free conditions.
The cement clinker prepared in this example was subjected to X-ray diffraction analysis and the mineral composition of the cement clinker was tested by Rietveld quantitative analysis, wherein:
the mineral composition of the cement clinker prepared by calcining at 1150 ℃ for 20min is as follows: 12% by mass of calcium aluminoferrite, 34% by mass of calcium sulfosilicate, 14% by mass of calcium sulfoaluminoferrite, 10% by mass of dicalcium silicate, 7% by mass of anhydrite, 23% by mass of calcium aluminate, and insufficient formation of cement clinker minerals.
The mineral composition of the cement clinker prepared by calcining at 1150 ℃ for 90min is as follows: 25% by mass of calcium aluminoferrite, 45% by mass of calcium sulfosilicate, 30% by mass of calcium sulfoaluminoferrite, and 0% by mass of dicalcium silicate, and the cement clinker minerals can be sufficiently formed, but a long holding time is required, and this process is industrially difficult to realize. Therefore, the alkali in the red mud is crucial to the firing of cement clinker.
Comparative test example 3
A preparation method of cement clinker comprises the following steps:
(1) by weight, 50 parts of carbide slag, 15 parts of fly ash, 20 parts of bauxite tailings and 20 parts of boron gypsum are uniformly mixed, ground and sieved by a 100-mesh sieve to obtain the cement raw material.
(2) And (2) sprinkling water on the cement raw material obtained in the step (1), pressing the cement raw material into a cake in a mould, drying the obtained raw material cake, calcining the raw material cake at 1100 ℃ for 30min and 90min, and then quenching the obtained product in air to obtain the cement clinker.
Performance testing
In this test example, fly ash was used in place of barium or strontium slag to compare the effects of firing of cement clinker minerals and the activity of calcium aluminoferrite and calcium sulfosilicate in the absence of barium and strontium.
(1) The cement clinker prepared in the embodiment is subjected to X-ray diffraction analysis, and the mineral composition of the cement clinker is tested by a Rietveld quantitative analysis method, wherein the main mineral composition of the cement clinker prepared by calcining at 1100 ℃ for 30min is as follows: 50% by mass of calcium aluminoferrite, 23% by mass of calcium sulfosilicate, 25% by mass of calcium sulfoaluminoferrite, and 2% by mass of dicalcium silicate.
(2) The cement clinker of the embodiment is not melted in the calcining process, so that the problem of kiln skinning and even blockage is avoided.
(3) The cement clinker prepared in this example has a radioactivity IRa＝1.17、Ir1.43, the radioactivity of the burned cement clinker exceeds the standard.
(4) 10 parts by weight of limestone, 10 parts by weight of silica fume and 80 parts by weight of the cement clinker prepared in the example were mixed, and the mixture was made into slurry at a water-cement ratio of 0.30, and poured into a mold to be molded and naturally cured for 28 days without causing a whiskering phenomenon, and the test results showed that the 28-day hydration degrees of calcium aluminoferrite and calcium sulfosilicate were 50.21% and 15.46%. Therefore, barium or strontium has an important influence on the activity of calcium aluminoferrite and calcium sulfosilicate.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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. The red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material comprises the following raw materials:
2. the red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material as set forth in claim 1, wherein said calcareous raw material comprises at least one of limestone and carbide slag.
3. The red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material as set forth in claim 1, wherein said barium and/or strontium containing raw material comprises at least one of barium slag and/or strontium slag.
4. The red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material as set forth in claim 1, wherein the aluminum raw material comprises at least one of aluminum ash and bauxite tailings.
5. The red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material as set forth in any one of claims 1 to 4, wherein each raw material in the red mud-based calcium sulfosilicate-calcium aluminoferrite cement raw material is in the form of powder.
6. A calcium sulfosilicate-calcium aluminoferrite cement clinker comprises the following components in percentage by mass: 25-60% of calcium aluminoferrite, 25-45% of calcium sulfosilicate, 15-30% of calcium sulfoaluminoferrite and 0-2% of dicalcium silicate.
7. The calcium sulfosilicate-calcium aluminoferrite cement clinker of claim 6, wherein said calcium aluminoferrite comprises C2F、C6AF2、C4AF、C6A2F.
8. The method for producing a calcium sulfosilicate-calcium aluminoferrite cement clinker according to claim 6 or 7, characterized by comprising the steps of:
(1) uniformly mixing the calcareous raw material, the red mud, the barium-and/or strontium-containing raw material, the aluminum raw material and the gypsum according to any one of claims 1 to 5 in proportion to obtain cement raw materials;
(2) and (2) calcining the cement raw material obtained in the step (1), and then quenching in air to obtain the cement.
9. The method for producing calcium sulfosilicate-calcium aluminoferrite cement clinker according to claim 8, wherein in the step (1), the raw materials are mixed, ground and then sieved with a 100-mesh sieve to obtain cement raw materials;
or, in the step (2), pressing the cement raw material into cakes or balls, drying, and calcining the obtained raw material cakes or raw material balls at 1050-.
10. Calcium sulfosilicate-calcium aluminoferrite cement comprises the following components in parts by weight: 5-15 parts limestone, 5-10 parts silica fume, 80-100 parts of said cement clinker of claim 6 or 7 or of a calcium sulfosilicate-calcium aluminoferrite cement clinker prepared by the process of claim 8 or 9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149476A (en) * | 2021-04-10 | 2021-07-23 | 浙江红狮环保股份有限公司 | Method for disposing electrolytic aluminum ash in cement clinker production |
| CN113816628A (en) * | 2021-09-30 | 2021-12-21 | 登电集团水泥有限公司 | Preparation process of sulphoaluminate cement clinker |
| CN113880475A (en) * | 2021-10-25 | 2022-01-04 | 福州大学 | Red mud-based magnesium phosphate cement and preparation method thereof |
| CN113968705A (en) * | 2021-11-10 | 2022-01-25 | 中铁十二局集团有限公司 | Multi-element gel system STC (concrete-time-dependent temperature) ultrahigh-toughness concrete material for bridge deck pavement |
| CN114014567A (en) * | 2021-11-22 | 2022-02-08 | 济南大学 | Method for directly preparing cement clinker from high-alkali red mud |
| CN115838250A (en) * | 2022-12-01 | 2023-03-24 | 济南大学 | Red mud-based admixture and clinker as well as preparation method and application thereof |
| CN116282981A (en) * | 2023-01-17 | 2023-06-23 | 济南大学 | Iron-rich multi-element cement clinker capable of efficiently utilizing red mud and preparation method thereof |
| CN116730638A (en) * | 2023-06-15 | 2023-09-12 | 济南大学 | Alkali-resistant iron-rich sulphoaluminate cement composite cementing material and preparation process thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533473A (en) * | 2020-03-30 | 2020-08-14 | 洲际环境科学研究院(广州)有限公司 | Method for preparing ferrous aluminate cement clinker by using Bayer process red mud |
-
2020
- 2020-09-03 CN CN202010914232.3A patent/CN111943533B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533473A (en) * | 2020-03-30 | 2020-08-14 | 洲际环境科学研究院(广州)有限公司 | Method for preparing ferrous aluminate cement clinker by using Bayer process red mud |
Non-Patent Citations (1)
| Title |
|---|
| 程新: "硫铝酸钡(锶)钙水泥的制备及应用", 《硅酸盐学报》 * |
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| CN113816628B (en) * | 2021-09-30 | 2022-08-16 | 登电集团水泥有限公司 | Preparation process of sulphoaluminate cement clinker |
| CN113816628A (en) * | 2021-09-30 | 2021-12-21 | 登电集团水泥有限公司 | Preparation process of sulphoaluminate cement clinker |
| CN113880475A (en) * | 2021-10-25 | 2022-01-04 | 福州大学 | Red mud-based magnesium phosphate cement and preparation method thereof |
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| CN114014567B (en) * | 2021-11-22 | 2023-01-24 | 济南大学 | Method for directly preparing cement clinker from high-alkali red mud |
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| CN115838250B (en) * | 2022-12-01 | 2023-10-27 | 济南大学 | Red mud-based admixture, clinker, and preparation method and application thereof |
| CN116282981A (en) * | 2023-01-17 | 2023-06-23 | 济南大学 | Iron-rich multi-element cement clinker capable of efficiently utilizing red mud and preparation method thereof |
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