CN111187011A - High-strength cement and preparation method thereof - Google Patents

High-strength cement and preparation method thereof Download PDF

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Publication number
CN111187011A
CN111187011A CN202010028710.0A CN202010028710A CN111187011A CN 111187011 A CN111187011 A CN 111187011A CN 202010028710 A CN202010028710 A CN 202010028710A CN 111187011 A CN111187011 A CN 111187011A
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cement
raw materials
cement clinker
volcanic ash
percent
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CN111187011B (en
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苗晓川
琚瑞喜
赵新辉
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Dengfeng Songji Cement Co ltd
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Dengfeng Songji Cement Co ltd
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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
    • C04B7/12—Natural pozzuolanas; Natural pozzuolana cements; Artificial pozzuolanas or artificial pozzuolana cements other than those obtained from waste or combustion residues, e.g. burned clay; Treating inorganic materials to improve their pozzuolanic characteristics
    • C04B7/13—Mixtures thereof with inorganic cementitious materials, e.g. Portland cements
    • 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
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
    • 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
    • C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
    • 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
    • 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 discloses high-strength cement and a preparation method thereof, belonging to the technical field of cement manufacture. The high-strength cement comprises cement clinker and a mixed material, wherein the cement clinker is mainly prepared from the following raw materials in parts by weight: 8-10 parts of limestone, 2.5-3.5 parts of volcanic ash, 0.25-0.35 part of pyrite cinder and 0.4-0.45 part of copper slag. The preparation method of the high-strength cement comprises the following steps: mixing and grinding the raw materials of the cement clinker to prepare raw materials, then pre-sintering the raw materials, then sintering the raw materials for 20-25min at 1250-; and mixing and grinding the prepared cement clinker and the mixed material to obtain the cement clinker. The volcanic ash is added into the raw materials of the cement clinker in the high-strength cement, so that the compression strength of the cement clinker is improved through the high-temperature sintering process of the volcanic ash, in addition, the reaction efficiency is improved, and the sintering time is shortened.

Description

High-strength cement and preparation method thereof
Technical Field
The invention relates to the technical field of cement manufacturing, in particular to high-strength cement and a preparation method thereof.
Background
At present, many projects are constructed by adopting underground or tunnel projects, wherein the adopted concrete has high strength and good impermeability to prevent water seepage. The cement with higher impermeability is generally pozzolan cement, which has higher impermeability, higher durability, better chemical corrosion resistance and the like. However, the strength of the pozzolan cement is not generally high, and for example, the 28d compressive strength of the pozzolan cement at a content of 30% is mostly around 35-40 MPa. In order to improve the strength of cement, the mixing amount of the pozzolana is reduced in most cases.
The invention discloses a novel slag silicate P.SA32.5 cement which is prepared by grinding cement clinker, limestone, slag, volcanic ash, fly ash and desulfurized gypsum together, wherein the content of the volcanic ash is 4-7%, the final strength in 3 days is 14MPa, the strength in 28 days is 38MPa, and the strength is still lower.
Disclosure of Invention
In view of the defects of the prior art, the first object of the present invention is to provide a high strength cement, which can improve the strength of the cement while ensuring the high impermeability of the cement.
The second purpose of the invention is to provide a preparation method of high-strength cement, which has simple process and short sintering time.
In order to achieve the first object, the invention provides the following technical scheme:
the high-strength cement comprises cement clinker and a mixed material, wherein the cement clinker is mainly prepared from the following raw materials in parts by weight: 8-10 parts of limestone, 2.5-3.5 parts of volcanic ash, 0.25-0.35 part of pyrite cinder and 0.4-0.45 part of copper slag.
By adopting the technical scheme, when the cement clinker is fired, the volcanic ash is used as a main raw material, and the volcanic ash is subjected to a sintering process. In the high-temperature sintering process, the silicon phase and the aluminum phase in the volcanic ash are easier to melt out, the melting amount is larger, and the silicon phase and the aluminum phase are easier to react with components in other raw materials to generate a required phase. In the high-temperature sintering process, the volcanic ash component can also promote the generation of a material containing air holes, so that the impermeability of the cement is improved, and the spalling resistance and impact resistance of the cement are improved. The material containing air holes has low temperature expansion coefficient, excellent anti-shrinkage performance and difficult generation of cracks.
The raw materials of the cement clinker are added with the pyrite cinder, the copper slag and the like, so that the industrial waste slag can be fully utilized, and the cement clinker meets the requirement of environmental protection. The sulfuric acid slag contains ferric oxide, aluminum oxide and the like, so that the raw materials can be accelerated to be melted, more liquid phases can be generated, the reaction efficiency is improved, and the energy consumption of raw material melting is also saved. The crystal nucleus of the internal crystal of the copper slag has more defects, the activation energy is lower, and more FeO is contained, so that the minimum co-dissolution temperature of the fired material can be reduced, the liquid phase amount is increased, the reaction efficiency is improved, and the using amount of a mineralizer is reduced.
The invention is further configured to: the cement clinker is mainly prepared from the following raw materials in parts by weight: 8.5-10 parts of limestone, 2.8-3.5 parts of volcanic ash, 0.3-0.35 part of pyrite cinder and 0.4-0.42 part of copper slag.
By adopting the technical scheme, the proportion of the raw materials is optimized, the utilization rate of the raw materials is improved, the cement clinker with higher overall performance can be obtained, and the cost of the raw materials is reduced.
The invention is further configured to: the volcanic ash comprises the following components: 48.5-50.2% SiO25.05 to 9.36 percent of Al2O35.81-6.12% of Fe2O315.88 to 19.27 percent of CaO and 6.49 to 7.92 percent of MgO.
By adopting the technical scheme, the volcanic ash contains silicon, aluminum, calcium and other components with relatively balanced contents, belongs to a volcanic ash material with a loose particle structure, is easier to be uniformly mixed with other raw materials, and has higher reaction efficiency at high temperature. The higher calcium content can also provide more calcium components for high-temperature reaction, avoid using more gypsum, further avoid introducing more sulfur and enhance the corrosion resistance of the cement.
The invention is further configured to: the specific surface area of the volcanic ash is 360-375m2/kg。
By adopting the technical scheme, the volcanic ash material with larger specific surface area is adopted, the adsorption performance is better, and the raw material with high specific surface area is easier to mix evenly when being mixed with other raw materials.
The invention is further configured to: the raw materials also comprise 0.5-0.8 part by weight of plant waste treatment substances, and the plant waste treatment substances are obtained by soaking straws or rice husks in hydrochloric acid and then drying.
By adopting the technical scheme, the plant waste treatment substance is added into the raw materials of the cement clinker, most organic matters in the plant waste treatment substance are removed after the straws or rice hulls are soaked in hydrochloric acid, a small amount of organic matters and most inorganic mineral matters are remained, in the temperature rising stage of high-temperature treatment, the residual organic matters generate gas to be separated from a system, and silicon in the inorganic matters can generate loose nano-scale silicon dioxide materials and fully react with the melted calcium and aluminum components at higher temperature to generate corresponding phases.
The invention is further configured to: the mass fraction of the hydrochloric acid adopted during the hydrochloric acid soaking is 5-8%.
By adopting the technical scheme, hydrochloric acid with lower concentration is adopted during soaking, so that the treatment of organic matters can be met, the cost is reduced, and waste hydrochloric acid with low concentration can be used for treatment.
The invention is further configured to: the hydrochloric acid is soaked for 3-5 h.
By adopting the technical scheme, as hydrochloric acid with lower concentration is adopted for soaking, in order to fully remove the organic matters and avoid consuming more energy in subsequent high-temperature sintering, the soaking is carried out for a longer time, and the full action of the organic matters and the hydrochloric acid is ensured.
The invention is further configured to: the drying is carried out at the temperature of 100 ℃ and 110 ℃ for 0.5-1 h.
By adopting the technical scheme, the soaked solid matter can be completely removed by drying at the temperature of 100-110 ℃ for 0.5-1h, so that the amount of moisture introduced when the solid matter is mixed with other raw materials is reduced to the maximum extent, and agglomeration caused when the materials are mixed and agglomeration caused when the materials are sintered is avoided.
The invention is further configured to: the weight ratio of the cement clinker to the mixed material is 65-75:25-35, and the mixed material is formed by mixing volcanic ash, desulfurized gypsum and converter slag.
By adopting the technical scheme, the volcanic ash is added into the cement admixture, and highly dispersed active oxides in the volcanic ash can be combined with calcium components to react with each other to form hydration product gel taking hydrated calcium silicate as a main body, so that the initial setting time of cement is shortened, hydration products of cement clinker can be consumed, and further mineral hydration reactions in the cement clinker are promoted.
In order to achieve the second object, the invention provides the following technical scheme:
the preparation method of the high-strength cement comprises the following steps:
1) mixing and grinding the raw materials of the cement clinker to prepare raw materials, then pre-sintering the raw materials, then sintering the raw materials for 20-25min at 1250-;
2) mixing and grinding the cement clinker prepared in the step 1) and the mixed material to obtain the cement clinker.
By adopting the technical scheme, the raw material after being ground is ground, pre-sintered firstly and then sintered, and limestone in the raw material is pre-decomposed firstly during pre-sintering, so that the time of high-temperature sintering at the later stage is shortened, and the energy is saved.
In conclusion, the invention has the following beneficial effects:
firstly, when the cement clinker in the high-strength cement is prepared, the volcanic ash is added, so that the components in the volcanic ash are more easily reacted with other raw materials in the high-temperature sintering process, and the volcanic ash can form an excitation effect on the other raw materials, so that the reaction is more sufficient in the high-temperature sintering process, the compressive strength of the cement clinker is improved, in addition, the reaction efficiency is also improved, and the sintering time is shortened.
Secondly, the high-strength cement has good cement clinker adsorption performance and is convenient for preparing aerated concrete. In addition, the prepared concrete has low temperature expansion coefficient, excellent anti-shrinkage performance and difficult generation of cracks.
Thirdly, the raw materials of the cement clinker of the high-strength cement of the invention adopt the pyrite cinder, the copper slag, the fly ash and the like, thereby greatly improving the utilization degree of wastes and being green and environment-friendly.
Fourthly, the high-strength cement of the invention adds the volcanic ash in the raw materials and the mixed materials of the cement clinker, fully utilizes the existing active components of the volcanic ash and the active components generated by high temperature, and greatly improves the strength of the cement.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The raw materials for preparing the cement clinker of the high-strength cement also comprise 0.16-0.28 weight part of hydrated lime, and in the process of firing the cement clinker, the hydrated lime can promote silicon in the volcanic ash to participate in reaction more quickly, so that the reaction efficiency is improved.
The straw used in the plant waste treatment substance is wheat straw or rice straw. Before treatment, the straws and rice hulls are crushed and sieved, and the granularity is controlled to be 30-40 meshes.
The limestone adopted in the invention comprises the following components in percentage by weight: 49.54 percent of CaO and 3.76 percent of SiO2And 2.63% of MgO. The volcanic ash comprises the following components: 48.5-50.2% SiO25.05 to 9.36 percent of Al2O35.81-6.12% of Fe2O315.88 to 19.27 percent of CaO and 6.49 to 7.92 percent of MgO. Preferably, the volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The loss on ignition was 2.81%. The fineness of the volcanic ash is 5.1%. The specific surface area of the volcanic ash is preferably 366m2In terms of/kg. The volcanic ash density is preferably 2.61m3In terms of/kg. The water content was about 0.8%.
The pyrite cinder adopted by the invention comprises the following components in percentage by weight: 40-48% Fe2O328-35% of SiO26.3-9.7% of Al2O34.3 to 6.4 percent of CaO and 0.8 to 1.5 percent of MgO. The pyrite cinder also contains 1-2% of SO3. Preferably, the pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO.
The copper slag adopted in the invention comprises the following components in percentage by weight: 31-39% of SiO233-42% of FeO and 3-10% of Fe2O34-12% of Al2O36 to 19 percent of CaO and 0.8 to 7 percent of MgO. Preferably, the copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. Preferably, the copper slag further contains 0.35 to 2.4% of Cu.
The converter slag adopted in the invention comprises the following components in percentage by weight: 41.14 to 49.30 percent of CaO and 13.99 to 15.38 percent of SiO22.88-3.73% of Al2O38.32-12.57% Fe2O38.12-9.35% of MgO and 0.50-1.17% of P2O50.80-1.21% of f-CaO. Preferably, the converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
In the preparation method of the high-strength cement, the temperature of the plant waste treatment material is 50-60 ℃ when the straw or the rice hull is soaked by hydrochloric acid. After soaking, filtration is carried out, then washing is carried out twice by water, filtration is carried out again, and then drying is carried out again.
In the preparation method of the high-strength cement, the pre-sintering is performed for 30-50min at the temperature of 300-. Further preferably, the pre-sintering is followed by cooling, grinding and then sintering. The grinding time is 10-30 min.
In the preparation method of the high-strength cement, rapid cooling is carried out during cooling, then slow cooling is carried out, the cooling speed of the rapid cooling is 250-. The slow cooling speed is 30-50 ℃/min, and the slow cooling time is 10-15 min.
Example 1
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 75:25, wherein the cement clinker is prepared from the following raw materials by weight: 8.0kg of limestone, 2.5kg of volcanic ash, 0.25kg of pyrite cinder and 0.45kg of copper slag. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The preparation method of the high-strength cement of the embodiment comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed volcanic ash, sulfuric acid slag and copper slag, adding the mixture into a grinding machine, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) sintering the homogenized raw material obtained in the step 1) at 320 ℃ for 50min, then heating to 750 ℃ for 25min, then heating to 1300 ℃ for 25min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 260 ℃/min, and the quenching time is 3 min; the slow cooling speed is 50 ℃/min, and the slow cooling time is 10 min;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Example 2
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 72:28, wherein the cement clinker is prepared from the following raw materials by weight: 10.0kg of limestone, 2.8kg of volcanic ash, 0.35kg of pyrite cinder, 0.4kg of copper slag and 0.5kg of plant waste treatment substances. The plant waste treatment substance is obtained by soaking rice straws in waste acid for 3h, washing with water, and drying at 105 ℃ for 1 h. The waste acid is waste hydrochloric acid with HCl of which the mass fraction is 8 percent. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The preparation method of the high-strength cement of the embodiment comprises the following steps:
1) firstly, adding rice hulls into waste hydrochloric acid (the mass fraction of HCl is 8%), soaking for 3 hours, then filtering, washing with water, filtering, transferring filter residues into a drying furnace, and drying at the temperature of 105 ℃ for 1 hour to obtain a plant waste treatment substance;
2) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed volcanic ash, sulfuric acid slag, copper slag and plant waste treatment substances, adding the mixture into a grinding machine, grinding, screening to obtain raw materials, and homogenizing the raw materials;
3) sintering the homogenized raw material obtained in the step 2) at 360 ℃ for 30min, then heating to 720 ℃ for sintering for 30min, then heating to 1350 ℃ for sintering for 20min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 280 ℃/min, and the quenching time is 3 min; the slow cooling speed is 40 ℃/min, and the slow cooling time is 11 min;
4) mixing and grinding the cement clinker prepared in the step 3) and the mixed material to obtain the cement clinker.
Example 3
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 65:35, wherein the cement clinker is prepared from the following raw materials by weight: 8.5kg of limestone, 3.0kg of volcanic ash, 0.32kg of pyrite cinder, 0.41kg of copper slag and 0.55kg of plant waste treatment substances. The plant waste treatment substance is obtained by soaking rice hulls in waste acid for 5h, washing with water, and drying at 110 ℃ for 0.5 h. The waste acid is waste hydrochloric acid with HCl of which the mass fraction is 5 percent. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The preparation method of the high-strength cement of the embodiment comprises the following steps:
1) firstly, adding rice hulls into waste hydrochloric acid (the mass fraction of HCl is 5%), soaking for 5 hours, then filtering, washing with water, filtering, transferring filter residues into a drying furnace, and drying at the temperature of 110 ℃ for 0.5 hour to obtain a plant waste treatment substance;
2) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed volcanic ash, sulfuric acid slag, copper slag and plant waste treatment substances, adding the mixture into a grinding machine, grinding, screening to obtain raw materials, and homogenizing the raw materials;
3) sintering the homogenized raw material obtained in the step 2) at 300 ℃ for 50min, then heating to 800 ℃ for 20min, then heating to 1250 ℃ for 25min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 300 ℃/min, and the quenching time is 3 min; the slow cooling speed is 30 ℃/min, and the slow cooling time is 10 min;
4) mixing and grinding the cement clinker prepared in the step 3) and the mixed material to obtain the cement clinker.
Example 4
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 68:32, wherein the cement clinker is prepared from the following raw materials by weight: 8.8kg of limestone, 3.2kg of volcanic ash, 0.3kg of pyrite cinder, 0.41kg of copper slag and 0.6kg of plant waste treatment substances. The plant waste treatment substance is obtained by soaking rice hulls in waste acid for 4h, washing with water, and drying at 100 ℃ for 1 h. The waste acid is waste hydrochloric acid with the mass fraction of HCl being 6%. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The preparation method of the high-strength cement of the embodiment comprises the following steps:
1) firstly, adding rice hulls into waste hydrochloric acid (the mass fraction of HCl is 6%), soaking for 4 hours, then filtering, washing with water, filtering, transferring filter residues into a drying furnace, and drying for 1 hour at the temperature of 100 ℃ to obtain a plant waste treatment substance;
2) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed volcanic ash, sulfuric acid slag, copper slag and plant waste treatment substances, adding the mixture into a grinding machine, grinding, screening to obtain raw materials, and homogenizing the raw materials;
3) sintering the homogenized raw material obtained in the step 2) at 350 ℃ for 30min, then heating to 770 ℃ for 20min, then heating to 1300 ℃ for 20min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 260 ℃/min, and the quenching time is 3 min; the slow cooling speed is 40 ℃/min, and the slow cooling time is 12 min;
4) mixing and grinding the cement clinker prepared in the step 3) and the mixed material to obtain the cement clinker.
Example 5
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 68:32, wherein the cement clinker is prepared from the following raw materials by weight: 9.2kg of limestone, 3.5kg of volcanic ash, 0.32kg of pyrite cinder, 0.42kg of copper slag and 0.75kg of plant waste treatment substance. The plant waste treatment substance is obtained by soaking rice hulls in waste acid for 4h, washing with water, and drying at 100 ℃ for 1 h. The waste acid is waste hydrochloric acid with the mass fraction of HCl being 6%. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The method for preparing the high strength cement of this example is the same as that of example 4.
Example 6
The high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 68:32, wherein the cement clinker is prepared from the following raw materials by weight: 8.8kg of limestone, 3.2kg of volcanic ash, 0.3kg of pyrite cinder, 0.4kg of copper slag, 0.8kg of plant waste treatment substance and 0.22kg of hydrated lime. The plant waste treatment substance is obtained by soaking rice hulls in waste acid for 4h, washing with water, and drying at 100 ℃ for 1 h. The waste acid is waste hydrochloric acid with the mass fraction of HCl being 6%. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The volcanic ash comprises the following components: 49.25% SiO25.62% of Al2O36.17% of Fe2O317.56 percent of CaO and 7.17 percent of MgO. The pyrite cinder comprises the following components in percentage by weight: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The copper slag comprises the following components in percentage by weight: 33.70% SiO235.16% FeO, 7.23% Fe2O35.25% of Al2O310.99% of CaO and 5.33% of MgO. The converter slag comprises the following components in percentage by weight: 48.32% CaO, 14.28% SiO22.88% of Al2O38.99% of Fe2O38.79% of MgO and 0.56% of P2O50.87 percent of f-CaO.
The preparation method of the high-strength cement of the embodiment comprises the following steps:
1) firstly, adding rice hulls into waste hydrochloric acid (the mass fraction of HCl is 6%), soaking for 4 hours, then filtering, washing with water, filtering, transferring filter residues into a drying furnace, and drying for 1 hour at the temperature of 100 ℃ to obtain a plant waste treatment substance;
2) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed volcanic ash, sulfuric acid slag, copper slag, plant waste treatment substances and hydrated lime, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
3) sintering the homogenized raw material obtained in the step 2) at 350 ℃ for 30min, then heating to 770 ℃ for sintering for 20min, then cooling, grinding for 10min, then heating to 1300 ℃ for sintering for 20min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 260 ℃/min, and the quenching time is 3 min; the slow cooling speed is 40 ℃/min, and the slow cooling time is 12 min;
4) mixing and grinding the cement clinker prepared in the step 3) and the mixed material to obtain the cement clinker.
Comparative example
The cement of the comparative example is prepared by mixing cement clinker and mixed materials according to the weight ratio of 75:25, wherein the cement clinker is prepared from the following raw materials by weight: 8.0kg of limestone, 2.10kg of pyrite cinder and 0.45kg of copper slag. The mixed material is formed by mixing volcanic ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 25.2:12.5: 5.8.
The preparation process of the cement of the comparative example comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight, mixing the limestone with weighed sulfuric acid slag and copper slag, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) sintering the homogenized raw material obtained in the step 1) at 320 ℃ for 50min, then heating to 750 ℃ for 25min, then heating to 1300 ℃ for 25min, discharging and cooling to obtain cement clinker; when the steel is taken out of the furnace and cooled, quenching is firstly carried out, then slow cooling is carried out, the cooling speed of the quenching is 260 ℃/min, and the quenching time is 3 min; the slow cooling speed is 50 ℃/min, and the slow cooling time is 10 min;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Test examples
(1) The cements prepared in examples 1 to 6 and comparative example were used, according to the cement: fly ash: water: the concrete mixture is prepared with sand in a weight ratio of 310:53:190:750, poured and sprayed with water for curing, test pieces are prepared, and the impermeability of the concrete is tested according to the method in GB/T50082-2009 Standard test methods for Long-term Performance and durability of ordinary concrete, with the results shown in the following table.
(2) The cements prepared in examples 1 to 6 and comparative examples were tested for compressive strength according to the method of GB/T17671-1999 Cement mortar Strength test, the results of which are shown in the following Table.
(3) The initial setting time of the cement produced in examples 1 to 6 and comparative example was measured according to the test method of JC/T453-2004 "physical test method for self-stressed cement", and the results are shown in the following table.
TABLE 1 Cement Performance test results in examples 1-6 and comparative examples
Figure BDA0002363439220000091
As can be seen from the above table, the high-strength cement of the invention has high compressive strength, and the 28d compressive strength can reach 45.7-55.9MPa, which is obviously higher than that of the common pozzolan cement. The high-strength cement also greatly improves the impermeability of the cement, and the impermeability grades are not smaller than S12 grade.

Claims (10)

1. The high-strength cement comprises cement clinker and a mixed material, and is characterized in that the cement clinker is mainly prepared from the following raw materials in parts by weight: 8-10 parts of limestone, 2.5-3.5 parts of volcanic ash, 0.25-0.35 part of pyrite cinder and 0.4-0.45 part of copper slag.
2. The high strength cement of claim 1, wherein: the cement clinker is mainly prepared from the following raw materials in parts by weight: 8.5-10 parts of limestone, 2.8-3.5 parts of volcanic ash, 0.3-0.35 part of pyrite cinder and 0.4-0.42 part of copper slag.
3. The high strength cement of claim 1, wherein: the volcanic ash comprises the following components: 48.5-50.2% SiO25.05 to 9.36 percent of Al2O35.81-6.12% of Fe2O315.88 to 19.27 percent of CaO and 6.49 to 7.92 percent of MgO.
4. The high strength cement of claim 3, wherein: the specific surface area of the volcanic ash is 360-375m2/kg。
5. The high strength cement of claim 1, wherein: the raw materials also comprise 0.5-0.8 part by weight of plant waste treatment substances, and the plant waste treatment substances are obtained by soaking straws or rice husks in hydrochloric acid and then drying.
6. The high strength cement of claim 5, wherein: the mass fraction of the hydrochloric acid adopted during the hydrochloric acid soaking is 5-8%.
7. The high strength cement of claim 6, wherein: the hydrochloric acid is soaked for 3-5 h.
8. The high strength cement of claim 5, wherein: the drying is carried out at the temperature of 100 ℃ and 110 ℃ for 0.5-1 h.
9. The high strength cement of claim 1, wherein: the weight ratio of the cement clinker to the mixed material is 65-75:25-35, and the mixed material is formed by mixing volcanic ash, desulfurized gypsum and converter slag.
10. A method of preparing the high strength cement of claim 1, wherein: the method comprises the following steps:
1) mixing and grinding the raw materials of the cement clinker to prepare raw materials, then pre-sintering the raw materials, then sintering the raw materials for 20-25min at 1250-;
2) mixing and grinding the cement clinker prepared in the step 1) and the mixed material to obtain the cement clinker.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992662A (en) * 2012-12-13 2013-03-27 安徽珍珠水泥集团股份有限公司 Process for producing cement by using limestone powder and crushed straws
CN103086622A (en) * 2012-12-13 2013-05-08 四川利森建材集团有限公司 Process for producing cement clinkers by straws instead of partial fuel coals
CN105585262A (en) * 2014-10-20 2016-05-18 边宏光 High-strength cement clinker and preparation method thereof
CN106316172A (en) * 2016-08-25 2017-01-11 中国建筑材料科学研究总院 Superfine high-strength high-belite cement and preparation method thereof
CA3065488A1 (en) * 2017-05-29 2018-12-06 Ravi Kant AHALAWAT Method for manufacturing cement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992662A (en) * 2012-12-13 2013-03-27 安徽珍珠水泥集团股份有限公司 Process for producing cement by using limestone powder and crushed straws
CN103086622A (en) * 2012-12-13 2013-05-08 四川利森建材集团有限公司 Process for producing cement clinkers by straws instead of partial fuel coals
CN105585262A (en) * 2014-10-20 2016-05-18 边宏光 High-strength cement clinker and preparation method thereof
CN106316172A (en) * 2016-08-25 2017-01-11 中国建筑材料科学研究总院 Superfine high-strength high-belite cement and preparation method thereof
CA3065488A1 (en) * 2017-05-29 2018-12-06 Ravi Kant AHALAWAT Method for manufacturing cement

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