CN111187013A - Environment-friendly high-strength cement and preparation method thereof - Google Patents
Environment-friendly high-strength cement and preparation method thereof Download PDFInfo
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- CN111187013A CN111187013A CN202010028716.8A CN202010028716A CN111187013A CN 111187013 A CN111187013 A CN 111187013A CN 202010028716 A CN202010028716 A CN 202010028716A CN 111187013 A CN111187013 A CN 111187013A
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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
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
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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
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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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- 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
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Abstract
The invention discloses environment-friendly high-strength cement and a preparation method thereof, belonging to the technical field of cement manufacture. The environment-friendly 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: 350 parts of limestone 330-. The preparation method of the environment-friendly high-strength cement comprises the following steps: mixing and grinding the raw materials of the cement clinker to prepare raw materials, preheating and decomposing the raw materials, then sintering the raw materials for 20 to 25min at 1250-; and mixing and grinding the cement clinker and the mixed material to obtain the cement clinker. The environment-friendly high-strength cement has reasonable raw material proportion in the cement clinker, can fully play the role of each component in the cement clinker, and greatly improves the strength of the cement.
Description
Technical Field
The invention relates to the technical field of cement manufacturing, in particular to environment-friendly high-strength cement and a preparation method thereof.
Background
With the acceleration of urban construction, the use amount of cement is larger and larger, and according to statistical data, the annual output of cement in China in 2018 is 21.8 billion tons, and the output of premixed concrete is 17.96 billion cubic meters. Many raw materials adopted in cement production are natural non-renewable resources, the resources are gradually reduced along with the increase of the using amount, and the search for new alternative resources is trending. With the increasing requirements of the country on reduction, recycling and harmless treatment of industrial solid wastes, the cement industry has become a new development trend of the industry by utilizing the inherent product advantages and increasing the consumption of industrial solid wastes.
The Chinese patent with application publication number CN110482885A discloses a raw material formula of portland cement, which comprises the following components in parts by weight: 70-73 parts of limestone, 10-12 parts of sandstone, 9-10 parts of carbide slag, 2-3 parts of iron raw material, 2-3 parts of filter residue and 2-3 parts of shale. The raw material of the portland cement adopts industrial waste residue such as carbide slag, and the waste is recycled. However, the cement raw material has a large carbide slag content and a calcium hydroxide content of more than 80% in the carbide slag, so that the proportions of the components in the raw material are inconsistent, and the finally prepared cement has low strength.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide environment-friendly high-strength cement, which recycles industrial waste residues and improves the strength of the cement.
The second purpose of the invention is to provide a preparation method of environment-friendly high-strength cement, which has simple preparation process and high production efficiency.
In order to achieve the first object, the invention provides the following technical scheme:
the environment-friendly 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: 350 parts of limestone 330-.
By adopting the technical scheme, the cement clinker is added with the pyrite cinder, the sandstone and the fly ash, the raw materials are reasonably matched in proportion, the effects of the components in the raw materials can be fully exerted, the strength of the finally prepared cement is improved, the industrial waste residues such as pyrite cinder, copper slag and the like are fully utilized, and the cement clinker meets the requirements of environmental protectionAnd (4) requiring. 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, the energy consumption for melting the raw materials is saved, and the sintering cost is reduced. Other components such as sulfur, fluorine and the like contained in the sulfate slag can also play a role of mineralization during sintering, promote dicalcium silicate to quickly and fully absorb calcium oxide in a liquid phase, and further improve the reaction efficiency. Due to the increase of the amount of the liquid phase, the raw material for generating the liquid phase can be more fully contacted with the sandstone. The invention adopts more sandstone, and on one hand, more free SiO can be provided2The silicon is contacted with a liquid phase, so that the reaction efficiency of silicon is improved; on the other hand, when limestone ore is mined in a cement plant, more sandstone can be left in the mine and cannot be treated, and more sandstone is added as a raw material, so that waste materials can be fully utilized, and sustainable production is facilitated.
The invention is further configured to: 345 parts of limestone 337-si-doped slag, 10.5-12.5 parts of pyrite cinder, 55.3-57.8 parts of sandstone, 13.6-15.8 parts of fly ash and 3.5-7.2 parts 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 uniform distribution of the components and uniform and stable performance is obtained, and meanwhile, the raw material cost is integrally reduced.
The invention is further configured to: the sandstone consists of coarse sandstone and fine sandstone according to the weight ratio of 16.8-17.5:37.8-40.6, wherein the median particle size of the coarse sandstone is 25 mu m, and the median particle size of the fine sandstone is 8 mu m.
By adopting the technical scheme, the invention adopts two kinds of sandstone with different specifications, and in addition to the coarse-grain sandstone with the conventional grain diameter, the fine-grain sandstone with the finer grain diameter is also added. Because the hardness of the sandstone is higher, the sandstone with the common granularity is not easy to be completely refined in the grinding process, so that the sandstone is prevented from being fully contacted with other raw materials in the later mixed sintering process, and after the fine-grained sandstone is added, the sandstone and the other raw materials are matched for use, so that the full mixing contact of the sandstone and the other raw materials can be promoted, and the reaction efficiency is improved.
The invention is further configured to: the thickness is greaterThe granulated sandstone comprises the following components in percentage by weight: 81.22-89.05% SiO20.3-1.2% of Al2O30.67-2.5% Fe2O30.05 to 0.82 percent of CaO, 0.51 to 1.6 percent of MgO; the fine-grained sandstone comprises the following components in percentage by weight: 65.31-68.16% SiO29.85-11.23% of Al2O33.22-4.36% of Fe2O35.38 to 6.27 percent of CaO and 1.55 to 1.70 percent of MgO.
By adopting the technical scheme, the coarse-grain sandstone and the fine-grain sandstone have different component contents, and the coarse-grain sandstone contains more silicon and less other components and can provide more free silicon dioxide for the sintering process. The fine sandstone contains more aluminum and iron besides silicon dioxide, has better fast-melting property, can shorten the sintering time and reduce the energy consumption.
The invention is further configured to: the raw material also comprises 5.8 to 9.5 weight parts of phosphorous slag.
By adopting the technical scheme, the added phosphorus slag contains more calcium oxide, and a certain amount of calcium can be provided for reaction before limestone is decomposed in the sintering process, so that the raw materials can be fully reacted at high temperature.
The invention is further configured to: the composite material also comprises 1.5-2.2 parts by weight of an activating agent, wherein the activating agent comprises one or more of lead-zinc tailings and vanadium tailings.
By adopting the technical scheme, the lead-zinc tailings contain Pb, Zn and other elements, so that the exciting and activating effects are achieved on the sintering process, the sintering reaction is promoted, and the reaction efficiency is improved. The elements such as V and the like in the vanadium tailings can also play a role in activating in the sintering process, and the two activators can provide a certain amount of iron, so that the generation of a tetracalcium aluminoferrite mineral phase is facilitated. In addition, lead-zinc tailings and vanadium tailings are used as activating agents, so that effective treatment and reutilization of mining waste residues are facilitated.
The invention is further configured to: and the mineralizer comprises 2.8-3.6 parts by weight of one or more of calcium chloride, calcium formate and barium slag.
By adopting the technical scheme, a small amount of mineralizer is added, wherein the binding force between calcium chloride and calcium formate and other raw materials is strong, so that the raw material dispersing uniformity is improved, and the melting temperature is reduced. The barium slag also has good cohesive action, and the alkaline substances in the barium slag play a certain role in activating the silicon phase and the aluminum phase in the sintering process, so that the reaction efficiency is further improved. .
The invention is further configured to: the copper slag 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.
By adopting the technical scheme, 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 lowest eutectic temperature of the sintered material can be reduced. The copper slag contains more vitreous bodies and trace elements, so that a liquid phase can appear in advance, the liquid phase amount is increased, and the reaction efficiency is further improved.
The invention is further configured to: the weight ratio of the cement clinker to the mixed material is 68-85:15-32, and the mixed material comprises limestone, fly ash, gypsum and converter slag.
By adopting the technical scheme, the mixed material comprises the converter slag besides limestone, fly ash and gypsum, wherein the converter slag is waste slag discharged during pig iron smelting, contains rich Ca, most importantly contains tricalcium silicate and dicalcium silicate, and can improve the hydration efficiency of cement after being mixed with cement clinker.
In order to achieve the second object, the invention provides the following technical scheme:
the preparation method of the environment-friendly high-strength cement comprises the following steps:
1) mixing and grinding the raw materials of the cement clinker to prepare raw materials, preheating and decomposing the raw materials, then sintering the raw materials for 20 to 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, after the raw materials are preheated and decomposed, the subsequent sintering time can be shortened to a certain extent, and the energy consumption is reduced.
In conclusion, the invention has the following beneficial effects:
firstly, the cement clinker of the environment-friendly high-strength cement has different components, the content proportion of the raw materials is reasonable, the functions of the components in the cement clinker can be fully exerted, and the strength of the cement is finally improved.
Secondly, the cement clinker raw materials of the environment-friendly high-strength cement adopt the sulfate slag, the copper slag, the fly ash and the like, so that the utilization degree of wastes is greatly improved, and the environment-friendly high-strength cement is environment-friendly. In addition, the components are mutually cooperated, so that the reaction efficiency during sintering is improved, and the energy is saved.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
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 coarse sandstone adopted by the invention comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 percent of MgO. The loss on ignition of the coarse sandstone was 4.05%. The loss on ignition of the fine sandstone was 5.5%. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2.
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 phosphorous slag adopted in the invention comprises the following components in percentage by weight: 41.66-43.57% SiO243.81-46.33% of CaO, 2.07-4.53% of Al2O30.81-2.62% of Fe2O31.22-2.67% of P2O5. Further preferably, the phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5. The phosphorous slag also contains 2.56-2.92% of F.
The lead-zinc tailings adopted by the invention comprise the following components in percentage by weight: 47.78% SiO210.86% of Al2O311.8% of Fe2O315.11 percent of CaO and 3.75 percent of MgO. The vanadium tailings comprise the following components in percentage by weight: 63.78% SiO210.13% of Al2O34.89% of Fe2O34.12 percent of CaO, 1.55 percent of SO31.86% of MgO and 0.45% of V2O50.32% of TiO2。
The barium slag adopted in the invention comprises the following components in percentage by weight: BaO 41.36%, SO312.52％、SiO216.78％、Al2O33.66％、CaO 5.58％、MgO 2.12％、Fe2O31.05 percent. The loss on ignition was 9.86%.
The converter slag adopted by 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.
The fly ash adopted in the invention is grade II fly ash.
In the preparation method of the environment-friendly cement, when the raw material is prepared, the limestone is homogenized and then mixed with other raw materials. Specifically, firstly, the limestone is homogenized, then the sulfuric acid slag, coarse sandstone, fine sandstone, fly ash, copper slag and phosphorus slag are added and mixed uniformly, then the lead-zinc tailings, the vanadium tailings, the calcium chloride and the barium slag are added and mixed uniformly, and then the mixture is added into a pulverizer to be pulverized. When preheating and decomposing are carried out, the decomposition temperature is 800-900 ℃. The temperature is the furnace top temperature of the decomposing furnace. Preheating is to send the cooling heat exchange gas of the grate cooler into a kiln tail preheater to preheat the raw material.
Example 1
The environment-friendly high-strength cement is prepared by mixing cement clinker and a mixed material according to a weight ratio of 85:15, wherein the cement clinker is prepared from the following raw materials in parts by weight: 350.0t of limestone, 11.8t of pyrite cinder, 17.0t of coarse sandstone, 40.6t of fine sandstone, 12.5t of fly ash and 5.5t of copper slag. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein, 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 coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 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 environment-friendly high-strength cement comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight by a belt weigher, mixing the limestone with sulfuric acid residue, coarse sandstone, fine sandstone, fly ash and copper slag weighed by the belt weigher, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) adding the homogenized raw material obtained in the step 1) into a kiln tail preheater for preheating, then feeding the raw material into a decomposing furnace, wherein the top temperature of the decomposing furnace is 865 ℃, then feeding the raw material into a rotary kiln, calcining the raw material for 20min at 1350 ℃, rapidly cooling the raw material by a grate cooler, and discharging the raw material to obtain cement clinker; sending the cooled heat exchange gas of the grate cooler to a kiln tail preheater to preheat the raw material;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Example 2
The environment-friendly high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 78:22, wherein the cement clinker is prepared from the following raw materials by weight: 345.0t of limestone, 10.5t of pyrite cinder, 16.8t of coarse sandstone, 38.5t of fine sandstone and fly ash15.8t, 3.5t of copper slag and 5.8t of phosphorous slag. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein, 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 coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 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 phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5. 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 environment-friendly high-strength cement comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight by a belt weigher, mixing the limestone with sulfuric acid residue, coarse sandstone, fine sandstone, fly ash, copper slag and phosphorus slag weighed by the belt weigher, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) adding the homogenized raw material obtained in the step 1) into a kiln tail preheater for preheating, then feeding the raw material into a decomposing furnace, wherein the top temperature of the decomposing furnace is 850 ℃, then feeding the raw material into a rotary kiln, calcining the raw material for 20min at 1300 ℃, quenching the raw material by a grate cooler, and discharging the raw material to obtain cement clinker; sending the cooled heat exchange gas of the grate cooler to a kiln tail preheater to preheat the raw material;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Example 3
The environment-friendly 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: 336.0t of limestone, 12.5t of sulfuric acid residue, 17.5t of coarse-grained sandstone, 37.8t of fine-grained sandstone, 13.6t of fly ash, 4.5t of copper slag, 6.2t of phosphorous slag, 1.2t of lead-zinc tailings, 0.3t of vanadium tailings, 1.4t of calcium chloride and 1.4t of barium residue. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein, 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 coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 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 phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5。
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 environment-friendly high-strength cement comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight by a belt weigher, uniformly mixing the limestone with sulfuric acid residue, coarse sandstone, fine sandstone, fly ash, copper slag and phosphorus slag which are weighed by the belt weigher, adding lead-zinc tailings, vanadium tailings, calcium chloride and barium slag, mixing, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) adding the homogenized raw material obtained in the step 1) into a kiln tail preheater for preheating, then feeding the raw material into a decomposing furnace, wherein the top temperature of the decomposing furnace is 835 ℃, then feeding the raw material into a rotary kiln, calcining the raw material for 25min at 1250 ℃, quenching the raw material by a grate cooler, and discharging the raw material to obtain cement clinker; sending the cooled heat exchange gas of the grate cooler to a kiln tail preheater to preheat the raw material;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Example 4
The environment-friendly high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 78:22, wherein the cement clinker is prepared from the following raw materials by weight: 332.0t of limestone, 11.2t of sulfuric acid residue, 17.1t of coarse-grained sandstone, 39.2t of fine-grained sandstone, 14.5t of fly ash, 7.2t of copper slag, 9.2t of phosphorous slag, 1.7t of lead-zinc tailings, 0.5t of vanadium tailings, 1.4t of calcium chloride, 0.6t of calcium formate and 2.2t of barium slag. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein, 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 coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO, 1.60 percent of MAnd gO. 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 phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5. 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 environment-friendly high-strength cement comprises the following steps:
1) pre-homogenizing limestone, weighing the limestone with required weight by a belt weigher, uniformly mixing the limestone with sulfuric acid residue, coarse sandstone, fine sandstone, fly ash, copper slag and phosphorus slag which are weighed by the belt weigher, adding lead-zinc tailings, vanadium tailings, calcium chloride, calcium formate and barium slag, mixing, adding the mixture into a pulverizer, grinding, screening to obtain raw materials, and homogenizing the raw materials;
2) adding the homogenized raw material obtained in the step 1) into a kiln tail preheater for preheating, then feeding the raw material into a decomposing furnace, wherein the top temperature of the decomposing furnace is 820 ℃, then feeding the raw material into a rotary kiln, calcining the raw material for 25min at 1250 ℃, quenching the raw material by a grate cooler, and discharging the raw material to obtain cement clinker; sending the cooled heat exchange gas of the grate cooler to a kiln tail preheater to preheat the raw material;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Example 5
The environment-friendly high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 78:22, wherein the cement clinker is prepared from the following raw materials by weight: 337.0t of limestone, 11.7t of sulfuric acid residue, 17.2t of coarse-grained sandstone, 40.6t of fine-grained sandstone, 13.6t of fly ash, 5.8t of copper slag, 8.1t of phosphorous slag, 1.5t of lead-zinc tailings, 0.3t of vanadium tailings, 1.2t of calcium chloride, 0.8t of calcium formate and 1.2t of barium slag. Mixing ofThe composite material is prepared by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein, 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 coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 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 phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5. 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 environment-friendly high-strength cement of the embodiment is the same as that of embodiment 4.
Example 6
The environment-friendly high-strength cement of the embodiment is prepared by mixing cement clinker and a mixed material according to the weight ratio of 78:22, wherein the cement clinker is prepared from the following raw materials by weight: 337.0t of limestone, 11.7t of sulfuric acid residue, 17.2t of coarse-grained sandstone, 40.6t of fine-grained sandstone, 13.6t of fly ash, 5.8t of copper slag, 7.5t of phosphorous slag, 1.2t of lead-zinc tailings, 0.5t of vanadium tailings, 1.2t of calcium chloride, 0.5t of calcium formate and 1.5t of barium slag. The mixed material is formed by mixing limestone powder, fly ash, desulfurized gypsum powder and converter slag powder according to the weight ratio of 10.8:17.5:11.5: 7.2. Wherein the pyrite cinder comprises the following componentsThe components by weight percentage are as follows: 42.62% Fe2O332.11% SiO28.87% of Al2O35.70 percent of CaO and 1.26 percent of MgO. The coarse sandstone comprises the following components in percentage by weight: 89.05% SiO20.38% of Al2O30.75% of Fe2O30.05% of CaO and 0.60% of MgO. The fine-grained sandstone comprises the following components in percentage by weight: 68.36% SiO210.15% of Al2O33.63% of Fe2O35.48 percent of CaO and 1.60 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 phosphorous slag comprises the following components in percentage by weight: 43.14% SiO245.25 percent of CaO, 3.42 percent of Al2O31.74% Fe2O31.88% of P2O5. 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 environment-friendly high-strength cement of the embodiment is the same as that of embodiment 4.
Comparative example
The cement of the comparative example is prepared by mixing cement clinker and mixed materials according to the weight ratio of 95:5, wherein the cement clinker is prepared from the following raw materials by weight: 350.0t of limestone, 58t of coarse sandstone, 15t of desulfurized gypsum and 10.5t of fly ash. The mixed material is formed by mixing limestone and desulfurized gypsum according to the weight ratio of 10: 15.
The preparation process of the cement of the comparative example comprises the following steps:
1) mixing and grinding the raw materials, screening to obtain raw materials, and homogenizing the raw materials;
2) preheating the homogenized raw material obtained in the step 1), then feeding the raw material into a decomposing furnace, wherein the top temperature of the decomposing furnace is 850 ℃, then calcining the raw material at 1450 ℃ for 30min, cooling and discharging the raw material to obtain cement clinker;
3) mixing and grinding the cement clinker prepared in the step 2) and the mixed material to obtain the cement clinker.
Test examples
The cements prepared in examples 1 to 6 and comparative example were tested for their compressive strength according to the method in GB/T17671-1999 Cement mortar Strength test, and for their initial setting time and final setting time according to the test method in JC/T453-2004 self-stress Cement physical test method, the test results are shown in the following Table.
TABLE 1 Cement Performance test results in examples 1-6 and comparative examples
As shown in the table, the cement has high compressive strength which can reach 33.3-43.7MPa after 3d and 51.5-69.4MPa after 28 d. The initial setting time of the cement is short and can reach 78-85 min. The cement of the invention adopts various waste slag, realizes waste utilization, is green and environment-friendly, and greatly reduces the manufacturing cost of the cement.
Claims (10)
1. The environment-friendly 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: 350 parts of limestone 330-.
2. The environment-friendly high strength cement according to claim 1, characterized in that: the cement clinker is mainly prepared from the following raw materials in parts by weight: 345 parts of limestone 337-si-doped slag, 10.5-12.5 parts of pyrite cinder, 55.3-57.8 parts of sandstone, 13.6-15.8 parts of fly ash and 3.5-7.2 parts of copper slag.
3. The environment-friendly high strength cement according to claim 1, characterized in that: the sandstone consists of coarse sandstone and fine sandstone according to the weight ratio of 16.8-17.5:37.8-40.6, wherein the median particle size of the coarse sandstone is 25 mu m, and the median particle size of the fine sandstone is 8 mu m.
4. The environment-friendly high strength cement according to claim 3, characterized in that: the coarse sandstone comprises the following components in percentage by weight: 81.22-89.05% SiO20.3-1.2% of Al2O30.67-2.5% Fe2O30.05 to 0.82 percent of CaO, 0.51 to 1.6 percent of MgO; the fine-grained sandstone comprises the following components in percentage by weight: 65.31-68.16% SiO29.85-11.23% of Al2O33.22-4.36% of Fe2O35.38 to 6.27 percent of CaO and 1.55 to 1.70 percent of MgO.
5. The environment-friendly high strength cement according to claim 1, characterized in that: the raw material also comprises 5.8 to 9.5 weight parts of phosphorous slag.
6. The environment-friendly high strength cement according to claim 1, characterized in that: the raw material also comprises 1.5-2.2 parts by weight of an activating agent, wherein the activating agent comprises one or two of lead-zinc tailings and vanadium tailings.
7. The environment-friendly high strength cement according to claim 1, characterized in that: and the mineralizer comprises 2.8-3.6 parts by weight of one or more of calcium chloride, calcium formate and barium slag.
8. The environment-friendly high-strength cement according to any one of claims 1 to 7, characterized in that: the copper slag 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.
9. The environment-friendly high strength cement according to claim 1, characterized in that: the weight ratio of the cement clinker to the mixed material is 68-85:15-32, and the mixed material comprises limestone, fly ash, desulfurized gypsum and converter slag.
10. The method for preparing environment-friendly high-strength cement according to claim 1, characterized in that: the method comprises the following steps:
1) mixing and grinding the raw materials of the cement clinker to prepare raw materials, preheating and decomposing the raw materials, then sintering the raw materials for 20 to 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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