CN108298838B - Portland cement clinker and preparation method and application thereof - Google Patents
Portland cement clinker and preparation method and application thereof Download PDFInfo
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- CN108298838B CN108298838B CN201711463890.XA CN201711463890A CN108298838B CN 108298838 B CN108298838 B CN 108298838B CN 201711463890 A CN201711463890 A CN 201711463890A CN 108298838 B CN108298838 B CN 108298838B
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- portland cement
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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
-
- 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
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali 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
- C04B7/36—Manufacture of hydraulic cements in general
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/40—Dehydrating; Forming, e.g. granulating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of building materials, and particularly relates to a portland cement clinker and a preparation method and application thereof. The portland cement clinker is prepared from the following raw material components in parts by mass: 60-70 parts of limestone; 10-15 parts of fly ash; 1-3 parts of phosphorous slag; 3-5 parts of copper slag; 5-10 parts of zirconium slag. The invention overcomes the defects of low grade and poor quality of industrial waste residue, changes waste into valuable, saves energy and reduces emission, solves the problems of environmental pollution and land occupation caused by stacking of waste on one hand, recycles waste on the other hand, reduces the production cost of cement, and the prepared portland cement has the characteristics of high compressive strength and high flexural strength and has good stability.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a portland cement clinker and a preparation method and application thereof.
Background
Cement is a material which has the greatest influence on the use amount of building materials, and almost all the people in the world can develop the cement at every step. With the deep adjustment of the structure of the cement industry, the specific gravity of a novel dry-process cement production line in the industry is increased, the cement production capacity is rapidly increased, and the competition of cement enterprises is increasingly violent. How to reduce the production cost, improve the market share and stably improve the economic benefit becomes the core problem of cement enterprises. The raw materials of the traditional cement clinker production mainly comprise calcareous raw materials, clayey raw materials, calibration materials, mineralizers and the like, and the cement clinker is matched with gypsum and mixed materials to be ground to prepare the cement. Most of cement raw materials are non-renewable resources, and mass production of cement inevitably leads to resource exhaustion.
The production of cement by using industrial waste slag not only accords with the concept of environmental protection and pollution reduction, but also has the positive social effects of changing waste into valuable and reducing the disposal and production cost of the industrial waste slag, at present, some cement enterprises successfully produce cement by using the industrial waste slag, however, the following defects are hardly seen in the prior art for producing cement by using the industrial waste slag: the cement has unstable quality and low strength, and cannot meet the use requirement of large-scale construction engineering.
The fly ash mainly comprises silicon-aluminum glass, microcrystalline mineral particles and unburned carbon residue particles, and the components of the fly ash are similar to those of clay, so that the fly ash can partially replace the clay ingredient to produce cement clinker. For the fly ash produced by a combustion furnace with poor coal quality or poor combustion effect, the loss on ignition is higher due to incomplete mechanical combustion, and at the moment, the residual combustible material can be used for generating heat to be used in raw material proportioning, the doping amount is about 3-5%, and the heat consumption of clinker can be reduced. However, most fly ash in China is low-calcium ash, the network structure of the vitreous body of the fly ash is complete, the structure of the fly ash is difficult to dissociate even in an alkaline environment formed by hydration of cement clinker, the hydration activity is low, and the utilization of the fly ash in cement and concrete is greatly limited. At present, the actual utilization rate of the fly ash in China is less than 40%, the fly ash is mostly utilized in an extensive manner, and the economic benefit is not high.
Disclosure of Invention
In order to overcome the disadvantages and drawbacks of the prior art, the primary object of the present invention is to provide a portland cement clinker.
Another object of the present invention is to provide a method for producing the above portland cement clinker.
It is a further object of the present invention to provide the use of the portland cement clinker described above.
The purpose of the invention is realized by the following technical scheme:
the portland cement clinker is prepared from the following raw material components in parts by mass:
the portland cement clinker is preferably prepared from the following raw material components in parts by mass:
the preparation method of the portland cement clinker comprises the following steps:
(1) mixing limestone, fly ash, phosphorus slag, copper slag and zirconium slag, and grinding to obtain a raw material;
(2) homogenizing the raw material prepared in the step (1);
(3) calcining the homogenized raw material in the step (2) at high temperature, and cooling to obtain portland cement clinker;
the fineness of the raw material in the step (1) is preferably that the residue of a square-hole sieve with 0.08mm is less than 5 percent;
the fly ash and zirconium slag in the step (1) are preferably treated as follows:
mixing fly ash and zirconium slag, crushing, ball-milling, then mixing with water, carrying out ultrasonic treatment, carrying out solid-liquid separation, washing and drying to obtain a modified fly ash/zirconium slag mixture;
the mass ratio of the total mass of the fly ash and the zirconium slag to the water is preferably 1: (3-5);
the ultrasonic treatment condition is preferably 100-150 w ultrasonic treatment for 30-60 min;
the calcination temperature in the step (3) is preferably 1250-1350 ℃;
the calcination time in the step (3) is preferably 30-60 min;
the fineness of the portland cement clinker in the step (3) is preferably below 2 percent of the residue of a square-hole sieve with the size of 0.08mm, and the specific surface area is preferably not less than 400m2/kg；
The application of the portland cement clinker in the technical field of building materials;
a portland cement comprising the above portland cement clinker;
the portland cement further comprises gypsum;
the portland cement also comprises an excitant and an industrial waste residue mixed material;
the gypsum is preferably at least one of dihydrate gypsum, salt pan gypsum, desulfurized gypsum, phosphogypsum, anhydrous gypsum and calcined gypsum;
the industrial waste residue mixed material is preferably at least one of steel slag, copper slag, fly ash and granulated blast furnace slag;
the preparation method of the portland cement comprises the following steps:
mixing the components of the portland cement, crushing and ball milling to obtain the portland cement;
the fineness of the portland cement is preferably below 2% of the screen residue of a square-hole sieve with the thickness of 0.08 mm;
the application of the silicate cement in the technical field of building materials;
the principle of the invention is as follows:
the fly ash mainly comprises silicon-aluminum glass, microcrystalline mineral particles and unburned carbon residue particles, and the chemical components of the fly ash mainly comprise silicon oxide and aluminum oxide. The components of the fly ash are similar to those of clay, and in the prior art, the fly ash can partially replace clay ingredients to produce cement clinker. The invention adopts fly ash and phosphorous slag to completely replace clay, and adds copper slag and zirconium slag, wherein the phosphorous slag mainly exists in a vitreous form (the vitreous content can generally reach 85% -90%), in addition, some potential mineral phases of wollastonite, kyanite and the like exist, and partial crystalline phases of quartz, pseudo-wollastonite, calcite, calcium fluoride and the like exist, and the main chemical components of the phosphorous slag are CaO and Al2O3、SiO2And P2O5The copper slag can be used as a mineralizer and P in the phosphorus slag besides providing an iron raw material2O5Synergistic effect, can stabilize C2S, the liquid phase appears in advance when the clinker is calcined, simultaneously the viscosity of the liquid phase is reduced, the ion diffusion resistance is reduced, the mass point diffusion speed is increased, and C is facilitated3And S growth and development. The zirconium slag contains a large amount of amorphous SiO2SiO of the type2Has higher activity, provides a huge number of growth attachment points for the crystallization and growth of cement hydration products, effectively promotes the hydration reaction, and can obviously improve the early strength of the hydration of the cement-based materials.
In addition, the zirconium slag has acidity, the pH value after water immersion is less than 1, the zirconium slag is mixed with the fly ash by utilizing the characteristic, then the water immersion is carried out with ultrasonic treatment, on one hand, the surface modification is carried out on the fly ash by utilizing the acidity, so that the internal fracture surface of the fly ash is increased, the pore channels are increased, the impurities blocking the pores are removed, the specific surface area is increased, the subsequent high-temperature calcination is further facilitated, meanwhile, the water immersion ultrasonic treatment is also facilitated for removing the chloride ions in the zirconium slag, and the problem of corrosion of the chloride ions caused by overhigh concentration of the chloride ions is avoided.
Compared with the prior art, the invention has the following advantages and effects:
(1) the scientific raw material proportion and process parameter control of the invention overcome the defects of low grade and poor quality of industrial waste residue, change waste into valuable, save energy and reduce emission, solve the problems of environmental pollution and land occupation caused by stacking of waste on one hand, recycle waste on the other hand, and reduce the production cost of cement.
(2) The invention effectively reduces the sintering temperature of the clinker and the sintering cost.
(3) Simple process, easy operation, easily obtained raw materials, low cost and easy popularization.
(4) The fly ash Portland cement has the characteristics of high compressive strength and flexural strength and good stability.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The portland cement clinker is prepared from the following raw material components in parts by mass:
the preparation method of the portland cement clinker comprises the following steps:
(1) mixing fly ash and zirconium slag, crushing, ball-milling, then mixing with water (the mass ratio of the total mass of the fly ash and the zirconium slag to the water is 1: 4.5), carrying out ultrasonic treatment for 50min at 130w, carrying out solid-liquid separation, washing, and drying to obtain a modified fly ash/zirconium slag mixture; then mixing limestone, the modified fly ash/zirconium slag mixture, phosphorus slag and copper slag, and grinding to obtain a raw material, wherein the fineness of the raw material is less than 5% of the residue of a square-hole sieve with the fineness of 0.08 mm;
(2) homogenizing the raw material prepared in the step (1);
(3) calcining the homogenized raw material in the step (2) at 1300 ℃ for 60min, cooling and grinding to obtain portland cement clinker; wherein the fineness of the portland cement clinker is 2 percent of the residue of a square-hole sieve with the fineness of 0.08mmThe specific surface area is more than 400m2/kg。
Example 2
The portland cement clinker is prepared from the following raw material components in parts by mass:
the preparation method of the portland cement clinker comprises the following steps:
(1) mixing fly ash and zirconium slag, crushing, ball-milling, then mixing with water (the mass ratio of the total mass of the fly ash and the zirconium slag to the water is 1: 3), carrying out 150w ultrasonic treatment for 30min, carrying out solid-liquid separation, washing, and drying to obtain a modified fly ash/zirconium slag mixture; then mixing limestone, the modified fly ash/zirconium slag mixture, phosphorus slag and copper slag, and grinding to obtain a raw material, wherein the fineness of the raw material is less than 5% of the residue of a square-hole sieve with the fineness of 0.08 mm;
(2) homogenizing the raw material prepared in the step (1);
(3) calcining the homogenized raw material in the step (2) at 1350 ℃ for 30min, cooling and grinding to obtain portland cement clinker; wherein the fineness of the portland cement clinker is less than 2 percent of the residue of a square-hole sieve with the fineness of 0.08mm, and the specific surface area is more than 400m2/kg。
Example 3
The portland cement clinker is prepared from the following raw material components in parts by mass:
the preparation method of the portland cement clinker comprises the following steps:
(1) mixing fly ash and zirconium slag, crushing, ball-milling, then mixing with water (the mass ratio of the total mass of the fly ash and the zirconium slag to the water is 1: 5), carrying out 100w ultrasonic treatment for 60min, carrying out solid-liquid separation, washing, and drying to obtain a modified fly ash/zirconium slag mixture; then mixing limestone, the modified fly ash/zirconium slag mixture, phosphorus slag and copper slag, and grinding to obtain a raw material, wherein the fineness of the raw material is less than 5% of the residue of a square-hole sieve with the fineness of 0.08 mm;
(2) homogenizing the raw material prepared in the step (1);
(3) calcining the homogenized raw material in the step (2) at 1250 ℃ for 60min, cooling and grinding to obtain portland cement clinker; wherein the fineness of the portland cement clinker is less than 2 percent of the residue of a square-hole sieve with the fineness of 0.08mm, and the specific surface area is more than 420m2/kg。
Comparative examples
The portland cement clinker is prepared from the following raw material components in parts by mass:
68 parts of limestone;
12 parts of fly ash;
4 parts of copper slag;
the preparation method of the portland cement clinker comprises the following steps:
(1) crushing and ball-milling the fly ash, mixing the pulverized fly ash with water (the mass ratio of the total mass of the fly ash to the water is 1: 4.5), carrying out ultrasonic treatment for 50min at 130w, carrying out solid-liquid separation, washing and drying to obtain modified fly ash; then mixing limestone, modified fly ash and copper slag, and grinding to obtain a raw material, wherein the fineness of the raw material is less than 5% of the residue of a square-hole sieve with the fineness of 0.08 mm;
(2) homogenizing the raw material prepared in the step (1);
(3) calcining the homogenized raw material in the step (2) at 1300 ℃ for 60min, cooling and grinding to obtain portland cement clinker; wherein the fineness of the portland cement clinker is less than 2 percent of the residue of a square-hole sieve with the fineness of 0.08mm, and the specific surface area is more than 400m2/kg。
Effects of the embodiment
(1) The cement clinker prepared in examples 1 to 3 and the cement clinker prepared in the comparative example are respectively mixed with dihydrate gypsum to obtain Portland cement, wherein the dosage of the dihydrate gypsum is 4% of the total mass of the cement, and then the compressive strength and the flexural strength of the cement are detected.
The results are shown in Table 1, and examples 1 to 3 have excellent compressive strength and flexural strength as compared with comparative examples.
TABLE 1 compression and flexural strengths of Portland cement
(2) The f-CaO content of the cement clinker was measured and the results are shown in Table 2.
TABLE 2F-CaO content in cement clinker
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The portland cement clinker is characterized by being prepared from the following raw material components in parts by mass:
2. the portland cement clinker according to claim 1, characterized by being prepared from the following raw material components in parts by mass:
3. a method for producing portland cement clinker according to claim 1 or 2, characterized by comprising the steps of:
(1) mixing limestone, fly ash, phosphorus slag, copper slag and zirconium slag, and grinding to obtain a raw material;
(2) homogenizing the raw material prepared in the step (1);
(3) and (3) calcining the homogenized raw material in the step (2) at high temperature, and cooling to obtain the portland cement clinker.
4. The method for producing portland cement clinker according to claim 3, wherein:
the fineness of the raw material in the step (1) is that the residue of a square-hole sieve with the fineness of 0.08mm is less than 5 percent.
5. The method for producing portland cement clinker according to claim 3, wherein:
the fly ash and zirconium slag in the step (1) are treated as follows:
mixing the fly ash and zirconium slag, crushing, ball-milling, then mixing with water, carrying out ultrasonic treatment, carrying out solid-liquid separation, washing and drying to obtain a modified fly ash/zirconium slag mixture.
6. The method for producing portland cement clinker according to claim 5, wherein:
the mass ratio of the total mass of the fly ash and the zirconium slag to the water is 1: (3-5);
the ultrasonic treatment condition is 100-150 w ultrasonic treatment for 30-60 min.
7. The method for producing portland cement clinker according to claim 3, wherein:
the calcining temperature in the step (3) is 1250-1350 ℃.
8. The method for producing portland cement clinker according to claim 3, wherein:
the fineness of the portland cement clinker in the step (3) is less than 2 percent of the screen residue of a square-hole screen with the fineness of 0.08mm, and the specific surface area is not less than 400m2/kg。
9. Use of the Portland cement clinker according to claim 1 or 2 in the technical field of building materials.
10. A portland cement characterized by comprising the portland cement clinker according to claim 1 or 2.
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| CN109704602A (en) * | 2019-02-22 | 2019-05-03 | 武汉理工大学 | Cementitious material and preparation method without entringite in a kind of hydrated product |
| CN110228956B (en) * | 2019-05-29 | 2022-02-22 | 山西卓越水泥有限公司 | Portland cement clinker with high compressive strength and preparation method thereof |
| CN113213785B (en) * | 2021-06-04 | 2023-03-17 | 嘉华特种水泥股份有限公司 | High-strength low-hydration heat cementing cement and preparation method thereof |
| CN114409283A (en) * | 2021-12-27 | 2022-04-29 | 滁州学院 | Alite-ylimide cement and preparation method thereof |
| CN115286267A (en) * | 2022-08-18 | 2022-11-04 | 河北鼎星水泥有限公司 | Low-alkali high-strength cement clinker and processing technology thereof |
| CN115448620B (en) * | 2022-10-28 | 2023-03-31 | 辽宁银盛水泥集团有限公司 | High-performance cement using waste residues and preparation method thereof |
| CN116573869B (en) * | 2023-05-26 | 2024-05-28 | 安徽建筑大学 | Method for producing cement clinker by using slag waste |
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| CN106587674A (en) * | 2016-12-13 | 2017-04-26 | 刘勇英 | Portland cement as well as preparation method and application thereof |
| CN106698982A (en) * | 2016-12-13 | 2017-05-24 | 刘勇英 | Cement clinker and preparation method and application thereof |
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| CN106587674A (en) * | 2016-12-13 | 2017-04-26 | 刘勇英 | Portland cement as well as preparation method and application thereof |
| CN106698982A (en) * | 2016-12-13 | 2017-05-24 | 刘勇英 | Cement clinker and preparation method and application thereof |
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