CN113461348B - Method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid - Google Patents
Method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid Download PDFInfo
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- CN113461348B CN113461348B CN202110529300.9A CN202110529300A CN113461348B CN 113461348 B CN113461348 B CN 113461348B CN 202110529300 A CN202110529300 A CN 202110529300A CN 113461348 B CN113461348 B CN 113461348B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/47—Cooling ; Waste heat management
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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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- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid, which specifically comprises the following steps: (a) preparation of cement raw meal: weighing aluminum profile waste liquid, calcareous raw materials and correction materials, mixing and adjusting the water-solid ratio and the pH value, reacting while stirring, and drying precipitates obtained by the reaction to obtain cement raw materials; (b) preparation of cement clinker: calcining the cement raw material obtained in the step (a), and then quenching to obtain the sulphoaluminate cement clinker. Compared with the prior art, the method has the advantages that the aluminum profile waste liquid is used for replacing high-grade bauxite to be used as all aluminum raw materials to produce the sulphoaluminate cement, so that the resource utilization of the aluminum profile waste liquid is realized, the suction filtration and drying processes of the aluminum profile waste liquid for treating into waste residues are reduced, the pollution problem caused by stockpiling is solved, the exploitation of natural resources is reduced, and the production cost of the sulphoaluminate cement is reduced.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid.
Background
Compared with portland cement, the sulphoaluminate cement has the advantages of obvious energy saving and low carbon due to the characteristics of low calcination temperature and low limestone consumption, and is considered to be low-carbon ecological cement with wide development prospect. Meanwhile, the sulphoaluminate cement has the characteristics of early strength, high strength, low alkalinity, freeze thawing resistance, corrosion resistance and the like, and has a good application prospect in emergency repair engineering, winter construction engineering, glass fiber reinforced cement products and ocean engineering. Al is required for producing sulphoaluminate cement 2 O 3 The content is more than 55 percent and SiO 2 High grade bauxite with content less than 10%. In recent years, the price of high-grade bauxite has been kept high due to the development of the alumina industry, resulting in the continuous increase in the production cost of sulphoaluminate cement. Related researches are carried out to produce sulphoaluminate cement clinker by partially replacing high-grade bauxite with industrial waste residue of aluminum, but because the industrial waste residue has complex and unstable components, the clinker quality is difficult to control in actual production, and the industrial waste residue is hardly applied to the actual production at present.
The aluminum profile waste liquid is industrial waste liquid generated in the aluminum profile production process, and at present, about 600 million tons of aluminum profile waste liquid are generated in China every year. Is most commonly used at presentThe treatment method comprises the steps of treating the aluminum profile waste liquid into sludge by adopting a neutralization precipitation method, further performing suction filtration and drying to obtain aluminum profile waste residue, and storing the aluminum profile sludge or waste residue by adopting a damming wet method, so that precious land and farmland resources are occupied, and a large amount of funds are consumed to build and maintain a storage yard. Meanwhile, the stockpiling of leachate also causes serious environmental problems such as soil alkalization, swampiness, surface pollution, and underground water source pollution. Drying aluminum profile waste residue (105 ℃/24 h), and adding Al 2 O 3 The content is more than 50 percent, siO 2 Less than 2% of SO 3 The content is about 10 percent, and CaO and Na 2 The total content of O, F and the like is less than 5 percent and is close to that of high-grade bauxite; if calcined at high temperature (1200 ℃/2 h), al 2 O 3 The content is more than 90%. The aluminum profile waste residue has simple and stable chemical composition and less impurity content, and is more suitable to be used as an aluminum raw material of sulphoaluminate cement than other aluminum industrial waste residues. However, the waste aluminum profile liquid is colloidal and has a high water content, the water content is generally about 95%, the water content is still over 30% after the waste aluminum profile liquid is subjected to suction filtration and drying to form waste aluminum profile slag, the waste aluminum profile slag can be agglomerated and adhered to a sphere in the grinding process, the preparation of cement raw materials is not facilitated, and the waste aluminum profile liquid can be used as a raw material to prepare the cement raw materials after being dried again.
Disclosure of Invention
The invention aims to provide a method for preparing sulphoaluminate cement clinker by directly utilizing aluminum profile waste liquid, which realizes resource utilization of the aluminum profile waste liquid by utilizing the aluminum profile waste liquid to replace high-grade bauxite as a whole aluminum raw material to produce the sulphoaluminate cement, solves the pollution problem caused by stockpiling, reduces exploitation of natural resources, reduces the production cost of the sulphoaluminate cement, has safe and simple production process and low energy consumption, reduces the suction filtration and drying process of treating the aluminum profile waste liquid into waste residue, effectively solidifies harmful elements in the aluminum profile waste liquid, does not need to adopt any pretreatment method, obviously reduces the production energy consumption, and does not discharge carbon dioxide in the calcining process.
The purpose of the invention is realized by the following technical scheme:
a method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid specifically comprises the following steps:
(a) Preparing cement raw materials: weighing aluminum profile waste liquid, calcareous raw materials and correction materials, mixing, adjusting the water-solid ratio and the pH value, reacting while stirring, and drying precipitates obtained by the reaction to obtain cement raw materials;
(b) Preparing cement clinker: calcining the cement raw material obtained in the step (a), and then quenching to obtain the sulphoaluminate cement clinker.
In the step (a), the main chemical components of the aluminum profile waste liquid comprise aluminum oxide, sulfur trioxide, calcium oxide, sodium oxide, silicon oxide, ferric oxide, phosphorus pentoxide, potassium oxide, chromium oxide, fluorine element and the like.
In the step (a), the calcareous raw material is selected from one or more of carbide slag, lithium slag or nickel slag.
In the step (a), the correcting material is selected from one or more of phosphogypsum or desulfurized gypsum.
In the step (a), aluminum profile waste liquid: calcium raw materials: the mass percentage ratio of the correction material is 90-95 percent, 4-10 percent and 0.3-2 percent. Preferably, the aluminum profile waste liquid: calcium raw material: the mass percentage ratio of the correction material is 90-95 percent, 4.5-4.7 percent and 0.3-0.5 percent.
In step (a), the water-solid ratio is adjusted to (9.
In the step (a), the pH value is adjusted to 12.0-12.5.
In the step (a), stirring is carried out while the reaction is carried out, and the rotating speed of the stirring is 600r/min.
In the step (a), the reaction temperature is room temperature, and the reaction time is 2-8 h.
In the step (a), the drying temperature is 100-105 ℃, and the drying time is 1-2 h.
In step (b), the cement raw meal is calcined in an electric furnace or rotary kiln.
In the step (b), the calcining temperature is 1100-1200 ℃, and the calcining time is 0.5-1.0 h. Preferably, the temperature of calcination is 1150 ℃ and the time of calcination is 1.0h.
In the step (b), the quenching speed is 40-55 ℃/min, the quenching is carried out to 60-120 ℃, and the quenching time is 20-30 min.
In step (b), the final sulphoaluminate cement clinker has the main phase components
And C 2 S。
The method takes the aluminum profile waste liquid as all aluminum raw materials, takes the carbide slag, the lithium slag, the nickel slag and the like as calcium raw materials, takes the phosphogypsum, the desulfurized gypsum and the like as correction materials, directly utilizes the aluminum profile waste liquid to synthesize and prepare the cement raw material, and reduces the suction filtration and drying process of the waste slag treated by the aluminum profile waste liquid; the aluminum profile waste liquid is adopted to completely replace bauxite, so that the resource utilization of the aluminum profile waste liquid is realized; the preparation of the cement raw material is carried out at normal temperature and normal pressure, hydrothermal or high-pressure reaction is not needed, the production process is safe and simple, and the energy consumption is low; harmful elements in the aluminum profile waste liquid are effectively solidified, and any pretreatment method is not needed; compared with the prior art, the calcination temperature is reduced by 150-200 ℃, the production energy consumption is obviously reduced, and no carbon dioxide is discharged in the calcination process.
Compared with the prior art, the invention has the following advantages:
1. the cement raw material is prepared by directly utilizing the aluminum profile waste liquid, so that the suction filtration and drying process of treating the aluminum profile waste liquid into waste residues is reduced; the aluminum profile waste liquid is adopted to replace high-grade bauxite to serve as all aluminum raw materials, the aluminum profile waste liquid can be recycled, the pollution problem caused by stockpiling is solved, natural resource exploitation is reduced, and the production cost of the aluminum sulfate cement is reduced.
2. The preparation of the cement raw material is carried out at normal temperature and normal pressure, hydrothermal or high-pressure reaction is not needed, the production process and the process are safe and simple, and the energy consumption is low; the sintering temperature of the cement clinker is reduced by 150-200 ℃ compared with the temperature of the prior art, and the sintering energy consumption is reduced.
3. The cement raw meal synthesized by the aluminum profile waste liquid has higher specific surface area, and the components of F, na and the like contained in the aluminum profile waste liquid have good mineralization effect, so the invention can reduce the content of the components
The formation temperature of the mineral phase, thereby reducing the production energy consumption and the production cost of the cement clinker.
4. Harmful elements such as F, cr and the like in the aluminum profile waste liquid can be solidified by ettringite in the raw material preparation process and enter in the calcining process
Mineral phase and has no influence on the performance of cement clinker. Compared with other aluminum profile waste liquid utilization modes, the method can effectively solidify harmful elements without adopting any pretreatment method.
5. If calcium raw materials with low silicon content such as carbide slag and the like are adopted, clinker with high calcium sulphoaluminate content can be obtained, and the method is suitable for preparing high-strength-grade quick-hardening sulphoaluminate cement.
6. The calcareous raw material does not adopt limestone, no carbon dioxide is discharged in the calcining process, the calcining temperature is low, and the energy-saving low-carbon cement clinker is obtained.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cement raw material obtained in example 1;
FIG. 2 is an X-ray diffraction pattern of cement clinker obtained in example 1;
FIG. 3 is an X-ray diffraction pattern of a cement raw material obtained in example 2;
FIG. 4 is an X-ray diffraction pattern of cement clinker obtained in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid specifically comprises the following steps:
(a) Preparing cement raw materials: weighing aluminum profile waste liquid, a calcareous raw material and a correcting material, mixing, adjusting the water-solid ratio to be (9: calcium raw materials: the mass percentage ratio of the correction material is 90-95 percent, 4-10 percent and 0.3-2 percent;
(b) Preparing cement clinker: calcining the cement raw material obtained in the step (a) at 1100-1200 ℃ for 0.5-1.0 h, and then quenching the calcined cement raw material to 60-120 ℃ at the speed of 40-55 ℃/min to obtain the sulphoaluminate cement clinker.
Example 1
The chemical composition of the raw materials used in this example is shown in table 1.
TABLE 1 Main chemical composition of raw materials (wt/%)
The raw material formulation of this example is shown in table 2.
TABLE 2 raw material proportions
A method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid comprises the following specific implementation steps:
(a) Preparing cement raw materials:
weighing the raw materials according to the proportion in the table 2, mixing the raw materials, adjusting the water-solid ratio to be 10 and the pH value to be 12.3, stirring at normal temperature (the stirring speed is 600 r/min) for reaction for 6 hours, filtering precipitates obtained by the reaction, and drying at 105 ℃ for 2 hours to obtain cement raw meal, wherein the main phase of the cement raw meal is ettringite, and a small amount of unreacted calcium hydroxide and gypsum can be seen from an X-ray diffraction pattern (detailed in figure 1).
(b) Preparing cement clinker:
calcining the cement raw material prepared in the step (a) in an electric furnace, calcining at 1150 ℃ for 1.0h, and rapidly cooling at 50 ℃/min toAt 60 ℃, the sulphoaluminate cement clinker is obtained, and as can be seen from an X-ray diffraction pattern (shown in figure 2), the cement clinker is mainly
By calculating the X-ray map
About 91% in C 2 The S content is about 3%. Can be used for preparing high-strength sulphoaluminate cement with the strength grade of more than 62.5.
Example 2
The chemical composition of the raw materials used in this example is shown in table 3.
TABLE 3 Main chemical composition of raw materials (wt/%)
The raw material formulation of this example is shown in table 4.
TABLE 4 raw material proportions
A method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid comprises the following specific implementation steps:
(a) Preparing cement raw materials:
weighing the raw materials according to the proportion in the table 4, mixing the raw materials, adjusting the water-solid ratio to be 10 and the pH value to be 12.3, stirring at normal temperature (the stirring speed is 600 r/min) for reaction for 6 hours, filtering precipitates obtained by the reaction, and drying at 105 ℃ for 2 hours to obtain cement raw materials, wherein the main phases of the cement raw materials are ettringite and calcium hydroxide according to an X-ray diffraction pattern (detailed in figure 3).
(b) Preparing cement clinker:
calcining the cement raw meal prepared in the step (a) in an electric furnace, rapidly cooling to 60 ℃ at the speed of 50 ℃/min after calcining for 1.0h at 1150 ℃,the sulphoaluminate cement clinker is obtained, and as can be seen from an X-ray diffraction spectrum (shown in figure 4), the cement clinker is mainly
And C 2 S, the X-ray atlas is calculated to obtain
About 55% in C 2 The S content is about 38%. Can be used for preparing low-strength sulphoaluminate-belite cement with the strength grade below 52.5.
The contents which are not explained and explained in detail in the present invention are common knowledge of cement technology.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. A method for preparing sulphoaluminate cement clinker by using aluminum profile waste liquid is characterized by comprising the following steps:
(a) Preparing cement raw materials: weighing aluminum profile waste liquid, calcareous raw materials and correction materials, mixing and adjusting the water-solid ratio and the pH value, reacting while stirring, and filtering and drying precipitates obtained by the reaction to obtain cement raw materials;
(b) Preparing cement clinker: calcining the cement raw material obtained in the step (a), and then quenching to obtain sulphoaluminate cement clinker;
in the step (a), the main chemical components of the aluminum profile waste liquid comprise aluminum oxide, sulfur trioxide, calcium oxide, sodium oxide, silicon oxide, ferric oxide, phosphorus pentoxide, potassium oxide, chromium oxide and fluorine elements;
in the step (a), the calcareous raw material is selected from one or more of carbide slag, lithium slag or nickel slag;
in the step (a), the correcting material is selected from one or more of phosphogypsum or desulfurization gypsum;
in the step (b), the calcining temperature is 1100-1200 ℃, and the calcining time is 0.5h-1.0 h;
in the step (b), the quenching speed is 40 ℃/min-55 ℃/min, the quenching is carried out to 60-120 ℃, and the quenching time is 20-30min.
2. The method for preparing sulphoaluminate cement clinker by using the aluminum profile waste liquid as claimed in claim 1, wherein in the step (a), the aluminum profile waste liquid: calcium raw materials: the mass percentage ratio of the correction material is 90-95 percent to 4-10 percent to 0.3-2 percent, and the sum of the mass percentages of the aluminum profile waste liquid, the calcareous raw material and the correction material is less than or equal to 100 percent.
3. The method for preparing the sulphoaluminate cement clinker by using the aluminum profile waste liquid as claimed in claim 1, wherein in the step (a), the water-solid ratio is adjusted to be (9).
4. The method for preparing the sulphoaluminate cement clinker by using the aluminum profile waste liquid as claimed in claim 1, wherein in the step (a), the pH value is adjusted to be 12.0 to 12.5.
5. The method for preparing the sulphoaluminate cement clinker by using the aluminum profile waste liquid as claimed in claim 1, wherein in the step (a), the reaction temperature is room temperature, and the reaction time is 2h to 8h.
6. The method for preparing the sulphoaluminate cement clinker by using the aluminum profile waste liquid as claimed in claim 1, wherein in the step (b), the cement raw materials are calcined in an electric furnace or a rotary kiln.
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| CN105669058B (en) * | 2014-11-18 | 2017-11-10 | 登封电厂集团有限公司 | A kind of method that sulphate aluminium cement is produced with aluminium section bar sludge |
| CN104860687B (en) * | 2015-04-15 | 2016-11-09 | 东莞理工学院 | Corundum slag-waste aluminum sludge castable refractory |
| CN211770967U (en) * | 2019-11-21 | 2020-10-27 | 北京中科领向环保研究院有限公司 | System for preparing refractory aggregate by using aluminum profile sludge wet method |
| CN211471243U (en) * | 2019-11-21 | 2020-09-11 | 北京中科领向环保研究院有限公司 | System for producing aluminate cement by using aluminum profile sludge |
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