CN112174551A - Method for preparing cement clinker by using molybdenum tailings, cement clinker and application - Google Patents
Method for preparing cement clinker by using molybdenum tailings, cement clinker and application Download PDFInfo
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- CN112174551A CN112174551A CN202010948564.3A CN202010948564A CN112174551A CN 112174551 A CN112174551 A CN 112174551A CN 202010948564 A CN202010948564 A CN 202010948564A CN 112174551 A CN112174551 A CN 112174551A
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- cement clinker
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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
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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
- C04B7/36—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
- C04B7/475—Cooling ; Waste heat management using the waste heat, e.g. of the cooled clinker, in an other way than by simple heat exchange in the cement production line, e.g. for generating steam
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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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of cement manufacturing, in particular to a method for preparing cement clinker by using molybdenum tailings, the cement clinker and application. The method comprises the following steps: (1) weighing the raw materials according to the proportion, and then transferring the raw materials into a middle-discharge type drying and pulverizing mill for grinding to obtain a raw material with the screen residue percentage of 10-15 percent of a 80-micron square-hole sieve; (2) homogenizing the raw material obtained in the step (1), then transferring the raw material to a dry rotary kiln system for calcination, and then cooling to obtain the cement clinker. The molybdenum tailings contain higher SiO2And Al2O3Spontaneous combustion with aluminium slagUnder the combined action of the coal gangue and the like, not only can the comprehensive utilization of the molybdenum tailings be effectively realized, but also the production cost of the cement can be reduced, and the prepared cement has high compressive strength.
Description
Technical Field
The invention relates to the technical field of cement manufacturing, in particular to a method for preparing cement clinker by using molybdenum tailings, the cement clinker and application.
Background
Mineral resources are natural resources on which human society relies to survive. Currently 70% of the raw materials for industrial products and 90% of the energy in the world are derived from mineral resources. And 30% of industrial value in China comes from mining industry and processing industry using mineral resources as raw materials, and people engaged in relevant work of mining industry are nearly 2000 ten thousand. Since 2000, with the rapid advance of the modernization process of society, the demand of society for mineral resources is increasing day by day, and the contradiction of the whole mineral resource shortage is also highlighted day by day. The low utilization rate of mineral resources is one of the important reasons, and a large amount of solid wastes are generated in the processes of mining, ore dressing, smelting and the like. Tailings are one type of solid waste to be utilized. According to incomplete statistics, the discharge amount of tailings in China is up to more than 15 hundred million tons in recent 5 years, and the stockpiling amount of various tailings is up to 146 hundred million tons at the end of 2015. The tailings usually contain huge nonmetallic minerals, so that the development and utilization of the tailings in relatively developed countries in the world are more important at present, a large amount of exploration research and application are carried out, better results are obtained, the annual output and the total reserve of the tailings in China are in a trend of increasing continuously, and most of the tailings are treated by mining processing enterprises in a stockpiling mode. The large amount of stockpiling of the solid waste of the tailings not only occupies a large amount of land, but also causes resource waste because the useful components in the tailings cannot be fully utilized, and simultaneously faces the problems of tailings leakage, environmental pollution and the like, thereby forming a serious threat to the safety of people in mining areas. The approach for solving the problems is required to depend on realizing the comprehensive utilization of the tailings, and is the most effective and fundamental approach for solving the shortage of mineral resources and developing the circular economy. Therefore, the strengthening of the comprehensive treatment of the tailings is urgent.
The comprehensive utilization rate of tailings in China is low and is far lower than the utilization level of developed countries. However, the history of the research on molybdenum extraction from stone coal in China is not long, and the level of the comprehensive utilization of tailings after molybdenum extraction from stone coal is not high. Therefore, a new comprehensive utilization way of the molybdenum tailings can be developed by taking the comprehensive utilization ways of other tailings as reference and combining the characteristics of the molybdenum tailings extracted from stone coal, so that certain economic benefits are generated. The tailings mostly belong to tailings with high silicon content, and the main mineral composition of the tailings mainly comprises quartz, and simultaneously contains a small amount of minerals such as feldspar, gypsum, pyrite and the like. A great deal of research shows that the high-silicon tailings after being subjected to superfine grinding have the same Ca (OH)2Activity of alkaline compound reaction, wherein active SiO2And Al2O3And Ca (OH)2-CaSO4Can react to form calcium silicate, calcium aluminate or calcium sulphoaluminate, etc. Therefore, the tailings are used as siliceous materials to produce building materials, which is an effective way for improving the comprehensive utilization rate of the tailings.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a method for preparing cement clinker by using molybdenum tailings, the cement clinker and application.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing cement clinker using molybdenum tailings, the method comprising the steps of:
(1) weighing the raw materials according to the proportion, and then transferring the raw materials into a middle-discharge type drying and pulverizing mill for grinding to obtain a raw material with the screen residue percentage of 10-15 percent of a 80-micron square-hole sieve;
(2) homogenizing the raw material obtained in the step (1), then transferring the raw material to a dry rotary kiln system for calcining, and then cooling to obtain cement clinker;
wherein the raw material comprises 55-64 wt% of carbide slag, 20-30 wt% of molybdenum tailings, 3-6 wt% of aluminum slag, 4-7 wt% of spontaneous combustion coal gangue and 1.5-4.5 wt% of fly ash;
the calcination temperature is 1050-1250 ℃, and the calcination time is 10-40 min.
Preferably, in the step (1), the raw material contains 57-61 wt% of carbide slag, 24-29 wt% of molybdenum tailings, 4-5 wt% of aluminum slag, 5-6 wt% of spontaneous combustion coal gangue and 2-4 wt% of fly ash.
Preferably, in the step (1), the chemical components of the molybdenum tailings are as follows by mass percent: CaO: 10-12% of SiO2：51-53％，Fe2O3：10-14％，Al2O3: 10-12%, MgO: 1-3 percent of the total weight of the composition, and the balance of other chemical components.
Preferably, in step (1), the parameters of the center-discharge type drying and pulverizing machine are as follows: the grinding granularity is less than 25 mm; the grinding water content is less than 3 percent; grinding gas temperature: 300 ℃ and 330 ℃.
Preferably, in the step (1), the drying heat source of the middle discharge type drying and pulverizing mill is from kiln tail waste gas.
Preferably, in step (2), the homogenization is performed in a storage homogenizer silo.
Preferably, in step (2), preheating is further performed before the calcination, and the preheating temperature is 700-800 ℃.
Preferably, in step (2), the cooling is performed in a grate cooler.
The second aspect of the invention provides the cement clinker prepared by the method.
In a third aspect, the present invention provides the use of the above cement clinker for the preparation of cement or in the construction field.
According to the method, the molybdenum tailings contain high SiO content2And Al2O3The method has the advantages that the method can effectively realize the comprehensive utilization of the molybdenum tailings under the combined action of the aluminum slag, the spontaneous combustion coal gangue and the like, the production cost of the cement can be reduced, and the prepared cement has high compressive strength.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing cement clinker using molybdenum tailings, the method comprising the steps of:
(1) weighing the raw materials according to the proportion, and then transferring the raw materials into a middle-discharge type drying and pulverizing mill for grinding to obtain a raw material with the screen residue percentage of 10-15 percent of a 80-micron square-hole sieve;
(2) homogenizing the raw material obtained in the step (1), then transferring the raw material to a dry rotary kiln system for calcining, and then cooling to obtain cement clinker;
wherein the raw material comprises 55-64 wt% of carbide slag, 20-30 wt% of molybdenum tailings, 3-6 wt% of aluminum slag, 4-7 wt% of spontaneous combustion coal gangue and 1.5-4.5 wt% of fly ash;
the calcination temperature is 1050-1250 ℃, and the calcination time is 10-40 min.
Preferably, in step (1), the raw material contains 57-61 wt% of carbide slag, 24-29 wt% of molybdenum tailings, 4-5 wt% of aluminum slags, 5-6 wt% of spontaneous combustion coal gangue and 2-4 wt% of fly ash.
In the method, in the step (1), the chemical components of the molybdenum tailings are as follows by mass percent: CaO: 10-12% of SiO2：51-53％，Fe2O3：10-14％，Al2O3: 10-12%, MgO: 1-3 percent of the total weight of the composition, and the balance of other chemical components.
In the method of the invention, wollastonite is accompanied in the molybdenum tailings, and the main mineral of the cement clinker is 3CaO.SiO2And 2CaO. SiO2The constituent elements of the wollastonite are the same, the wollastonite absorbs CaO to form the cement clinker minerals, and the structure of the wollastonite is similar to that of the wollastonite. Because the wollastonite has higher activity, the activation energy of the C3S forming reaction can be reduced, the formation of C3S is accelerated, the heat consumption of cement clinker is reduced, and the yield and the quality are improved.
In the method, the pyrrhotite remaining in the aluminum slag and wollastonite accompanied with the molybdenum tailings have a fluxing action in the calcining process of the cement clinker, thereby being beneficial to the sintering of the clinker. The use of the spontaneous combustion coal gangue as the aluminum correction raw material can increase the alumina in the raw material, bring some active silica and alumina, and is beneficial to improving the easy-burning property of the raw material.
In the method of the invention, in the step (1), the parameters of the middle-discharge type drying and pulverizing mill are as follows: the grinding granularity is less than 25 mm; the grinding water content is less than 3 percent; grinding gas temperature: 300 ℃ and 330 ℃.
In the method of the invention, in the step (1), the drying heat source of the middle discharge type drying and pulverizing mill is from kiln tail waste gas.
In the method of the present invention, in the step (2), the homogenization is performed in a storage homogenizer silo.
In a specific embodiment, in the step (2), the calcination temperature may be 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃ or 1250 ℃, and the calcination time may be 10, 12min, 15min, 17min, 20min, 22min, 25min, 27min, 30min, 35min or 40 min.
In the method of the present invention, in step (2), preheating is further performed before the calcination, and the preheating temperature is 700-800 ℃. Specifically, the preheating temperature may be 700 deg.C, 705 deg.C, 710 deg.C, 715 deg.C, 720 deg.C, 730 deg.C, 745 deg.C, 755 deg.C, 760 deg.C, 765 deg.C, 770 deg.C, 775 deg.C, 780 deg.C, 785 deg.C, 790 deg.C, 795 deg.C or 800 deg.C.
In the method of the present invention, in the step (2), the cooling is performed in a grate cooler.
The second aspect of the invention provides the cement clinker prepared by the method.
In a third aspect, the present invention provides the use of the above cement clinker for the preparation of cement or in the construction field.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
Example 1
(1) Weighing raw materials according to a ratio, and then transferring the raw materials to a middle-discharge type drying and pulverizing mill (the grinding particle size is less than 25mm, the grinding water content is less than 3%, the grinding gas temperature is 300-330 ℃, and the drying heat source is from kiln tail waste gas) for pulverizing to obtain a raw material with the screen residue percentage of 14% of an 80-micron square-hole sieve, wherein the raw material contains 60 wt% of carbide slag, 26 wt% of molybdenum tailings, 5 wt% of aluminum slag, 5 wt% of spontaneous combustion coal gangue and 4 wt% of fly ash;
(2) homogenizing the raw materials obtained in the step (1) in a storage homogenizing warehouse, then transferring the raw materials to a dry rotary kiln system for preheating (the temperature is 750 ℃), then calcining (the temperature is 1200 ℃ for 15min), and then cooling in a grate cooler to obtain cement clinker A1;
the molybdenum tailings comprise the following chemical components in percentage by mass: CaO: 11.5% of SiO2：53％，Fe2O3：12％，Al2O3: 11%, MgO: 2 percent and the balance of other chemical components.
Example 2
(1) Weighing raw materials according to a ratio, and then transferring the raw materials to a middle-discharge type drying and pulverizing mill (the grinding particle size is less than 25mm, the grinding water content is less than 3%, the grinding gas temperature is 300-330 ℃, and the drying heat source is from kiln tail waste gas) for pulverizing to obtain a raw material with the sieving residue percentage of 13% of an 80-micron square-hole sieve, wherein the raw material contains 62% by weight of carbide slag, 25% by weight of molybdenum tailings, 6% by weight of aluminum slag, 5% by weight of spontaneous combustion coal gangue and 2% by weight of fly ash;
(2) homogenizing the raw materials obtained in the step (1) in a storage homogenizing warehouse, then transferring the raw materials to a dry rotary kiln system for preheating (the temperature is 775 ℃), then calcining (the temperature is 1240 ℃, the time is 12min), and then cooling in a grate cooler to obtain cement clinker A2;
the molybdenum tailings comprise the following chemical components in percentage by mass: CaO: 11.5% of SiO2：53％，Fe2O3：12％，Al2O3: 11%, MgO: 2 percent and the balance of other chemical components.
Example 3
(1) Weighing raw materials according to a ratio, and then transferring the raw materials to a middle-discharge type drying and pulverizing mill (the grinding particle size is less than 25mm, the grinding water content is less than 3 percent, the grinding gas temperature is 300-330 ℃, and the drying heat source is from kiln tail waste gas) for pulverizing to obtain a raw material with the screen residue percentage of a 80-micron square-hole sieve of 12 percent, wherein the raw material contains 61 percent by weight of carbide slag, 27 percent by weight of molybdenum tailings, 4 percent by weight of aluminum slag, 4.5 percent by weight of spontaneous combustion coal gangue and 3.5 percent by weight of fly ash;
(2) homogenizing the raw materials obtained in the step (1) in a storage homogenizing warehouse, then transferring the raw materials to a dry rotary kiln system for preheating (the temperature is 780 ℃), then calcining (the temperature is 1140 ℃, the time is 12min), and then cooling in a grate cooler to obtain cement clinker A3;
the molybdenum tailings comprise the following chemical components in percentage by mass: CaO: 12% of SiO2：51％，Fe2O3：12.5％，Al2O3: 11.3%, MgO: 2.7 percent, and the balance being other chemical components.
Comparative example 1
The process was carried out as described in example 1, except that limestone was used instead of the same weight of molybdenum tailings.
Test example
The cement clinker obtained in the examples and the cement clinker obtained in the comparative examples were prepared into cement in the same manner, and the compressive strength of the cement was measured, and the results are shown in table 1.
TABLE 1
| Example numbering | Compressive strength (3d) | Compressive strength (28d) |
| Example 1 | 35.2MPa | 62.5MPa |
| Example 2 | 34.7MPa | 67.3MPa |
| Example 3 | 35.5MPa | 66.4MPa |
| Comparative example 1 | 32.6MPa | 62.3MPa |
The results in table 1 show that cement clinker prepared by the method of the present invention can prepare cement with excellent compressive strength, and can realize resource utilization of molybdenum tailings.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing cement clinker by using molybdenum tailings, which is characterized by comprising the following steps:
(1) weighing the raw materials according to the proportion, and then transferring the raw materials into a middle-discharge type drying and pulverizing mill for grinding to obtain a raw material with the screen residue percentage of 10-15 percent of a 80-micron square-hole sieve;
(2) homogenizing the raw material obtained in the step (1), then transferring the raw material to a dry rotary kiln system for calcining, and then cooling to obtain cement clinker;
wherein the raw material comprises 55-64 wt% of carbide slag, 20-30 wt% of molybdenum tailings, 3-6 wt% of aluminum slag, 4-7 wt% of spontaneous combustion coal gangue and 1.5-4.5 wt% of fly ash;
the calcination temperature is 1050-1250 ℃, and the calcination time is 10-40 min.
2. The method for preparing cement clinker by using molybdenum tailings as recited in claim 1, wherein the raw material comprises 57-61 wt% of carbide slag, 24-29 wt% of molybdenum tailings, 4-5 wt% of aluminum slag, 5-6 wt% of spontaneous combustion coal gangue and 2-4 wt% of fly ash in step (1).
3. The method for preparing cement clinker by using molybdenum tailings as claimed in claim 1, wherein in the step (1), the chemical components of the molybdenum tailings are as follows by mass percent: CaO: 10-12% of SiO2：51-53％，Fe2O3：10-14％，Al2O3: 10-12%, MgO: 1-3 percent of the total weight of the composition, and the balance of other chemical components.
4. The method for preparing cement clinker by using molybdenum tailings as claimed in claim 1, wherein in the step (1), the parameters of the middle discharge type drying and pulverizing mill are as follows: the grinding granularity is less than 25 mm; the grinding water content is less than 3 percent; grinding gas temperature: 300 ℃ and 330 ℃.
5. The method for preparing cement clinker by using molybdenum tailings as claimed in claim 1, wherein in the step (1), the drying heat source of the medium discharge type drying and pulverizing mill is kiln tail waste gas.
6. The method for preparing cement clinker by using molybdenum tailings as claimed in claim 1, wherein in the step (2), the homogenization is performed in a storage homogenization silo.
7. The method for preparing cement clinker by using molybdenum tailings as recited in claim 1, wherein the preheating is performed before the calcination in step (2), and the preheating temperature is 700 ℃ and 800 ℃.
8. The method for preparing cement clinker by using molybdenum tailings as recited in claim 1, wherein the cooling is performed in a grate cooler in the step (2).
9. A cement clinker obtainable by the process according to any one of claims 1 to 8.
10. Use of the cement clinker according to claim 9 for the preparation of cement or in the construction sector.
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| CN116282986A (en) * | 2022-12-29 | 2023-06-23 | 伊春鹿鸣矿业有限公司 | Low-hydration heat molybdenum tailing micro-powder type composite silicate cement and preparation method thereof |
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