CN108516709B - Sulphoaluminate cement clinker taking lead-zinc tailings as raw materials and preparation method thereof - Google Patents
Sulphoaluminate cement clinker taking lead-zinc tailings as raw materials and preparation method thereof Download PDFInfo
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- CN108516709B CN108516709B CN201810312695.5A CN201810312695A CN108516709B CN 108516709 B CN108516709 B CN 108516709B CN 201810312695 A CN201810312695 A CN 201810312695A CN 108516709 B CN108516709 B CN 108516709B
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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
- C04B7/32—Aluminous cements
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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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Abstract
The invention provides sulphoaluminate cement clinker taking lead-zinc tailings as raw materials, which utilizes the lead-zinc tailings, desulfurized gypsum and aluminum ashThe carbide slag is taken as a raw material, and the weight percentage of each raw material is as follows: 5 to 40 percent of lead-zinc tailings; 20 to 50 percent of aluminum ash; 20 to 55 percent of carbide slag; 5 to 35 percent of desulfurized gypsum. The method uses lead-zinc tailings to partially replace partial calcareous raw materials for producing the conventional sulphoaluminate cement clinker, completely replaces siliceous raw materials and lead-zinc raw materials, grinds the mixture to a certain fineness, and passes through a basicity coefficient CmAnd the aluminum-sulfur ratio P is used for controlling the generation of main minerals in the cement clinker, and the cement clinker is prepared by mixing the main minerals with the aluminum ash, the carbide slag, the desulfurized gypsum and other ingredients. The properties of the sulphoaluminate cement clinker meet the current regulations of relevant national standards.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to sulphoaluminate cement clinker taking lead-zinc tailings as a raw material and a preparation method thereof.
Background
The tailings become one of the bulk solid wastes with the largest output and the lowest comprehensive utilization rate in China at present. The lead-zinc tailings refer to minerals which have low lead-zinc component content and cannot be used for producing parts after lead and zinc are separated in ore dressing. Compared with other bulk solid wastes (such as coal gangue, fly ash and the like), the comprehensive utilization technology of the lead-zinc tailings is difficult and more complex. At present, the comprehensive utilization rate of the fly ash reaches about 70%, the comprehensive utilization rate of the coal gangue in the industrial solid waste of China reaches about 30%, the comprehensive utilization rate of the lead-zinc tailings is only 7%, the lead-zinc tailings are large in accumulation amount, and if the lead-zinc tailings can be fully utilized, land resources and mineral resources can be saved, and the environment can be protected. Therefore, the problem of comprehensive recycling of lead-zinc tailings needs to be solved urgently.
The main minerals in the sulphoaluminate cement clinker include anhydrous calcium sulphoaluminate
Dicalcium silicate (C)2S) and tetracalcium aluminoferrite (C)4AF), the most important mineral of which is
The chemical composition of the lead-zinc tailings comprises SiO2、Fe2O3、Al2O3、CaO、SO3And the like, and a small amount of trace elements such as Pb, Zn, Cu and the like, because the chemical composition of the lead-zinc tailings is similar to the properties of the raw materials for preparing the sulphoaluminate cement clinker, the sulphoaluminate cement clinker can be prepared by using the lead-zinc tailings, and the trace elements such as Pb, Zn, Cu and the like in the lead-zinc tailings also have a certain effect on the formation of the clinker. The oxides of Zn and Cu play a role in mineralization and can reduce the appearance temperature of a liquid phase in the sintering process of the sulphate aluminium cement clinker, namely the sintering temperature is reduced; the Pb ions can be partially doped into the clinker minerals, and the properties of the clinker can be changed accordingly.
Through the research of a plurality of researchers, the China has made certain progress in the preparation of the sulphoaluminate cement clinker. The invention patent with the application number of CN201210301372.9 provides a method for preparing sulphoaluminate cement from fluorine-containing sludge, limestone, alumina, gypsum and fluorine-containing sludge are used as raw materials, curing agent and stabilizing agent are added into the sludge to cure fluorine in the sludge, and then the raw materials are calcined to produce sulphoaluminate cement clinker; the invention with the application number of CN201510834817.3 provides a method for calcining belite sulphoaluminate cement clinker by completely utilizing industrial waste residues, which takes carbide slag, fly ash, electrolytic aluminum slag and desulfurized gypsum as raw materials, the raw materials are dried firstly, boric acid is added after the drying to grind the raw materials, and then the high-temperature calcination is carried out to produce the sulphoaluminate cement clinker.
The above methods all use industrial solid waste to prepare sulphoaluminate cement clinker, but the method for preparing sulphoaluminate cement clinker by using lead-zinc tailings is hardly explored, and the patent is a research aiming at the aspect.
Disclosure of Invention
The invention relates to a sulphoaluminate cement clinker taking solid waste lead-zinc tailings as raw materials and a preparation method thereof, wherein the lead-zinc tailings are used for partially replacing partial calcareous raw materials for producing the conventional sulphoaluminate cement clinker, completely replacing siliceous raw materials and lead-zinc raw materials, grinding the mixture to a certain fineness, and passing through a basicity coefficient CmAnd the Al-to-S ratio P to control in cement clinker
And C4And (3) generating main minerals such as AF and the like, and preparing sulphoaluminate cement clinker with ingredients such as aluminum ash, carbide slag, desulfurized gypsum and the like. The properties of the sulphoaluminate cement clinker meet the current regulations of relevant national standards.
In order to achieve the purpose, the invention adopts the technical scheme that:
the sulphoaluminate cement clinker takes lead-zinc tailings as raw materials, and the sulphoaluminate cement clinker takes the lead-zinc tailings, desulfurized gypsum, aluminum ash and carbide slag as the raw materials, and the weight percentages of the raw materials are as follows:
5 to 40 percent of lead-zinc tailings;
20 to 50 percent of aluminum ash;
20 to 55 percent of carbide slag;
5 to 35 percent of desulfurized gypsum.
Preferably, the alkalinity coefficient C is ensured by the weight percentage of the raw materialsm0.98 to 1.20; the aluminum-sulfur ratio P is 2-4.
Preferably, the lead-zinc tailings comprise the following chemical components in percentage by weight: SiO 2250％～75％；CaO5％～20％；Fe2O31％～10％；Al2O31% -10%; 1% -5% of ZnO; PbO1% -5%; the balance being the rest.
Preferably, the aluminum ash comprises the following chemical components in percentage by weight: al (Al)2O365％～80％；SiO 25% -15%; 1-5% of CaO; the balance being the rest.
Preferably, the carbide slag comprises the following chemical components in percentage by weight: 70-95% of CaO; SiO 221％～10％；Al2O31％～10％；SO31% -10%; the balance being the rest.
Preferably, the desulfurized gypsum comprises the following chemical components in percentage by weight: SO (SO)350％～70％；CaO25％～45％；Al2O31% -5%; the balance being the rest.
Preferably, the sulphoaluminate cement clinker has a specific surface area of 350m after being ground by adding dihydrate gypsum with a clinker ratio of 0.05-0.252/Kg～450m2/Kg。
A preparation method of the sulphoaluminate cement clinker taking lead-zinc tailings as raw materials comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials in the first step according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at the speed of 10-30 ℃/min, calcining at the temperature of 1250-1350 ℃ for 30-60 min, preserving the heat for 30-60 min, and quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a new way for utilizing lead-zinc tailings, the solid waste lead-zinc tailings are used as raw materials to prepare sulphoaluminate cement clinker, the production cost is low, and the market prospect is wide; meanwhile, the lead-zinc tailings are effectively utilized, the resource utilization rate is improved, and the problem of comprehensive recycling of the lead-zinc tailings is solved.
2. The sulphoaluminate cement clinker disclosed by the invention utilizes the lead-zinc tailings to partially replace part of calcium raw materials for producing the conventional sulphoaluminate cement clinker, completely replaces siliceous and lead-zinc raw materials, saves the raw material cost, and enables the preparation process to be simpler compared with the prior art; meanwhile, oxides of Zn and Cu contained in the lead-zinc tailings play a role in mineralization, and the occurrence temperature of a liquid phase in the sintering process of the sulphate aluminum cement clinker can be reduced, namely the sintering temperature is reduced.
3. Pb ions can be partially doped into clinker minerals, so that the properties of the clinker are improved.
Drawings
FIG. 1 is a graph of the compressive strength of the sulphoaluminate cement of example 1 at different ages;
FIG. 2 is a graph of the compressive strength of the sulphoaluminate cement prepared in example 2 at different ages;
FIG. 3 is a graph of the compressive strength of the sulphoaluminate cement prepared in example 3 at different ages;
FIG. 4 is a graph of the compressive strength of the sulphoaluminate cement prepared in example 4 at different ages;
FIG. 5 is a graph of the compressive strength of various ages of the sulfoaluminate cements of the comparative examples.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The sulphoaluminate cement prepared in the embodiment comprises the following raw materials in parts by weight: 19.30 parts of lead-zinc tailings, 21.93 parts of aluminum ash, 44.73 parts of carbide slag, 14.04 parts of desulfurized gypsum and alkalinity coefficient CmIt is 1.04, and the aluminum-sulfur ratio P is 2.12. Detailed description of the inventionThe preparation process comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at the temperature of 10 ℃/min, calcining at the temperature of 1250 ℃ for 30min, preserving heat for 60min, and quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker, adding a proper amount of dihydrate gypsum into the clinker, grinding, and testing the compressive strength of the clinker under the condition that the water-cement ratio is 0.4.
The compressive strength of the sulphoaluminate cement prepared in this example at different ages is shown in figure 1. As can be seen from FIG. 1, the compressive strength of the sulphoaluminate cement prepared in this example meets the requirements of the current national standards.
Example 2
The sulphoaluminate cement prepared in the embodiment comprises the following raw materials in parts by weight: 16.30 parts of lead-zinc tailings, 27.41 parts of aluminum ash, 44.44 parts of carbide slag, 11.85 parts of desulfurized gypsum and alkalinity coefficient CmIt is 1.02, and the Al-to-S ratio P is 3.00. The specific preparation process comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at 15 ℃/min, calcining at 1280 ℃ for 50min, preserving heat for 40min, quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker, adding a proper amount of dihydrate gypsum into the clinker, grinding, and testing the compressive strength of the clinker under the condition that the water-cement ratio is 0.4.
The compressive strength of the sulphoaluminate cement prepared in this example at different ages is shown in figure 2. As can be seen from FIG. 2, the compressive strength of the sulphoaluminate cement prepared in this example meets the requirements of the current national standards.
Example 3
The sulphoaluminate cement prepared in the embodiment comprises the following raw materials in parts by weight: : lead (II)17.20 parts of zinc tailings, 26.99 parts of aluminum ash, 45.33 parts of carbide slag, 10.48 parts of desulfurized gypsum and alkalinity coefficient CmIt is 1.00, and the Al-S ratio P is 3.35. The specific preparation process comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at 20 ℃/min, calcining at 1300 ℃ for 60min, preserving heat for 30min, quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker, adding a proper amount of dihydrate gypsum into the clinker, grinding, and testing the compressive strength of the clinker under the condition that the water-cement ratio is 0.4.
The compressive strength of the sulphoaluminate cement prepared in this example at different ages is shown in figure 3. As can be seen from FIG. 3, the compressive strength of the sulphoaluminate cement prepared in this example meets the requirements of the current national standards.
Example 4
The sulphoaluminate cement prepared in the embodiment comprises the following raw materials in parts by weight: 14.08 parts of lead-zinc tailings, 31.69 parts of aluminum ash, 43.67 parts of carbide slag, 10.56 parts of desulfurized gypsum and alkalinity coefficient Cm0.99, and the aluminum-sulfur ratio P is 3.81. The specific preparation process comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at 30 ℃/min, calcining at 1350 ℃ for 60min, preserving heat for 30min, quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker, adding a proper amount of dihydrate gypsum into the clinker, grinding, and testing the compressive strength of the clinker under the condition that the water-cement ratio is 0.4.
The compressive strength of the sulphoaluminate cement prepared in this example at different ages is shown in figure 4. As can be seen from FIG. 4, the compressive strength of the sulphoaluminate cement prepared in this example meets the requirements of the current national standards.
Comparative example
The sulphoaluminate cement of the comparative example is low-alkalinity sulphoaluminate cement with the No. 42.5 of Henan Zhengzhou Dateng building materials, and the cement is a hydraulic material prepared by grinding bauxite, limestone and gypsum through proper ingredients, calcining at 1350 ℃ to form clinker containing anhydrous calcium sulphoaluminate and dicalcium silicate as main mineral components, and adding proper amount of gypsum for grinding together. The compressive strength of the test at a water-cement ratio of 0.4 is shown in FIG. 5.
Finally, it should be noted that: the above examples are merely examples for better illustrating the present invention and are not intended to limit the embodiments. It will be apparent to those skilled in the art that many more modifications and variations than those set forth above are possible in light of the above teaching, and it is not necessary or desirable to describe all such embodiments and accordingly such modifications and variations are to be regarded as being within the scope of the invention.
Claims (3)
1. The sulphoaluminate cement clinker taking lead-zinc tailings as raw materials is characterized in that the sulphoaluminate cement clinker takes lead-zinc tailings, desulfurized gypsum, aluminum ash and carbide slag as raw materials, and the weight percentages of the raw materials are as follows:
5 to 40 percent of lead-zinc tailings;
20 to 50 percent of aluminum ash;
20 to 55 percent of carbide slag;
5 to 35 percent of desulfurized gypsum;
the lead-zinc tailings comprise the following chemical components in percentage by weight: SiO 2250%～75%；CaO5%～20%；Fe2O31%～10%；Al2O31% -10%; 1% -5% of ZnO; PbO1% -5%; the balance being the rest;
the aluminum ash comprises the following chemical components in percentage by weight: al (Al)2O365%～80%；SiO25% -15%; 1-5% of CaO; the balance being the rest;
the carbide slag comprises the following chemical components in percentage by weight: 70-95% of CaO; SiO 221%～10%；Al2O31%～10%；SO31% -10%; the balance being the rest;
after the sulphoaluminate cement clinker is added with dihydrate gypsum with the ratio of 0.05-0.25 to the clinker and ground, the specific surface area is 350m2/Kg～450m2/Kg；
The preparation method comprises the following steps:
the first step is as follows: respectively grinding lead-zinc tailings, aluminum ash, carbide slag and desulfurized gypsum to below 200 meshes;
the second step is that: uniformly mixing the raw materials in the first step according to the proportion;
the third step: and (3) putting the mixed raw materials into a high-temperature furnace, heating at the speed of 10-30 ℃/min, calcining at the temperature of 1250-1350 ℃ for 30-60 min, preserving the heat for 30-60 min, and quenching to room temperature to obtain the lead-zinc tailing sulphoaluminate cement clinker.
2. The sulphoaluminate cement clinker taking lead-zinc tailings as raw materials according to claim 1, wherein the raw materials are in a weight percentage such that the alkalinity coefficient Cm is 0.98-1.20; the aluminum-sulfur ratio P is 2-4.
3. The sulphoaluminate cement clinker starting from lead-zinc tailings as claimed in claim 1, wherein the desulphurized gypsum comprises the following chemical components in weight ratio: SO (SO)350%～70%；CaO25%～45%；Al2O31% -5%; the balance being the rest.
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| CN109293260B (en) * | 2018-10-24 | 2021-03-02 | 河南理工大学 | Sulphoaluminate cement clinker taking copper tailings as raw material and preparation method thereof |
| CN109320110B (en) * | 2018-10-24 | 2021-02-23 | 河南理工大学 | Sulphoaluminate cement clinker taking sulphur tailings as raw material and preparation method thereof |
| CN110451823B (en) * | 2019-07-26 | 2022-02-18 | 三明微晶新材料科技有限公司 | Process for preparing portland cement by using carbide slag and tailing slag and portland cement |
| CN110734234A (en) * | 2019-09-19 | 2020-01-31 | 喀什天山水泥有限责任公司 | Production method and application of cement doped with lead-zinc tailing slag |
| CN110803875A (en) * | 2019-09-19 | 2020-02-18 | 喀什天山水泥有限责任公司 | PII42.5 cement applied to airport special requirements |
| CN112723814B (en) * | 2020-12-31 | 2022-06-03 | 山东大学 | Concrete for prefabricating solid waste base steam curing-free assembly type building, prefabricated part and preparation method |
| CN114920474B (en) * | 2022-04-21 | 2022-11-29 | 山东大学 | Method for preparing new mineral system high-temperature cement by using aluminum ash and carbide slag |
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| CN105645795A (en) * | 2016-02-03 | 2016-06-08 | 中国地质大学（北京） | Sulphate aluminum cement clinker prepared from iron tailings and preparation method thereof |
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