CN109293260B - Sulphoaluminate cement clinker taking copper tailings as raw material and preparation method thereof - Google Patents

Sulphoaluminate cement clinker taking copper tailings as raw material and preparation method thereof Download PDF

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CN109293260B
CN109293260B CN201811245757.1A CN201811245757A CN109293260B CN 109293260 B CN109293260 B CN 109293260B CN 201811245757 A CN201811245757 A CN 201811245757A CN 109293260 B CN109293260 B CN 109293260B
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cement clinker
sulphoaluminate cement
copper tailings
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CN109293260A (en
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朱建平
郭本凯
冯春花
朱丽飞
冯浩传
陈钰
冯玉洁
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Henan University of Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general

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Abstract

The invention provides sulphoaluminate cement clinker taking copper tailings as a raw material and a preparation method thereof, wherein the sulphoaluminate cement clinker comprises the following components in parts by weight: 6-25 parts of copper tailings; 20-35 parts of aluminum ash; 39-50 parts of carbide slag; 5-20 parts of titanium gypsum. The invention uses copper tailings to partially replace calcium, silicon and aluminum raw materials used for producing the conventional sulphoaluminate cement clinker, completely replace iron raw materials, control the formation of minerals in the cement clinker by the alkalinity coefficient Cm and the sulphoaluminate ratio P after grinding to a certain fineness, and prepare the sulphoaluminate cement clinker with the ingredients of aluminum ash, carbide slag, titanium gypsum and the like. The sulphoaluminate cement clinker prepared by the invention adopts the copper tailings and the titanium gypsum to be matched, and creative tests show that the sulphoaluminate cement clinker prepared by the invention has the compressive strength of 43MPa in 3 days, 55MPa in 7d and 59MPa in 28 d.

Description

Sulphoaluminate cement clinker taking copper tailings as raw material and preparation method thereof
Technical Field
The invention relates to the field of building materials, in particular to sulphoaluminate cement clinker taking copper tailings as a raw material and a preparation method thereof.
Background
The copper tailings refer to solid waste with low copper content left after copper ore is crushed and selected, plants are difficult to naturally grow on the solid waste due to the fact that the solid waste contains a lot of heavy metals, and meanwhile, the tailings are prone to polluting the living environment of people in the surrounding areas due to the modes of flying with wind, rainwater loss and the like. Besides a small amount of copper tailings serving as fillers of old mines, the majority of the copper tailings are stored in a manner of filling depressions and the like, and the piled copper tailings not only occupy a large amount of land, but also cover original vegetation and damage an ecological system. Therefore, the comprehensive utilization of the copper tailings is not slow.
The sulphoaluminate cement clinker is formed by using calcium, siliceous, aluminous, sulphurous and ferrous raw materials to form calcium sulphoaluminate serving as a main mineral
Figure BDA0001840478840000011
Dicalcium silicate (C)2S) and tetracalcium aluminoferrite (C)4AF) is low in requirements on the grade of raw materials, and at the present time when natural resources are extremely deficient, if natural resources are utilized to produce sulphoaluminate cement clinker, the production cost is greatly increased, so that industrial solid waste can be properly utilized to replace the raw materials to produce the sulphoaluminate cement clinker. The main chemical components of the copper tailings are CaO and SiO2、Fe2O3、Al2O3And a small amount of trace elements such as Cu, Mn, Zn, Ti and the like, and the main chemical components of the copper-containing sulfate clinker are similar to the raw material components of the sulfate clinker, so that the copper tailings can be used for partially replacing calcareous, siliceous, aluminous and ferrous raw materials to produce the sulfate clinker. The microelements such as Cu, Zn and Mn in the copper tailings and Ti in the titanium gypsum can reduce the sintering temperature of the clinker and promote the generation of minerals in the clinker, part of elements can enter the crystal lattices of the minerals, and because the radius of the entered elements is different from that of the original crystal lattice elements, the crystal lattice parameters can be changed, the crystal lattice distortion is generated, the activity of the minerals can be improved, and the properties of the clinker are changed.
Through the research of a plurality of researchers, the China has made certain progress in the preparation of the sulphoaluminate cement clinker. The invention with the application number of CN200610076718.4 provides a method for preparing sulphoaluminate cement clinker by using red mud, limestone, bauxite, gypsum and red mud are used as raw materials, calcined at the temperature of 1250-1350 ℃ and then quenched to prepare the sulphoaluminate cement clinker, and the method shows that the red mud can be directly used, but the red mud has higher alkali content and self radioactivity, and whether the prepared cement clinker has the radioactivity or not can not be ensured; the invention 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 above methods all use industrial solid wastes to prepare the sulphoaluminate cement clinker, but the method for preparing the sulphoaluminate cement clinker by using the copper tailings is hardly explored, and is still in the field of blank research at present.
Disclosure of Invention
The invention relates to sulphoaluminate cement clinker taking solid waste copper tailings as raw materials and a preparation method thereof, wherein the copper tailings are used for partially replacing calcium, silicon and aluminum raw materials for producing the conventional sulphoaluminate cement clinker, the iron raw materials are completely replaced, the copper tailings are ground to a certain fineness, and the alkalinity coefficient Cm and the sulphur-aluminum ratio P are used for controlling the cement clinker
Figure BDA0001840478840000021
C2S and C4And (3) forming AF minerals, and preparing sulphoaluminate cement clinker with the ingredients of aluminum ash, carbide slag, titanium gypsum and the like.
In order to achieve the above purpose, the invention provides the following technical scheme:
the sulphoaluminate cement clinker taking copper tailings as a raw material comprises the following components in parts by weight: 6-25 parts of copper tailings; 20-35 parts of aluminum ash; 39-50 parts of carbide slag; 5-20 parts of titanium gypsum.
The sulphoaluminate cement clinker comprises the following components in parts by weight: 7-24 parts of copper tailings; 21-34 parts of aluminum ash; 45-50 parts of carbide slag; 10-17 parts of titanium gypsum.
Preferably, the sulphoaluminate cement clinker is prepared by raw materials with the weight part of the sulphoaluminate cement clinker, and the alkalinity coefficient Cm is ensured to be 0.94-0.97; the range of the aluminum-sulfur ratio P is 2-4.
The sulphoaluminate cement clinker comprises the following components by weight percent: 30 to 40 percent of CaO; SiO 22，30％～40％；Fe2O3，15％～25％；Al2O31% -10%; 1% -3% of CuO; the balance being unavoidable impurities.
The sulphoaluminate cement clinker comprises the following components by weight percent: al (Al)2O3，67％～80％；SiO27% -15%; 5 to 20 percent of CaO; the balance being unavoidable impurities.
The sulphoaluminate cement clinker comprises the following components by weight percent: 75 to 90 percent of CaO; SiO 22，3％～10％；Al2O3，3％～10％；SO31% -7%; the balance being unavoidable impurities.
The sulphoaluminate cement clinker comprises the following components in percentage by weight: SO (SO)3，40％～55％；CaO，25％～40％；Fe2O3，5％～20％；Al2O3，1％～10％；TiO21% -5%; the balance being unavoidable impurities.
The sulphoaluminate cement clinker is preferably ground by adding dihydrate gypsum with the mass ratio of 0.07-0.20 to the clinker, and the specific surface area of the sulphoaluminate cement clinker is 360m2/Kg～440m2/Kg。
The preparation method of the sulphoaluminate cement clinker taking the copper tailings as the raw material is characterized by comprising the following steps:
1) respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing each raw material component according to the raw material proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 10-12 hours at 100-105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1260-1300 ℃, preserving heat for 40-55 min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker.
Compared with the closest prior art, the technical scheme provided by the invention has the following beneficial effects:
1) the invention provides a new way for utilizing copper tailings, which utilizes solid waste as a raw material, does not need to add any additive, and has the advantages of low production cost, low energy consumption and wide market and application prospects.
2) The preparation method is simple and easy to operate, and can realize industrial production.
3) The invention uses copper tailings to partially replace calcium, silicon and aluminum raw materials used for producing the conventional sulphoaluminate cement clinker, completely replaces iron raw materials, and controls the cement clinker by the alkalinity coefficient Cm and the sulphur-aluminum ratio P after grinding to a certain fineness
Figure BDA0001840478840000031
C2S and C4And (3) forming AF minerals, and preparing sulphoaluminate cement clinker with the ingredients of aluminum ash, carbide slag, titanium gypsum and the like. The sulphoaluminate cement clinker prepared by the invention adopts the copper tailings and the titanium gypsum to be matched, and creative tests show that the sulphoaluminate cement clinker prepared by the invention has the compressive strength of 43MPa in 3 days, 55MPa in 7d and 59MPa in 28 d.
Drawings
FIG. 1 is a graph showing the trend of compressive strength of copper tailing sulphoaluminate cement clinker prepared in the embodiment 1 of the present invention at different ages;
FIG. 2 is a graph showing the trend of the compressive strength of copper tailing sulphoaluminate cement clinker prepared in the embodiment 2 of the present invention at different ages;
FIG. 3 is a graph showing the trend of the compressive strength of copper tailing sulphoaluminate cement clinker prepared in the embodiment 3 of the present invention at different ages;
FIG. 4 is a graph showing the trend of the compressive strength of the copper tailing sulphoaluminate cement clinker prepared in the embodiment 4 of the present invention at different ages;
FIG. 5 is a graph showing the trend of the compressive strength of copper tailing sulphoaluminate cement clinker prepared in the embodiment 5 of the present invention at different ages;
FIG. 6 is a graph showing the trend of the compressive strength of copper tailing sulphoaluminate cement clinker prepared in the embodiment 6 of the present invention at different ages;
FIG. 7 is a graph showing the trend of the compressive strength of the copper tailing sulphoaluminate cement clinker prepared in the comparative example 1 in different ages;
FIG. 8 is a graph showing the trend of the compressive strength of the copper tailing sulphoaluminate cement clinker prepared in the comparative example 2 in different ages;
FIG. 9 is a graph showing the trend of the compressive strength of the copper tailing sulphoaluminate cement clinker prepared in the comparative example 3 in different ages.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides sulphoaluminate cement clinker taking copper tailings as a raw material, which comprises the following components in parts by weight: 6-25 parts (for example, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts) of copper tailings; 20-35 parts of aluminum ash (such as 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts and 35 parts); 39-50 parts of carbide slag (such as 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts and 50 parts); 5 to 20 parts of titanium gypsum (for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts and 20 parts).
In the specific embodiment of the invention, the sulphoaluminate cement clinker comprises the following components in parts by weight: 7-24 parts (e.g., 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, 16 parts, 16.5 parts, 17 parts, 17.5 parts, 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts) of copper tailings; 21 to 34 parts of aluminum ash (for example, 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts, 24 parts, 24.5 parts, 25 parts, 25.5 parts, 26 parts, 26.5 parts, 27 parts, 27.5 parts, 28 parts, 28.5 parts, 29 parts, 29.5 parts, 30 parts, 30.5 parts, 31 parts, 31.5 parts, 32 parts, 32.5 parts, 33 parts, 33.5 parts, 34 parts, 34.5 parts, 35 parts); 45-50 parts of carbide slag (such as 45 parts, 45.5 parts, 46 parts, 46.5 parts, 47 parts, 47.5 parts, 48 parts, 48.5 parts, 49 parts, 49.5 parts and 50 parts); 10-17 parts of titanium gypsum (for example, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, 16 parts, 16.5 parts and 17 parts).
In the embodiment of the invention, the raw material composition of the sulphoaluminate cement clinker is in a weight part range that ensures that the alkalinity factor Cm is in a range of 0.94-0.97 (such as 0.94, 0.942, 0.945, 0.948, 0.95, 0.952, 0.955, 0.958, 0.96, 0.962, 0.965, 0.968, 0.97); the aluminum-sulfur ratio P is in the range of 2-4 (e.g., 2, 2.2, 2.4, 2.5, 2.6, 2.8, 3, 3.2, 3.4, 3.5, 3.6, 3.8, 4).
In the specific embodiment of the invention, the copper tailings comprise the following components in percentage by weight: CaO, 30-40% (e.g., 31%, 31.5%, 32%, 32.5%, 33%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%); SiO 2230-40% (e.g. 31%, 31.5%, 32%, 32.5%),33％、34.5％、35％、35.5％、36％、36.5％、37％、37.5％、38％、38.5％、39％、39.5％、40％)；Fe2O315% to 25% (e.g., 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%); al (Al)2O31% to 10% (e.g., 1%, 1.5%, 2%, 2.5%, 3%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%); CuO, 1% to 3% (e.g., 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%); the balance being unavoidable impurities.
In the specific embodiment of the invention, the aluminum ash comprises the following components in percentage by weight: al (Al)2O367% -80% (e.g., 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%); SiO 227% -15% (e.g., 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%); CaO, 5% to 20% (e.g., 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%); the balance being unavoidable impurities.
In the specific embodiment of the invention, the carbide slag comprises the following components in percentage by weight: CaO, 75% to 90% (e.g., 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%); SiO 223% to 10% (e.g., 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%); al (Al)2O33% to 10% (e.g., 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%); SO (SO)31% to 7% (e.g., 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%); the balance being unavoidable impurities.
In the specific embodiment of the invention, the titanium gypsum comprises the following components in percentage by weight: SO (SO)340% -55% (e.g., 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%); CaO, 25-40% (e.g., 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%); fe2 O 35% to 20% (e.g., 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%); al (Al)2O31% to 10% (e.g., 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%); TiO 221% to 5% (e.g., 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.5%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.5%, 4.6%, 4.8%); the balance being unavoidable impurities.
In the specific embodiment of the invention, after the sulphoaluminate cement clinker is added with dihydrate gypsum with the mass ratio of 0.07-0.20 (such as 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 and 0.20) to the clinker and ground, the specific surface area ranges from 360m2/Kg～440m2Perkg (e.g. 365 m)2/Kg、370m2/Kg、375m2/Kg、380m2/Kg、385m2/Kg、390m2/Kg、395m2/Kg、380m2/Kg、390m2/Kg、400m2/Kg、410m2/Kg、420m2/Kg、430m2/Kg、440m2/Kg)。
A method for preparing the sulphoaluminate cement clinker taking the copper tailings as the raw material, which comprises the following steps:
1) respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the raw material proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 10-12 h (for example, 10.2h, 10.4h, 10.5h, 10.6h, 10.8h, 11h, 11.2h, 11.4h, 11.5h, 11.6h and 11.8h) under the condition of 100-105 ℃ (for example, 101 ℃, 101.5 ℃, 102 ℃, 102.5 ℃, 103 ℃, 103.5 ℃, 104 ℃, 104.5 ℃ and 105 ℃) for later use;
further preferably, the mixture is pressed into a test cake with the diameter of 30mm by a tablet press and dried for 12 hours at the temperature of 105 ℃ for standby.
3) Placing the test cake prepared in the step 2) into a high temperature furnace, heating to 1260-1300 ℃ (such as 1265 ℃, 1268 ℃, 1270 ℃, 1272 ℃, 1275 ℃, 1278 ℃, 1280 ℃, 1282 ℃, 1285 ℃, 1288 ℃, 1290 ℃, 1292 ℃, 1295 ℃, 1298 ℃ and 1230 ℃), keeping the temperature for 40-55 min (such as 41min, 42min, 43min, 44min, 45min, 46min, 47min, 48min, 49min, 50min, 51min, 52min, 53min and 54min), and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker.
Example 1
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 10.46 parts of titanium gypsum, 21.55 parts of aluminum ash, 24.06 parts of copper tailings and 43.93 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.95, and the aluminum-sulfur ratio P is 2.22.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1260 ℃, preserving heat for 40min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker. The specific surface area of the ground clinker is 384m after 9.1 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 1 shows a trend graph of the achieved compressive strength of the product.
The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Example 2
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 15.78 parts of titanium gypsum, 24.61 parts of aluminum ash, 16.08 parts of copper tailings and 43.53 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.96, and the aluminum-sulfur ratio P is 2.03.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1270 ℃, preserving heat for 45min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker. The specific surface area of the ground clinker is 380m after 10.2 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 2 shows a trend graph of the achieved compressive strength of the product.
The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Example 3
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 16.67 parts of titanium gypsum, 26.66 parts of aluminum ash, 16.67 parts of copper tailings and 40.00 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.94, and the aluminum-sulfur ratio P is 2.28.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) putting the test cake prepared in the step 2) into a high-temperature furnace, heating to 1280 ℃, preserving heat for 50min, and quenching to room temperature to obtain the copper tailing sulphoaluminateA salt cement clinker. The specific surface area of the ground clinker is 382m after 11.3 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 3 shows a trend graph of the achieved compressive strength of the product.
The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Example 4
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 12.98 parts of titanium gypsum, 29.01 parts of aluminum ash, 12.21 parts of copper tailings and 45.80 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.95, and the aluminum-sulfur ratio P is 2.98.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1285 ℃, preserving heat for 53min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker. The specific surface area of the ground clinker is 387m after 12.4 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 4 shows a trend graph of the achieved compressive strength of the product. The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Example 5
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 10.42 parts of titanium gypsum, 31.25 parts of aluminum ash, 12.50 parts of copper tailings and 45.83 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.96, and the aluminum-sulfur ratio P is 3.51.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1275 ℃, preserving heat for 47min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker. The specific surface area of the ground clinker is 387m after 13.5 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 5 shows a trend graph of the achieved compressive strength of the product.
The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Example 6
The copper tailing sulphoaluminate cement clinker provided by the embodiment comprises the following raw materials in parts by weight: 11.47 parts of titanium gypsum, 33.54 parts of aluminum ash, 7.76 parts of copper tailings and 47.23 parts of carbide slag, wherein the alkalinity coefficient Cm is 0.94, and the aluminum-sulfur ratio P is 3.96.
1) Respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing the raw material components according to the proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 12 hours at 105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1278 ℃, preserving heat for 43min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker. The specific surface area of the ground clinker is 391m after 14.6 percent of dihydrate gypsum is added into the clinker2and/Kg, simultaneously forming under the condition that the water-cement ratio is 0.4, and testing the mechanical property after curing in a standard curing room (the temperature is 20 ℃ and the relative humidity is more than or equal to 90%) to a certain age. Figure 6 shows a trend graph of the achieved compressive strength of the product. The prepared sulphoaluminate cement with the product performance superior to that of 42.5 grades on the market can be obtained.
Comparative example 1
The sulphoaluminate cement of comparative example 1 is low alkalinity sulphoaluminate cement with 42.5 of Hirtex Tech technologies Limited of Jian Wen, Henan Zheng, the cement is prepared by grinding bauxite, limestone and natural gypsum through proper ingredients, calcining at about 1350 ℃ to clinker containing calcium sulphoaluminate and dicalcium silicate as main mineral components, and adding proper amount of gypsum to grind together to prepare a hydraulic material. The mechanical properties were tested at a water-cement ratio of 0.4. Figure 7 shows a trend graph of the achieved compressive strength of the product.
Comparative example 2
Compared with the example 6, the copper tailings in the example 6 are replaced by the lead-zinc tailings in the same parts by weight, and the rest of the contents are the same as those in the example 6, which is not repeated herein. The basicity coefficient Cm after substitution was 0.95 and the aluminium-sulphur ratio P was 3.05. Figure 8 shows a trend graph of the achieved compressive strength of the product.
Comparative example 3
Compared with the example 6, the copper tailings in the example 6 are replaced by the tin tailings, the weight parts are the same, and the other contents are the same as the example 6 and are not repeated herein. After replacement, the alkalinity coefficient Cm is 0.90, the aluminum-sulfur ratio P is 3.40, and the alkalinity coefficient is smaller, so that the CaO content of various minerals is seriously insufficient, a plurality of transitional minerals are formed, the content of designed mineral components is reduced, and the performance of cement clinker is influenced. Figure 9 shows a trend graph of the achieved compressive strength of the product.
The properties of the articles prepared in the above examples are shown in table 1 below.
Table 1 results of performance index test of each example
Figure BDA0001840478840000111
In summary, by comparing examples 1 to 6 with comparative examples 1 to 3, it can be seen that the performance of the sulphoaluminate cement clinker prepared by the technical scheme provided by the invention is better than that of the sulphoaluminate cement clinker prepared by lead-zinc tailings and tin tailings, and various impurity ions in the raw materials can improve the combustibility and mineral activity of the clinker, improve the mechanical property of the clinker, comprehensively utilize solid wastes, and simultaneously produce the high-performance cement clinker, thereby having significant environmental protection and application significance. In addition, after the lead-zinc tailings and the tin tailings are adopted to replace the copper tailings in the comparative examples 2 and 3, the mineral composition in the comparative examples 2 and 3 is higher than that in the technical scheme of the invention, but the performance of the sulphoaluminate cement clinker prepared by the technical scheme provided by the invention is better, and the technical scheme provided by the invention is proved to be more creative.
In summary, the present invention also has the following technical effects:
1) the invention provides a new way for utilizing copper tailings, which utilizes solid waste as a raw material, does not need to add any additive, and has the advantages of low production cost, low energy consumption and wide market and application prospects.
2) The preparation method is simple and easy to operate, and can realize industrial production.
3) The invention uses copper tailings to partially replace calcium, silicon and aluminum raw materials used for producing the conventional sulphoaluminate cement clinker, completely replaces iron raw materials, and controls the cement clinker by the alkalinity coefficient Cm and the sulphur-aluminum ratio P after grinding to a certain fineness
Figure BDA0001840478840000121
C2S and C4And (3) forming AF minerals, and preparing sulphoaluminate cement clinker with the ingredients of aluminum ash, carbide slag, titanium gypsum and the like. The sulphoaluminate cement clinker prepared by the invention adopts the copper tailings and the titanium gypsum to be matched, and creative tests show that the sulphoaluminate cement clinker prepared by the invention has the compressive strength of 43MPa in 3 days, 55MPa in 7d and 59MPa in 28 d.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.

Claims (2)

1. The sulphoaluminate cement clinker taking copper tailings as a raw material is characterized by comprising the following components in parts by weight:
7-24 parts of copper tailings; 21-34 parts of aluminum ash; 45-50 parts of carbide slag; 10-17 parts of titanium gypsum;
the copper tailings comprise the following components in percentage by weight: 30 to 40 percent of CaO; SiO 22，30％～40％；Fe2O3，15％～25％；Al2O31% -10%; 1% -3% of CuO; the balance of inevitable impurities;
the aluminum ash comprises the following components in percentage by weight: al (Al)2O3，67％～80％；SiO27% -15%; 5 to 20 percent of CaO; the balance of inevitable impurities;
the carbide slag comprises the following components in percentage by weight: 75 to 90 percent of CaO; SiO 22，3％～10％；Al2O3，3％～10％；SO31% -7%; the balance of inevitable impurities;
the titanium gypsum comprises the following components in percentage by weight: SO (SO)3，40％～55％；CaO，25％～40％；Fe2O3，5％～20％；Al2O3，1％～10％；TiO21% -5%; the balance of inevitable impurities;
after the sulphoaluminate cement clinker is ground by adding dihydrate gypsum with the mass ratio of 0.07-0.20 to the clinker, the specific surface area range is 360m2/Kg～440m2/Kg；
The preparation method of the sulphoaluminate cement clinker taking the copper tailings as the raw material comprises the following steps:
1) respectively grinding copper tailings, aluminum ash, carbide slag and titanium gypsum to below 200 meshes for later use;
2) weighing each raw material component according to the raw material proportion, mixing and stirring uniformly, pressing the mixture into a test cake by using a tablet press, and drying for 10-12 hours at 100-105 ℃ for later use;
3) and (3) placing the test cake prepared in the step 2) into a high-temperature furnace, heating to 1260-1300 ℃, preserving heat for 40-55 min, and quenching to room temperature to obtain the copper tailing sulphoaluminate cement clinker.
2. The sulphoaluminate cement clinker of claim 1, wherein the sulphoaluminate cement clinker is prepared from raw materials in parts by weight such that the basicity coefficient Cm is within a range of 0.94-0.97; the range of the aluminum-sulfur ratio P is 2-4.
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