CN109354425B - Composite mineralizer suitable for calcining white sulphoaluminate cement clinker and preparation method thereof - Google Patents
Composite mineralizer suitable for calcining white sulphoaluminate cement clinker and preparation method thereof Download PDFInfo
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- CN109354425B CN109354425B CN201811295337.4A CN201811295337A CN109354425B CN 109354425 B CN109354425 B CN 109354425B CN 201811295337 A CN201811295337 A CN 201811295337A CN 109354425 B CN109354425 B CN 109354425B
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- sulphoaluminate cement
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
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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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- 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
Abstract
The invention relates to a composite mineralizer suitable for white sulphoaluminate cement, belonging to the technical field of cement mineralizers. The composite mineralizer comprises the following components in parts by weight: CaF20.2-1.0 part, 0.1-1.5 parts of SrO, 0.1-1.0 part of ZnO and 0.1-1.0 part of MgO. The composite mineralizer provided by the invention can realize low CaF2The mixed amount and other mineralizers act together to reduce the firing temperature of the raw material, reduce energy consumption, increase the liquid phase amount, stabilize high-temperature crystal phase and obviously improve the performance of white sulphoaluminate cement; meanwhile, the mineralizer has the advantages of easily available raw materials, low cost, simple and easy preparation method, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of cement preparation, and particularly relates to a composite mineralizer capable of remarkably improving calcination of white sulphoaluminate cement clinker and a preparation method thereof.
Background
The modern society and the building industry are developed vigorously, the amount of the used traditional decorative building materials is huge, and meanwhile, along with the improvement of the national attention degree on infrastructure construction, energy conservation, emission reduction and environmental protection, the problem of how to reduce the energy consumption of building material products and improve the performance of the building material products is in urgent need of solving at present. The sulphoaluminate cement has the advantages of early strength, high strength, low energy consumption, wear resistance, excellent long-term mechanical property and the like, and is special cement with good application prospect. By reducing the content of coloring elements in the raw material, especially Fe having a large influence on the whiteness2O3The white sulphoaluminate cement clinker prepared by the method mainly comprises
-C2S-C3A-C12A7The firing temperature of the formed mineral phase system is 1200-1300 ℃, but the firing temperature of the cement is still high, and the cement is made of Fe2O3The content is extremely low, the quantity of molten minerals is less during calcination, and the quantity of liquid phase is insufficient, so that the product quality is influenced.
Small amounts of substances added to the ingredients during clinker sintering to promote or control clinker mineral formationKnown as mineralizers. The addition of mineralizer can promote sintering and improve some properties of the product. The mineralizer mainly comprises manganese dioxide, a chromium-containing compound, a copper-containing compound, chromium slag and the like, and the main effective components of the mineralizer have certain colors, so that the mineralizer can promote the generation of minerals of the cement clinker to a certain degree, reduce the calcining temperature and increase the liquid phase, but has larger influence on the whiteness of the cement, and obviously reduces the product performance. Yet other scholars will CaF2The mineralizer can reduce the viscosity of liquid phase, promote the formation of dicalcium silicate, tricalcium aluminate and other substances, and reduce the sintering temperature of clinker when being applied to cement calcination as the mineralizer, but the mineralizer has certain corrosion effect on kiln linings and certain pollution to the environment.
In summary, the existing white sulphoaluminate cement mineralizing agents still have a plurality of problems, for example, the mineralizing agent with a single component often has the advantages and the disadvantages, and cannot be considered in the aspects of improving the performance, protecting the environment and the like, or the whiteness of the white sulphoaluminate cement is influenced, and the like; for this reason, there is a need to develop a new cement clinker mineralizer and to make it applicable to white sulphoaluminate cements in order to solve or ameliorate at least some of the above-mentioned problems of the prior art.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a composite mineralizer suitable for calcining white sulphoaluminate cement clinker and a preparation method thereof. The composite mineralizer provided by the invention can realize low CaF2The mixed amount and other mineralizers act together to reduce the sintering temperature of clinker, reduce energy consumption, increase the liquid phase amount, stabilize high-temperature crystal phase and obviously improve the performance of white sulphoaluminate cement; meanwhile, the mineralizer has the advantages of easily available raw materials, low cost, simple and easy preparation method, and is suitable for industrial production.
One of the objects of the present invention is to provide a composite mineralizer suitable for the calcination of white sulphoaluminate cement clinker.
The invention also aims to provide a preparation method of the composite mineralizer suitable for white sulphoaluminate cement.
The invention also aims to provide white sulphoaluminate cement clinker.
The fourth purpose of the invention is to provide the composite mineralizer suitable for calcining the white sulphoaluminate cement clinker and the application of the white sulphoaluminate cement clinker.
In order to achieve the purpose, the invention specifically discloses the following technical scheme:
the invention discloses a composite mineralizer suitable for white sulphoaluminate cement, which comprises the following components in parts by weight: CaF20.2-1.0 part, 0.1-1.5 parts of SrO, 0.1-1.0 part of ZnO and 0.1-1.0 part of MgO.
Further, the composite mineralizer preferably comprises the following components in parts by weight: CaF20.2-0.7 part, 0.1-0.8 part of SrO, 0.1-0.7 part of ZnO and 0.1-0.7 part of MgO. Tests prove that when the contents of the components of the mineralizer are in the range, the reduction of the firing temperature of the cement raw materials is larger, and meanwhile, the liquid phase amount during sintering can be further increased, so that the high-temperature crystal phase is more stable, and the performance of the white sulphoaluminate cement is obviously improved.
Further, the CaF2The low-iron strontium oxide is introduced from fluorite, the SrO is introduced from low-iron strontium slag, the ZnO is introduced from calamine, and the MgO is introduced from aluminum slag or/and white slag. The raw materials such as fluorite, low-iron strontium slag, calamine, aluminum slag, white slag and the like have wide sources and low cost, and the production cost of the mineralizer prepared by adopting the raw materials can be obviously reduced, so that the mineralizer is more favorable for popularization and application.
Preferably, CaF in said fluorite2The content of (A) is 50-70%, and the whiteness is 80-85%.
Preferably, the SrO content in the low-iron strontium slag is 30-70%, and the whiteness is 75-80%.
Preferably, the content of ZnO in the calamine is 40-75%, the whiteness is 70-80%, and the content of Fe in the calamine is Fe2O3The content is less than 0.1 percent.
Preferably, the aluminum slag is white aluminum slag, wherein Al2O380-90 wt%, MgO 0.15-2 wt%, Fe2O3The content is 0.1-0.4 wt%, and the density is 2.2-2.6 g/cm3。
Preferably, the content of MgO in the white slag is 8-12%, and Fe2O3The content is less than 0.15 wt%.
It should be noted that the invention is prepared by a mineralizer for preparing white sulphoaluminate cement clinker calcination, and the whiteness of other components such as the mineralizer added must be considered so as to avoid adverse effect on the whiteness of the sulphoaluminate cement finally obtained, even disqualification, and the research of the invention finds that when the whiteness of the above components is controlled within the above range, the whiteness of the sulphoaluminate cement can be remarkably improved; in addition, the Fe in the calamine and aluminum slag needs to be strictly controlled2O3Content of because of Fe2O3The self color is red, which has great influence on the whiteness, and the improper content control can cause the unqualified whiteness of the sulphoaluminate cement.
The invention further discloses a preparation method of the composite mineralizer suitable for calcining the white sulphoaluminate cement clinker, which comprises the following steps:
(1) uniformly mixing fluorite, low-iron strontium slag, calamine, aluminum slag and white slag according to a proportion, and drying to obtain a mixture for later use;
(2) and (2) grinding the mixture obtained in the step (1), sieving, and then sealing to obtain the material.
Further, in the step (1), the mixture is dried until the water content is lower than 1%. Too high a water content is inconvenient to grind and store.
Further, in the step (2), the mixture is ground into fine powder and then sieved by a 200-mesh sieve, and the residue on the sieve is less than 5 wt%. Thus being beneficial to more uniform mixing of the mineralizer and the cement raw materials when in use and improving the sintering stability.
The invention further discloses white sulphoaluminate cement clinker which comprises the composite mineralizer suitable for calcining the white sulphoaluminate cement clinker, wherein the addition proportion of the composite mineralizer can be adjusted according to actual needs, and the invention is not limited.
Further, the invention provides a preferable white sulphoaluminate cement clinker which comprises the following components in parts by weight: 31.0-36.0% of aluminum slag, 45.0-52.0% of limestone, 0-4.0% of quartz sand, 15.0-20.0% of gypsum and 0.7-1.5% of mineralizer, wherein the mineralizer is the composite mineralizer suitable for calcining white sulphoaluminate cement clinker.
The composite mineralizer contains part of CaF2，CaF2Not only can accelerate the decomposition of calcium carbonate and destroy SiO2The crystal lattices promote the solid phase reaction, and can also generate compounds such as sodium fluosilicate, calcium fluoroaluminate and the like with other components in the calcination of the white sulphoaluminate cement clinker through the solid phase reaction, the compounds are intermediate transition phases, and the formation of substances such as dicalcium silicate, tricalcium aluminate and the like can be promoted by the compounds, so that the mechanical property of the sulphoaluminate cement clinker is improved.
Secondly, the invention provides a preparation method of white sulphoaluminate cement clinker, which comprises the following steps:
s1, crushing, homogenizing and washing the preferable white sulphoaluminate cement raw material, drying, grinding and uniformly mixing for later use;
and S2, pressing the ground white sulphoaluminate cement raw material in the S1 into blocks, calcining, cooling and grinding to obtain the white sulphoaluminate cement clinker.
It is to be noted that: in step S2, when the components of the composite mineralizer are introduced through fluorite, low-iron strontium slag, calamine, aluminum slag and white slag, part of the components are overlapped with part of the raw materials of the cement raw material, for example, CaO and SiO are brought in2、Al2O3And the components are equal, and the components brought by the mineralizer are taken into account when the raw material batching calculation of the white sulphoaluminate cement clinker is carried out.
Further, in step S1, the ground white sulphoaluminate cement raw meal is sieved by a 200-mesh sieve, and the screen residue is less than 5 wt%.
Further, in step S2, the white sulphoaluminate cement raw material is pressed into a round block with a diameter of 60mm and a thickness of 10 mm.
Further, in step S2, the calcination is performed in an air atmosphere at 1050-1150 ℃ for 1-2 h.
Further, the white sulphoaluminate cement clinker obtained in the step S2 has a specific surface area of 300-400 m2The whiteness is 85-92%, and the 3d strength is 65-80 MPa.
Further, the mineral composition of the white sulphoaluminate cement clinker obtained in step S2 is:
68～78％、C2S 12～18％、C3A 8～14％、C12A70.3-0.8%; the above-mentioned
Refers to anhydrous calcium sulphoaluminate, C2S is dicalcium silicate, C3A is tricalcium aluminate, C12A7Refers to dodecacalcium heptaluminate.
Further, the white sulfoaluminate cement clinker obtained in step S2 contains C in addition to the above 4 main minerals2AS (dicalcium aluminosilicate), CaSO4Ⅱ、3C2S·CaF2MgO, SrO, ZnO, CaO, a metal component solid solution and the like, wherein the total amount of the impurities is 1.5-3.5%.
Finally, the invention discloses the composite mineralizer suitable for calcining the white sulphoaluminate cement clinker and the application of the white sulphoaluminate cement clinker in the field of buildings, in particular the application in the field of building decoration, because the whiteness of the white sulphoaluminate cement clinker prepared by the raw material containing the mineralizer reaches 85-92 percent, and the 3d strength also reaches 65-85 MPa, the composite mineralizer is very suitable for the application in building decoration.
The composite mineralizer of the invention is CaF2SrO, ZnO and MgO as effective components, CaF2Can accelerate the decomposition of calcium carbonate and destroy SiO2Lattice of the crystalPromoting solid phase reaction and, at the same time, CaF2And the cement raw material components can generate compounds such as sodium fluosilicate, calcium fluoroaluminate and the like through solid-phase reaction, the compounds are intermediate transition phases, and the formation of substances such as dicalcium silicate, tricalcium aluminate and the like can be promoted by the presence of the compounds. SrO has the functions of stabilizing a high-temperature crystalline phase, reducing the calcination temperature and improving the performance of clinker. ZnO can prevent beta-C2S direction gamma-C2And S is converted, and the cement fluidity is improved, the water demand is reduced, and the early strength is improved. MgO can combine with the cement clinker minerals into solid solution and dissolve in the glass phase, and can also reduce the calcination temperature of the cement clinker, increase the quantity of liquid phase, reduce the viscosity of the liquid phase, facilitate the calcination of the cement clinker and change the color of the cement. Meanwhile, the compounding of SrO and ZnO can stabilize the formation of a belite crystal phase (better than the addition of a single mineral), accelerate the reaction rate of an intermediate phase and generate more anhydrous calcium sulphoaluminate in a short time. Furthermore, from CaF2The composite solid solution formed by SrO, ZnO and MgO can well promote the obvious reduction of the viscosity of each mineral phase in the whole high-aluminum system, the obvious increase of the liquid phase amount, the acceleration of the intermediate transition phase reaction rate, the improvement of the activity of dicalcium silicate and the prevention of transition to gamma-C2S conversion is beneficial to the formation of clinker and the improvement of the early strength of the sulphoaluminate cement clinker. Therefore, the use of the composite mineralizer can obviously reduce the sintering temperature of the white sulphoaluminate cement clinker, increase the quantity of liquid phases and stabilize high-temperature crystalline phases, compared with common mineralizers such as fluorite and the like, the use of the composite mineralizer can reduce the sintering temperature of the white sulphoaluminate cement clinker by 150 ℃ again, and the whiteness and the early strength of the cement clinker are obviously improved because the composite mineralizer is white.
Compared with the prior art, the invention has the beneficial effects that:
(1) the main raw materials of the composite mineralizer provided by the invention are low-iron strontium slag, aluminum slag, calamine, white slag and fluorite. The low-iron strontium slag, the aluminum slag and the white slag belong to the category of solid wastes, and the wastes are recycled, so that the cost can be obviously reduced, and the energy conservation and environmental protection are facilitated; the calamine and fluorite are common low-grade minerals, have wide application, low price and wide sources, and are preferred materials for producing cement. The selection and the use of the raw materials reduce the production cost of the composite mineralizer, and are convenient for industrial application.
(2) The composite mineralizer can reduce the calcination temperature of the white sulphoaluminate cement clinker by more than 150 ℃ again, can effectively reduce coal consumption, is beneficial to energy conservation and environmental protection, reduces the cost, and has lower requirements on calcination equipment. Meanwhile, the composite mineralizer disclosed by the invention can play a role in increasing the liquid phase content of a mineral phase and stabilizing a high-temperature crystalline phase, so that the whiteness of the cement clinker can be improved, the mechanical property of the cement clinker can be improved, and the difference between the cement clinker and high-grade white cement is shortened. Moreover, the composite mineralizer is white, so that the whiteness of the cement clinker can be obviously improved.
(3) The invention provides an optimal white sulphoaluminate cement clinker, the calcination temperature of the clinker is further reduced to 1050-1150 ℃ under the action of the composite mineralizer, meanwhile, the whiteness and the mechanical property of the clinker are also obviously improved, the whiteness of the white sulphoaluminate cement clinker reaches 85-92%, the 3d strength of the clinker is up to 65-85 MPa, and the clinker has a wide application prospect in the field of building decoration.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the conventional mineralizers for calcining white sulphoaluminate cement clinker still have many problems, for example, the mineralizer with a single component often has the advantages and the disadvantages, cannot be compatible with the aspects of performance improvement, environmental protection and the like, or can affect the whiteness of the white sulphoaluminate cement. The invention thus proposes a composite mineralizer suitable for the calcination of white sulphoaluminate cement clinker and a process for its preparation, which is further described below with reference to specific embodiments.
In the following examples:
CaF of fluorite used2The content of (A) is 50-70%, and the whiteness is 80-85%.
The SrO content of the low-iron strontium slag is 30-70%, and the whiteness is 75-80%.
The calamine contains 40-75% ZnO, 70-80% whiteness, and Fe2O3The content is less than 0.1 percent.
The aluminum slag is white aluminum slag, and Al thereof2O380-90 wt%, MgO 0.15-2 wt%, Fe2O3The content is 0.1-0.4 wt%, and the density is 2.2-2.6 g/cm3。
The white slag contains 8-12% of MgO and Fe2O3The content is less than 0.15wt%
The quartz sand is common quartz sand, SiO2The content of Fe is 90-99 wt%2O3The content is 0.002-0.005 wt%.
The gypsum is natural gypsum, its SO330.0 to 35.0 wt%, 1 to 5wt% MgO, 90 to 95% whiteness, Fe2O3The content is less than 0.01 wt%.
The mineralizer is fluorite with CaF as effective component2The whiteness is 80-85%, Fe2O3The content is less than 0.35 wt%.
Example 1
A preparation method of a composite mineralizer suitable for white sulphoaluminate cement comprises the following steps:
(1) selecting fluorite, low-iron strontium slag, calamine, aluminum slag and white slag as composite materialsMixing mineralizing raw materials according to CaF20.4 part of composite mineralizer raw material, 0.4 part of SrO, 0.35 part of ZnO and 0.35 part of MgO are prepared according to the mixture ratio;
(2) uniformly mixing the raw materials in the step (1) according to the formula of the composite mineralizer, and then drying until the water content is lower than 1%;
(2) and (3) adding the dried raw materials in the step (2) into a KEQ-4L planetary ball mill, grinding and mixing uniformly, sieving with a 200-mesh sieve, and stopping grinding when the sieve residue is less than 5wt%, thus obtaining the composite mineralizer.
Example 2
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.65 part, 0.1 part of SrO, 0.1 part of ZnO, 0.65 part of MgO and parts by weight.
Example 3
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.3 part, 1.5 parts of SrO, 0.7 part of ZnO and 1.0 part of MgO.
Example 4
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.2 part, 0.8 part of SrO, 1.0 part of ZnO and 0.1 part of MgO.
Example 5
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF21.0 part, 0.1 part of SrO, 0.2 part of ZnO and 0.2 part of MgO.
Example 6
A preparation method of white sulphoaluminate cement clinker comprises the following steps:
(1) the designed mineral phase composition of the white sulphoaluminate cement clinker is as follows:
77.6％、C2S 13.3％、C3A 8.2％、C12A70.4 percent and 2.2 percent of impurities; according to the composition of the mineral phase, raw materials of aluminum slag, limestone, quartz sand, gypsum and a composite mineralizer are selected as raw materials, and the content of each raw material is as follows: 35.0% of aluminum slag, 46.2% of limestone, 1.2% of quartz sand, 16.1% of gypsum and 1.5% of a mineralizer, wherein the mineralizer is the mineralizer described in embodiment 1;
(2) putting the raw materials in the step (1) into a KEQ-4L planetary ball mill, grinding and mixing uniformly, and sieving the powder obtained after grinding with a 200-mesh sieve, wherein the sieve residue is less than 5 wt%;
(3) preparing the ground raw material in the step (2) into round blocks with the diameter of 60mm and the thickness of 10mm, then heating to 1150 ℃ in air atmosphere, calcining for 1.5h, and grinding to 400m specific surface area2And/kg, obtaining white sulphoaluminate cement clinker.
Example 7
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the composite mineralizer is the mineralizer described in example 2.
Example 8
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the composite mineralizer is the mineralizer described in example 3.
Example 9
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the composite mineralizer is the mineralizer described in example 4.
Example 10
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the composite mineralizer is the mineralizer described in example 5.
Example 11
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the calcined powder had a specific surface area of 350m2Per kg, i.e. a specific surface area of the white sulphoaluminate cement clinker of 350m2/kg。
Example 12
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the calcined powder had a specific surface area of 300m2Per kg, i.e. a specific surface area of the white sulphoaluminate cement clinker of 300m2/kg。
Example 13
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the calcination temperature of the clinker was 1100 ℃.
Example 14
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the calcination temperature was 1050 ℃.
Example 15
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
67.1％、C2S 17.1％、C3A 13.1％、C12A70.3 percent and 2.4 percent of miscellaneous minerals.
Example 16
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
70.4％、C2S 13.3％、C3A 12.0％、C12A70.8 percent and 3.5 percent of miscellaneous minerals.
Example 17
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
74.0％、C2S 12.2％、C3A 10.3％、C12A70.5% of, and3.0 percent of mineral.
Example 18
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
68.0％、C2S 18％、C3A 10.2％、C12A70.8 percent and 3.0 percent of miscellaneous minerals.
Example 19
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
78.0％、C2S 12％、C3A 8％、C12A70.3 percent and 1.7 percent of miscellaneous minerals.
Example 20
A process for the preparation of white sulphoaluminate cement clinker as in example 6, with the following differences: the mineral phase composition of the white sulphoaluminate cement clinker is as follows:
69.0％、C2S 15％、C3A 14％、C12A70.5 percent and 1.5 percent of miscellaneous minerals.
Comparative example 1
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.25 part, 1.6 parts of SrO, 0.08 part of ZnO and 1.1 part of MgO.
Comparative example 2
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF21.1 parts of SrO, 0.08 part of ZnO, 0.08 part of MgO and the weight parts of the components.
Comparative example 3
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.08 part, 0.5 part of SrO, 1.1 part of ZnO and 0.08 part of MgO.
Comparative example 4
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF21.1 parts of SrO, 0.2 part of ZnO, 1.0 part of MgO and the like.
Comparative example 5
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.3 part, 1.6 parts of SrO, 0.7 part of ZnO and 0.7 part of MgO.
Comparative example 6
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: 0.4 part of SrO, 0.35 part of ZnO and 0.35 part of MgO.
Comparative example 7
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 2, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.7 part, 1.0 part of ZnO, 0.15 part of MgO and the weight parts.
Comparative example 8
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 3, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF21.0 part, 0.1 part of SrO and 0.1 part of MgO.
Comparative example 9
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the example 4, and is characterized in that: the compound mineralizer comprises the following components in percentage by weight: CaF20.6 part, 0.2 part of SrO and 0.2 part of ZnO.
Comparative example 10
A method for preparing a composite mineralizer suitable for white sulphoaluminate cement, which is the same as the preparation method of the embodiment 1, and is characterized in that: the composite mineralizer is fluorite.
And (3) performance testing:
in order to verify the whiteness and early strength effects of the white sulphoaluminate cement clinker, the invention carries out the following experiments:
and (3) carrying out sealing and drying treatment on the white sulphoaluminate cement clinker obtained in the examples 6-10 and the comparative examples 1-6 to obtain an experimental sample, wherein the whiteness of the sample is determined according to a determination method specified in GB/T5950-2008 'method for measuring whiteness of building materials and non-metal minerals', and the mechanical property is determined according to a determination method specified in GB/T17671-1999 'method for testing cement mortar strength'. In addition, the invention also uses the common white cement clinker (mineral system C) sold in the market3S-C2S-C3A) And a common sulfoaluminate cement clinker (mineral system) on the market
-C2S-C4AF) as a blank control group; the results of the tests are shown in table 1.
TABLE 1
It can be seen that the whiteness and early strength of white sulphoaluminate cement clinker produced in examples 6 to 10 are generally higher than those obtained in comparative examples 1 to 10 and two blank controls, and further, the test results of comparative examples 6 to 10 and comparative examples 1 to 10 show that there is a rapid decline in whiteness and early strength of white sulphoaluminate cement clinker when the contents of the components in the mineraliser are not within the ranges specified in the present invention or when the mineraliser component as a whole is absent, because the components in the mineraliser of the present invention do not only act alone, for example: CaF2Can accelerate the decomposition of calcium carbonate and destroy SiO2The crystal lattice promotes the solid-phase reaction,in addition CaF2It also reduces the dissolving temperature of the sinter, improves the soft melting performance of the high-alumina sinter, reduces the liquid phase viscosity and improves the strength. And the components interact with each other to further improve the whiteness and early strength of white sulphoaluminate cement clinker, such as CaF2And the cement component can generate compounds such as sodium fluosilicate, calcium fluoroaluminate and the like through solid-phase reaction, and the compounds can promote the formation of substances such as dicalcium silicate, tricalcium aluminate and the like. SrO has the functions of stabilizing high-temperature crystalline phase, reducing calcination temperature and improving clinker performance, and ZnO can prevent beta-C2S direction gamma-C2The conversion of S, and has the effects of improving cement fluidity, reducing water demand and improving early strength, MgO can combine with cement clinker minerals into a solid solution and dissolve in a glass phase, and can also reduce the calcination temperature of the cement clinker, increase the quantity of liquid phases, reduce the viscosity of the liquid phases, be beneficial to the calcination of the cement clinker, and change the color and luster of the cement.
In addition, compared with common mineralizers such as fluorite and the like, the composite mineralizer can reduce the calcination temperature of the white sulphoaluminate cement clinker by about 150 ℃ compared with the compound mineralizer without the compound mineralizer, so that the quantity of liquid phase can be further increased, the viscosity of the liquid phase can be reduced, the calcination of the cement clinker can be facilitated, the color of the cement can be changed, and the whiteness and the early strength of the cement clinker can be further improved.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (5)
1. A composite mineralizer suitable for white sulphoaluminate cement is characterized in that: the composite mineralizer comprises the following components in parts by weight: CaF20.2-0.7 part of SrO, 0.1-0.8 part of ZnO, 0.1-0.7 part of MgO;
the CaF2The material is introduced from the fluorite, and then,the SrO is introduced from low-iron strontium slag, the ZnO is introduced from calamine, and the MgO is introduced from aluminum slag or/and white slag;
CaF in fluorite2The content of (A) is 50-70%, and the whiteness is 80-85%;
the SrO content of the low-iron strontium slag is 30-70%, and the whiteness is 75-80%;
the content of ZnO in the calamine is 40-75%, the whiteness is 70-80%, and the Fe content in the calamine is2O3The content is less than 0.1 percent;
the aluminum slag is white aluminum slag and Al thereof2O380-90 wt%, MgO 0.15-2 wt%, Fe2O3The content is 0.1-0.4 wt%, and the density is 2.2-2.6 g/cm3；
The white slag contains 8-12 wt% of MgO and Fe2O3The content is less than 0.15 wt%.
2. A white sulphoaluminate cement clinker which is characterized in that: the coating comprises the following components in parts by weight: 31.0-36.0% of aluminum slag, 45.0-52.0% of limestone, 0-4.0% of quartz sand, 15.0-20.0% of gypsum and 0.7-1.5% of a mineralizer, wherein the mineralizer is the composite mineralizer suitable for white sulphoaluminate cement as defined in claim 1;
the preparation method of the white sulphoaluminate cement clinker comprises the following steps:
s1, crushing, homogenizing and washing the white sulphoaluminate cement raw material, drying, grinding and uniformly mixing for later use;
s2, pressing the ground white sulphoaluminate cement raw material in the S1 into blocks, calcining, cooling and grinding to obtain white sulphoaluminate cement clinker;
in step S1, the ground white sulphoaluminate cement raw material is sieved by a 200-mesh sieve, and the residue on the sieve is less than 5 wt%; the white sulphoaluminate cement raw material consists of 31.0-36.0% of aluminum slag, 45.0-52.0% of limestone, 0-4.0% of quartz sand, 15.0-20.0% of gypsum and 0.7-1.5% of mineralizer;
in step S2, pressing the white sulphoaluminate cement raw material into round blocks with the diameter of 60mm and the thickness of 10 mm;
in the step S2, the calcination is carried out in an air atmosphere, the temperature is 1050-1150 ℃, and the time is 1-2 h;
the specific surface area of the white sulphoaluminate cement clinker obtained in the step S2 is 300-400 m2The whiteness is 85-92%, and the 3d strength is 65-80 MPa;
the mineral composition of the white sulphoaluminate cement clinker obtained in step S2 is: c4A3S̅ 68~78%、C2S 12~18%、C3A 8~14%、C12A70.3 to 0.8% by weight of a surfactant and further contains C2AS、CaSO4Ⅱ、3C2S•CaF2MgO, SrO, ZnO, CaO and solid solution impurities of metal components, wherein the total amount of the impurities is 1.5-3.5%.
3. A method of preparing a composite mineralising agent for white sulphoaluminate cement, as claimed in claim 1, wherein: the preparation method comprises the following steps:
(1) uniformly mixing fluorite, low-iron strontium slag, calamine, aluminum slag and white slag according to a proportion, and drying to obtain a mixture for later use;
(2) grinding the mixture obtained in the step (1), sieving, and then sealing to obtain the product;
in the step (1), drying the mixture until the water content is lower than 1%;
in the step (2), grinding the mixture into fine powder, and sieving the fine powder by a 200-mesh sieve, wherein the residue on the sieve is less than 5 wt%.
4. Use of a composite mineralizer according to claim 1, suitable for white sulphoaluminate cement, and/or white sulphoaluminate cement clinker according to claim 2, in the construction field.
5. Use according to claim 4, wherein the architectural field is the field of architectural decoration.
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| CN103664014A (en) * | 2013-12-19 | 2014-03-26 | 中国中材国际工程股份有限公司 | White sulphoaluminate cement and preparing method thereof |
| WO2015032482A1 (en) * | 2013-09-03 | 2015-03-12 | Heidelbergcement Ag | Fluxes/mineralizers for calcium sulfoaluminate cements |
| CN104446050A (en) * | 2014-12-19 | 2015-03-25 | 青岛理工大学 | Sulphoaluminate cement taking petroleum coke desulfurization residues and red mud as raw materials |
| CN106698986A (en) * | 2016-12-27 | 2017-05-24 | 嘉华特种水泥股份有限公司 | Production method of sulfoaluminate cement clinker |
| CN108395125A (en) * | 2018-05-18 | 2018-08-14 | 郑州市建文特材科技有限公司 | Partition plate, low alkalinity white sulphate aluminium cement and preparation method thereof |
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| WO2015032482A1 (en) * | 2013-09-03 | 2015-03-12 | Heidelbergcement Ag | Fluxes/mineralizers for calcium sulfoaluminate cements |
| CN103664014A (en) * | 2013-12-19 | 2014-03-26 | 中国中材国际工程股份有限公司 | White sulphoaluminate cement and preparing method thereof |
| CN104446050A (en) * | 2014-12-19 | 2015-03-25 | 青岛理工大学 | Sulphoaluminate cement taking petroleum coke desulfurization residues and red mud as raw materials |
| CN106698986A (en) * | 2016-12-27 | 2017-05-24 | 嘉华特种水泥股份有限公司 | Production method of sulfoaluminate cement clinker |
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