CN109369044B - Sulphoaluminate cement and preparation method thereof - Google Patents
Sulphoaluminate cement and preparation method thereof Download PDFInfo
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- CN109369044B CN109369044B CN201811430478.2A CN201811430478A CN109369044B CN 109369044 B CN109369044 B CN 109369044B CN 201811430478 A CN201811430478 A CN 201811430478A CN 109369044 B CN109369044 B CN 109369044B
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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
- C04B7/424—Oxides, Hydroxides
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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
- C04B7/38—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
- C04B7/36—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
- C04B7/425—Acids or salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a preparation method of sulphoaluminate cement, which comprises the following steps: selecting a material of sulphoaluminate cement, wherein the material comprises a lithium-containing substance, grinding the material to obtain raw material powder, and then calcining at 1200-1350 ℃ for 30min to obtain cement clinker; mixing the cement clinker with anhydrite, and grinding to obtain sulphoaluminate cement; the cement clinker comprises the following components in percentage by mass: 30-80% of anhydrous calcium sulphoaluminate, and dicalcium silicate: 10-40%, ferrite mineral 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3%, lithium oxide: 0.06-0.8% and boron oxide: 0 to 0.5 percent. The method can uniformly disperse the lithium salt or boric acid (salt) in the cement, and can synchronously release the lithium salt or boric acid (salt) when the lithium salt or boric acid (salt) reacts with water, thereby exerting the effect to the maximum extent and improving the early strength of the sulphoaluminate cement. The invention can utilize the lithium-containing and boron-containing waste as the raw material, and can utilize the waste while reducing the cost.
Description
Technical Field
The invention relates to the field of building materials, in particular to sulphoaluminate cement and a preparation method thereof.
Background
Sulphoaluminate cement is the cement which has the largest production quantity and the most extensive application besides silicate cement. Compared with Portland cement, sulphoaluminate cement has the outstanding advantage of rapid development of early performance, so the sulphoaluminate cement has wide application in the special construction fields of repair, rapid construction, low-temperature or negative-temperature construction and the like. Although the sulphoaluminate cement has the characteristics of quick hardening and early strength, the sulphoaluminate cement cannot completely meet increasingly diversified construction requirements such as rush repair, leakage stoppage and the like only by relying on the sulphoaluminate cement. Therefore, the sulphoaluminate cement still needs to be added with additives for performance control during the use process.
Lithium salt and boric acid (salt) are two types of additional components currently recognized as being most effective in adjusting early strength and setting time of sulphoaluminate cement, the former can promote setting and increase early strength, and the latter has a retarding effect on the former. However, these additional components are usually added in the cement application process, and are difficult to mix sufficiently and uniformly, and the solubility or dissolution rate of these two additional components is low, which results in the mismatch between the hydration rate of cement and the action time of the additional components, and further often causes unstable performance, even performance accidents. In addition, the lithium salt and boric acid (salt) which are used as the additional components are generally chemical raw materials, so the cost is high.
Disclosure of Invention
The invention mainly aims to provide sulphoaluminate cement and a preparation method thereof, and aims to solve the technical problems that lithium salt can be uniformly distributed in the cement and synchronously released in the hydration process, the efficacy of the sulphoaluminate cement is exerted to the maximum extent by cooperating with the action process of cement hydration, lithium salt and other additional components, the early strength of the sulphoaluminate cement is improved, and the sulphoaluminate cement is more suitable for practical use.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The preparation method of the sulphoaluminate cement provided by the invention comprises the following steps:
selecting a raw material of sulphoaluminate cement, wherein the raw material comprises a substance containing lithium elements, and grinding the raw material to obtain raw material powder; then calcining for 30min at 1200-1350 ℃ to obtain cement clinker;
mixing the cement clinker with anhydrite, and grinding to obtain sulphoaluminate cement;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate: 30-80%, dicalcium silicate: 10-40%, ferrite mineral: 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3% and lithium oxide: 0.06-0.8 percent.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the above method for producing a sulfoaluminate cement, the lithium element-containing material is at least one of a lithium salt and a lithium-containing waste.
Preferably, in the above method for preparing a sulfoaluminate cement, the lithium salt is lithium carbonate, lithium sulfate, lithium nitrate or lithium chloride; or the lithium-containing waste material is lithium slag or lithium-containing tailings.
Preferably, in the method for preparing the sulphoaluminate cement, the raw material further comprises a substance containing boron.
Preferably, in the method for preparing sulphoaluminate cement, the boron-containing substance is at least one of boric acid, boron gangue, borate and boron-containing waste.
Preferably, in the method for preparing sulphoaluminate cement, the borate is sodium tetraborate, calcium borate or magnesium borate; or the boron-containing waste is boron-containing waste residue or boron-containing tailings.
Preferably, the method for preparing sulphoaluminate cement, wherein the cement clinker further comprises: and the content of the boron oxide is not more than 0.5 percent in percentage by mass.
Preferably, in the preparation method of the sulphoaluminate cement, the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means.
The sulphoaluminate cement provided by the invention comprises cement clinker and gypsum,
wherein the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20 parts of;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate: 30-80%, dicalcium silicate: 10-40%, ferrite mineral: 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3%, lithium oxide: 0.06-0.8% and boron oxide: 0 to 0.5 percent.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the sulphoaluminate cement has a 2-hour strength of 12-17MPa, a 4-hour strength of 20-28MPa and a 1-day strength of 35-40 MPa.
By the technical scheme, the sulphoaluminate cement and the preparation method thereof provided by the invention at least have the following advantages:
1. firstly, adding a lithium-element-containing substance into a raw material of sulphoaluminate cement, and then calcining to obtain cement clinker; finally, mixing the cement clinker with anhydrite to obtain sulphoaluminate cement; the method is that a material containing lithium element is added into the raw material of the sulphoaluminate cement, and during high-temperature calcination, the lithium element can be dissolved in the cement melt, so that the lithium salt is uniformly dispersed in the sulphoaluminate cement product. Lithium in the cement raw meal can directly participate in a firing reaction in the formation process of cement clinker to form clinker minerals, and is finally dissolved in the clinker minerals in a solid solution mode. The cement prepared by the lithium-containing clinker only needs to be added with water during application, which is convenient for users to use and is more beneficial to quality control because the problems of uneven mixing of additional components, fluctuation of the quality of the additional components and the like are avoided. During the hydration process of cement prepared by the lithium-containing clinker after being mixed with water, lithium and other elements are released while the clinker minerals are hydrated, so that the hydration regulation function of the cement can be effectively exerted, and the early strength of the sulphoaluminate cement is improved. The technical scheme avoids the quality problems caused by mismatching of the hydration of the clinker minerals and the release rate of the additional components, fluctuation of the quality of the additional components and the like, and can effectively improve and regulate the quality of the sulphoaluminate cement. Experiments prove that the sulphoaluminate cement obtained by the method has the strength of 12-17MPa in 2 hours, 20-28MPa in 4 hours and 35-40MPa in 1 day.
2. According to the invention, the lithium-containing substance is added into the raw materials of the sulphoaluminate cement, the source of the lithium element is not limited, the chemical raw materials can be used as the source of lithium, the lithium slag can also be used as the raw materials, the boron-containing substance can also be added into the raw materials of the sulphoaluminate cement, the source of the boron element is not limited, the chemical raw materials can be used as the source of boron, the boron slag can also be used as the raw materials, and the waste can be utilized while the cost is reduced.
3. According to the invention, a proper amount of lithium element and boron element can be added into the raw material of the sulphoaluminate cement according to actual needs to adjust the setting time of the sulphoaluminate cement, so that the sulphoaluminate cement is not rapidly set, and the sulphoaluminate cement is not delayed for too long to lose early strength performance, thereby meeting increasingly diversified construction requirements, such as rush repair, leakage stoppage and the like.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the present invention provides a sulphoaluminate cement and a method for preparing the same, and the detailed implementation, structure, characteristics and effects thereof are described in detail below with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention provides a preparation method of sulphoaluminate cement, which comprises the following steps:
(1) selecting a raw material of sulphoaluminate cement, wherein the raw material comprises a substance containing lithium elements, and grinding the raw material to obtain raw material powder; then calcining for 30min at 1200-1350 ℃ to obtain cement clinker;
(2) mixing the cement clinker with anhydrite, and grinding to obtain sulphoaluminate cement;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate: 30-80%, dicalcium silicate: 10-40%, ferrite mineral: 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3% and lithium oxide: 0.06-0.8 percent.
The invention does not specifically limit the raw materials of the sulphoaluminate cement, preferably the raw materials for producing the conventional sulphoaluminate cement comprise: limestone, alumina, gypsum and the like, and some of the materials for the sulfoaluminate cement include iron ore and the like as required.
Further, the lithium element-containing material is at least one of a lithium salt and a lithium-containing waste material.
Preferably, the lithium salt is lithium carbonate, lithium sulfate, lithium nitrate or lithium chloride.
More preferably, the lithium salt is lithium carbonate.
Preferably, the lithium-containing waste material is lithium slag or lithium-containing tailings.
More preferably, the lithium-containing waste material is lithium slag.
In the prior art, although the lithium slag powder is used as a cement admixture to replace part of cement, the prior art mainly utilizes amorphous SiO with higher activity contained in the lithium slag2And Al2O3The invention has higher volcanic ash activity, and mainly utilizes the lithium element in the lithium slag; in addition, the present invention adds Li-containing element (including Li slag) into cement raw material and utilizes the high activity amorphous SiO contained in Li slag2And Al2O3Has high volcanic ash activity. The principles of the two are very different.
Firstly, adding a lithium-element-containing substance into a raw material of sulphoaluminate cement, and then calcining to obtain cement clinker; finally, mixing the cement clinker with anhydrite to obtain sulphoaluminate cement; the method is that a material containing lithium element is added into the raw material of the sulphoaluminate cement, and during high-temperature calcination, the lithium element can be dissolved in the cement melt and enter the crystal lattice of the clinker mineral, so that the lithium salt is uniformly dispersed in the sulphoaluminate cement product. Lithium in the cement raw meal can directly participate in a firing reaction in the formation process of cement clinker, and the lithium is synchronously released with conventional ions such as calcium, sulfur and the like to form clinker minerals and finally is dissolved in the clinker minerals in a solid mode. The cement prepared by the lithium-containing clinker only needs to be added with water during application, which is convenient for users to use and is more beneficial to quality control because the problems of uneven mixing of additional components, fluctuation of the quality of the additional components and the like are avoided. During the hydration process of cement prepared by the lithium-containing clinker after being mixed with water, lithium and other elements are released while the clinker minerals are hydrated, so that the hydration regulation function of the cement can be effectively exerted, and the early strength of the sulphoaluminate cement is improved. The technical scheme avoids the quality problems caused by mismatching of the hydration of the clinker minerals and the release rate of the additional components, fluctuation of the quality of the additional components and the like, and can effectively improve and regulate the quality of the sulphoaluminate cement. Effectively exerts the function of regulating hydration and improves the early strength of the sulphoaluminate cement.
Experiments prove that the sulphoaluminate cement obtained by the method has the strength of 12-17MPa in 2 hours, 20-28MPa in 4 hours and 35-40MPa in 1 day.
In the invention, the material containing lithium element is added into the material of the sulphoaluminate cement, the material containing lithium element is not limited, as long as the material containing lithium element can meet the condition of the invention; the source of lithium element is not limited, chemical raw materials can be used as the source of lithium, lithium slag can be used as the raw material, and the cost is reduced while the waste is utilized.
In a preferred embodiment, the raw material further includes a boron element-containing substance.
Further, the substance containing the boron element is at least one of boric acid, boron gangue, borate and boron-containing waste.
Preferably, the borate is sodium tetraborate, calcium borate or magnesium borate; the boron-containing waste is boron-containing waste residue or boron-containing tailings.
More preferably, the borate is sodium tetraborate, commonly known as borax.
According to the invention, the material containing the boron element is added into the raw materials of the sulphoaluminate cement, the material containing the boron element is not limited, and the material containing the boron element can meet the conditions of the invention; the source of boron is not limited, chemical raw materials can be used as the source of boron, boron slag can be used as the raw material, and the cost is reduced while the waste is utilized.
Firstly, adding a substance containing boron into a raw material of sulphoaluminate cement, and then calcining to obtain cement clinker; the method is that the material containing boron element is added into the raw material of sulphoaluminate cement, and during high-temperature calcination, the boron element can enter into the grid structure of the cement, so that boric acid (salt) can be uniformly dispersed in the cement. The boron has the functions of entering silicate minerals to activate the silicate minerals, delaying the hydration of calcium sulphoaluminate, prolonging the setting time of sulphoaluminate cement, keeping the plasticity of fresh concrete for a long time, facilitating the pouring and improving the construction. And the boric acid (salt) can regulate and control the early hydration speed and the setting time of the cement under the combined action of the boric acid (salt) and the lithium.
In the preparation process of the sulphoaluminate cement, a trace amount of Li is introduced by adding industrial reagents or utilizing waste residues2O or Li2O+B2O3. The introduction of the trace components can promote the sintering process of the clinker, and more importantly, the trace components are dissolved into the crystal lattices of the clinker minerals in a solid way and released synchronously with conventional ions such as calcium, sulfur and the like when the cement is hydrated, so that the hydration promotion effect of the cement is exerted most efficiently.
The lithium salt can promote the sulphoaluminate cement to be coagulated and increase early strength, the boric acid (salt) has a retarding effect on the sulphoaluminate cement to achieve the purpose of adjusting the coagulation time, and in the using process of the sulphoaluminate cement, a proper amount of lithium salt and boric acid (salt) are added according to actual needs to adjust the coagulation time of the sulphoaluminate cement, so that the sulphoaluminate cement is not rapidly coagulated, and the sulphoaluminate cement is not retarded too long to lose early strength performance, so as to meet increasingly diversified construction requirements, such as rush repair, leakage stoppage and the like.
Preferably, the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20.
The mass ratio of the cement clinker to the anhydrite is adjusted according to actual needs, and the setting and hardening speed of the cement can be adjusted by adding the gypsum. If gypsum is not mixed or the mixing amount of the gypsum is insufficient, the cement can be instantaneously set. However, if the amount of gypsum is too large, the setting of cement is accelerated, and the expansion, cracking and destruction of set cement are caused at a later stage.
The invention also provides sulphoaluminate cement, which comprises cement clinker and gypsum,
wherein the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20 parts of;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate (C)4A3$ h): 30-80% of dicalcium silicate (C)2S): 10-40% of ferrite mineral (C)4AF): 5-20%, free gypsum: 0-15%, perovskite (CT): 0-5%, free calcium oxide: 0-3%, lithium oxide (Li)2O): 0.06-0.8%, boron oxide (B)2O3):0-0.5%。
Preferably, the 2-hour strength of the sulphoaluminate cement is 12-17MPa, the 4-hour strength is 20-28MPa, and the 1-day strength is 35-40 MPa.
The present invention will be described in detail with reference to examples. The following examples are given to illustrate the detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
Example 1
A preparation method of sulphoaluminate cement comprises the following steps:
(1) limestone, alumina, anhydrite and lithium slag are used as raw materials, the specific components of the raw materials are shown in table 1, 60 parts of limestone, 28 parts of alumina, 8 parts of anhydrite and 4 parts of lithium slag are mixed in proportion, and the mixture is ground into raw material powder by a laboratory ball mill;
(2) adding 6-8% of water into raw material powder, stirring uniformly, pressing into raw material cakes, and drying;
(3) presintering the raw material cake in a muffle furnace at 950 ℃ for 30min, then transferring the raw material cake into a high-temperature electric furnace at 1300 ℃, preserving the heat for 1 hour, taking out the raw material cake, and cooling the raw material cake to room temperature by blowing to obtain clinker;
(4) mixing clinker and anhydrite according to the weight ratio of 85: 15, and grinding the mixture to obtain the cement with the specific surface area of 400cm 2/kg.
Table 1 raw material chemical composition (%)
Components | Loss | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | TiO2 | K2O | Na2O | SO3 | Li2O | Total |
Limestone | 41.25 | 3.62 | 0.95 | 0.41 | 52.68 | 0.31 | - | 0.17 | - | - | - | 99.39 |
Alumina (A) | 12.6 | 12.34 | 60.53 | 8.5 | 0.17 | 0.46 | 2.04 | - | 0.52 | 1.8 | - | 98.96 |
Anhydrite | 7.36 | 1.38 | 0.92 | 0.21 | 36.45 | 3.06 | - | - | 0.1 | 49.12 | - | 98.6 |
Lithium slag | 7.23 | 58.2 | 18.65 | 1.44 | 6.68 | 0.73 | - | 0.48 | - | 5.2 | 1.28 | 99.89 |
Example 2
A preparation method of sulphoaluminate cement comprises the following steps:
(1) limestone, alumina and desulfurized gypsum are used as main raw materials, industrial-grade lithium carbonate and borax are used as additives, and the specific components of the raw materials and the additives are shown in Table 2; mixing 55 parts of limestone, 32 parts of alumina, 12.3 parts of desulfurized gypsum, 0.5 part of lithium carbonate and 0.2 part of borax in proportion, and grinding the mixture into raw material powder;
(2) adding 6-8% of water into raw material powder, stirring uniformly, pressing into raw material cakes, and drying;
(3) preburning the raw material cake in a muffle furnace at 950 ℃ for 30min, then transferring the raw material cake into a high-temperature electric furnace at 1280 ℃, preserving heat for 1 hour, taking out, and cooling to room temperature by blowing to obtain clinker;
(4) mixing the clinker with the anhydrite according to a ratio of 84: 16, grinding to specific surface area of 400 +/-20 cm2/kg, and obtaining the cement.
Table 2 raw material chemical composition (%)
Components | Loss | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | TiO2 | Na2O | SO3 | Li2O | B2O3 | Total |
Limestone | 42.02 | 1.96 | 1.26 | 0.41 | 53.54 | 0.31 | - | - | - | - | - | 99.5 |
Alumina (A) | 11.4 | 10.21 | 65.53 | 6.5 | 1.12 | 0.46 | 1.86 | - | - | - | - | 97.08 |
Desulfurized gypsum | 8.59 | 4.06 | 1.84 | 0.67 | 34.14 | 3.34 | - | 0.18 | 46.3 | - | - | 99.12 |
Lithium carbonate | 59.9 | - | - | - | - | - | - | - | - | 40.1 | - | 100 |
Borax | 44.78 | - | - | - | - | - | - | 15.41 | - | - | 34.82 | 95.01 |
Example 3
A preparation method of sulphoaluminate cement comprises the following steps:
(1) limestone, alumina, natural gypsum, lithium slag, boron slag and the like are used as main raw materials, the specific components of each raw material are shown in table 3, the raw materials are ground into raw material powder according to the proportion of 54 parts of limestone, 24 parts of alumina, 11 parts of natural gypsum, 6 parts of lithium slag and 1 part of boron slag, the fineness of the raw material is controlled to 80 mu m, and the screen residue is 16-18%;
(2) the production of the ultra-early-strength sulphoaluminate cement is carried out on an industrial cement kiln, raw material powder enters the kiln after being preheated by a preheater, the temperature of a material in a burning zone in the kiln is controlled to be 1300-plus-energy 1350 ℃, the temperature is kept for 0.5 hour, coal powder is used as a fuel, and the entrainment of coal ash (the components are shown in a table 3) is 4 percent;
(3) mixing the fired clinker with anhydrite according to the weight ratio of 85: 15, and grinding the mixture to obtain the cement with the specific surface area of 400 +/-20 cm 2/kg.
Table 3 raw material chemical composition (%)
Components | Loss | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | TiO2 | K2O | Na2O | SO3 | Li2O | B2O3 | Total |
Limestone | 43.22 | 1.54 | 1.02 | 0.41 | 52.83 | 0.88 | - | - | - | - | - | - | 99.9 |
Alumina (A) | 14.4 | 10.21 | 66.11 | 5.8 | 0.82 | 0.41 | 2.01 | - | - | - | - | - | 99.76 |
Natural gypsum | 13.28 | 0.42 | 0.21 | 0.08 | 40.08 | 0.55 | - | 0.11 | - | 44.95 | - | - | 99.68 |
Lithium slag | 8.25 | 40.5 | 28.01 | 2.56 | 8.88 | 2.23 | 2.04 | 1.21 | 0.88 | 3.2 | 1.78 | - | 99.54 |
Boron slag | 40.2 | 9.34 | 2.24 | 1.21 | 3.01 | 35.2 | - | - | 3.58 | - | - | 3.72 | 98.5 |
Coal ash | 0.51 | 50.62 | 43.7 | 0.66 | 1.58 | 0.66 | 0.53 | 0.36 | 0.11 | - | - | - | 98.73 |
Comparative example
The cement was prepared from commercially available sulphoaluminate cement (containing 15% anhydrite) as the raw material, incorporating 0.3% lithium carbonate (analytical grade chemical) and 0.1% borax (analytical grade chemical).
The cement samples obtained in examples 1 to 3 and comparative example were measured according to GB/T20472-2006, and the specific surface area, initial setting time, final setting time, 2h compressive strength, 4h compressive strength, 1 day compressive strength and 28 day compressive strength were obtained, as shown in Table 4.
TABLE 4 physical Properties of the cements
It can be seen from examples 1-3 that the physical properties of the cement obtained in example 2 with the addition of industrial-grade lithium carbonate and borax and the cement obtained in example 3 with the addition of lithium slag and boron slag are almost completely consistent, which indicates that the effects achieved by using the lithium slag and the boron slag are the same as the effects achieved by industrial raw materials lithium carbonate and borax, and from the viewpoint of environmental protection and waste utilization, the lithium slag and the boron slag can be completely used to replace chemical raw materials.
As can be seen from examples 1-3 and comparative examples, the physical properties of the cement prepared in examples 1-3 are almost the same as, even improved or improved by the cement prepared in the comparative example, which shows that the measures taken in the examples of the present invention are effective, and the examples of the present invention add a lithium element-containing substance (and possibly a boron element-containing substance) to the material of the sulphoaluminate cement, do not limit the source of lithium (or boron), can use waste slag as the raw material, and can utilize waste while reducing the cost.
The recitation of numerical ranges herein includes all numbers subsumed within that range and includes any two numbers subsumed within that range. Different values of the same index appearing in all embodiments of the invention can be combined arbitrarily to form a range value.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of sulphoaluminate cement is characterized by comprising the following steps:
selecting a raw material of sulphoaluminate cement, wherein the raw material comprises a lithium-element-containing substance and a boron-element-containing substance, grinding the raw material to obtain raw material powder, and then calcining at 1200-1350 ℃ for 30min to obtain cement clinker;
mixing the cement clinker with anhydrite, and grinding to obtain sulphoaluminate cement;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate: 30-80%, dicalcium silicate: 10-40%, ferrite mineral: 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3%, lithium oxide: 0.06-0.8% and boron oxide: the content is not more than 0.5% and is not 0.
2. The process for producing a sulphoaluminate cement according to claim 1,
the lithium-containing material is at least one of lithium salt and lithium-containing waste.
3. The method of producing a sulfoaluminate cement of claim 2,
the lithium salt is lithium carbonate, lithium sulfate, lithium nitrate or lithium chloride; or the like, or, alternatively,
the lithium-containing waste material is lithium slag or lithium-containing tailings.
4. The process for producing a sulphoaluminate cement according to claim 1,
the substance containing the boron element is at least one of boric acid, boron gangue, borate and boron-containing waste.
5. The process for producing a sulphoaluminate cement according to claim 4,
the borate is sodium tetraborate, calcium borate or magnesium borate; or the like, or, alternatively,
the boron-containing waste is boron-containing waste residue or boron-containing tailings.
6. The process for producing a sulphoaluminate cement according to claim 1,
the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20.
7. The sulphoaluminate cement is characterized by comprising cement clinker and anhydrite,
wherein the mass ratio of the cement clinker to the anhydrite is 80-90: 10-20 parts of;
the cement clinker comprises the following components in percentage by mass:
anhydrous calcium sulfoaluminate: 30-80%, dicalcium silicate: 10-40%, ferrite mineral: 5-20%, free gypsum: 0-15%, perovskite: 0-5%, free calcium oxide: 0-3%, lithium oxide: 0.06-0.8% and boron oxide: 0-0.5% and not 0.
8. Sulphoaluminate cement according to claim 7,
the 2-hour strength of the sulphoaluminate cement is 12-17MPa, the 4-hour strength is 20-28MPa, and the 1-day strength is 35-40 MPa.
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CN112608047B (en) * | 2020-12-22 | 2023-05-09 | 中国建筑材料科学研究总院有限公司 | Modified sulphoaluminate cement and preparation method and application thereof |
CN112645617B (en) * | 2021-01-15 | 2022-03-04 | 济南大学 | Containing C7A5Magnesium aluminate cement material of M mineral |
WO2022203932A1 (en) * | 2021-03-26 | 2022-09-29 | University Of Kentucky Research Foundation | Production of activated-belite-csa clinkers at extremely low firing temperature |
CN113698116B (en) * | 2021-09-16 | 2022-04-19 | 南京工业大学 | Method for preparing high belite sulphoaluminate clinker by using lithium slag |
CN115710095B (en) * | 2022-12-13 | 2024-05-24 | 中国建筑材料科学研究总院有限公司 | Boron-phosphorus composite modified high belite sulphoaluminate cement clinker and preparation method thereof |
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