阅读说明：本技术 超高白度白色硫铝酸盐水泥及其制备方法 (Ultra-high whiteness white sulphoaluminate cement and preparation method thereof ) 是由 曾嵘 王振 黄少文 朱杰 鄢定英 李远华 张�荣 吴飞龙 于 2021-09-26 设计创作，主要内容包括：本发明涉及特种水泥技术领域,提供一种超高白度白色硫铝酸盐水泥及其制备方法。直接煅烧超高白度(亨特白度≥90)的硫铝酸盐水泥熟料是目前该领域尚未解决的技术难点。本发明采用石灰质原料、硅铝质原料、铝质原料、石膏和调整剂配料,磨细制成生料后,压片在高温炉(实验室条件)或生料粉喂入回转窑采用石油焦和生物质复合燃料(工业生产条件)煅烧一定时间,出窑(炉)熟料经冷却到100℃以下,得到白色硫铝酸盐熟料,将硫铝酸盐熟料与石膏、混合材、缓凝剂、增强剂计量配合后共同粉磨到一定细度,得到超高白度白色硫铝酸盐水泥。(The invention relates to the technical field of special cement, and provides white sulphoaluminate cement with ultrahigh whiteness and a preparation method thereof. The direct calcination of the sulphoaluminate cement clinker with ultrahigh whiteness (the Hunter whiteness is more than or equal to 90) is a technical difficulty which is not solved in the field at present. The invention adopts lime raw material, silicon-aluminum raw material, gypsum and regulator for batching, after grinding to make raw meal, the tablet is in the high temperature furnace (laboratory condition) or raw meal is fed into the rotary kiln and calcined for a certain time by petroleum coke and biomass composite fuel (industrial production condition), the clinker discharged from the kiln (furnace) is cooled to below 100 ℃ to obtain white sulphoaluminate clinker, the sulphoaluminate clinker is mixed with gypsum, mixed material, retarder and reinforcing agent in a metering way and then ground together to a certain fineness to obtain the white sulphoaluminate cement with ultrahigh whiteness.)

1. A preparation method of white sulphoaluminate cement with ultrahigh whiteness is characterized by comprising the following steps:

s1, metering and matching the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator, and then grinding to obtain a raw material;

s2, calcining the raw material at high temperature to obtain laboratory preparation clinker or industrial production clinker;

s3, cooling the clinker prepared in the laboratory or the clinker produced in the industrial production to be below 100 ℃ to obtain sulphoaluminate clinker;

and S4, metering and matching the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent, and then grinding to obtain the white sulphoaluminate cement with ultrahigh whiteness.

2. The method for preparing ultra-high whiteness white sulphoaluminate cement according to claim 1, wherein the method comprises the following steps:

in the step S1, the mixture ratio of the calcareous material, the aluminum material, the silicon-aluminum material, the gypsum and the regulator is as follows:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

3. The method of preparing ultra-high whiteness white sulphoaluminate cement according to claim 1 or 2, wherein:

in the step S1, the calcareous material, the aluminum material, the silicon-aluminum material, the gypsum and the regulator are weighed, matched and ground into powder until the fineness is 80 mu m and the screen residue of the square-hole sieve is less than or equal to 10 percent.

4. The method for preparing ultra-high whiteness white sulphoaluminate cement according to claim 1, wherein the method comprises the following steps:

in the step S2, the specific method of high-temperature calcination includes,

under the condition of a laboratory, the raw material is pressed and molded, and is placed into a high-temperature furnace and calcined under the environment of 1250-1350 ℃ to obtain laboratory preparation clinker, and the calcination time is 30-45 min;

under the condition of industrial production, the raw material is directly fed into a rotary kiln and calcined at 1250-1350 ℃ to obtain industrial production clinker, and the calcination time is 30-60 min.

5. The method for preparing ultra-high whiteness white sulphoaluminate cement according to claim 4, wherein the method comprises the following steps:

under industrial production conditions, the fuel used for high-temperature calcination comprises one or more of petroleum coke, biomass fuel, heavy oil, anthracite and bituminous coal.

6. The method for preparing ultra-high whiteness white sulphoaluminate cement according to claim 1, wherein the method comprises the following steps:

in step S3, the specific method for cooling the laboratory prepared clinker or the industrial produced clinker includes cooling the laboratory prepared clinker or the industrial produced clinker by using a cooling machine.

7. The method for preparing ultra-high whiteness white sulphoaluminate cement according to claim 1, wherein the method comprises the following steps:

in the step S4, the mixture ratio of the sulphoaluminate clinker, the gypsum, the mixed material, the retarder and the reinforcing agent is as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent;

wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate, boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

8. The method of preparing ultra-high whiteness white sulphoaluminate cement according to claim 1 or 7, wherein:

in the step S4, the sulphoaluminate clinker is metered and matched with gypsum, a mixture, a retarder and a reinforcing agent, and then the mixture is ground into powder with the specific surface area of 350-500 m²/kg。

9. The ultra-high whiteness white sulphoaluminate cement prepared by the method for preparing the ultra-high whiteness white sulphoaluminate cement of any one of claims 1 to 8, wherein the sulphoaluminate cement comprises sulphoaluminate clinker, gypsum, a mixing material, a retarder and a reinforcing agent, and the mixture ratio of the sulphoaluminate clinker, the gypsum, the mixing material, the retarder and the reinforcing agent is as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent;

wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate, boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

10. The ultra-high whiteness white sulfoaluminate cement of claim 9, wherein:

the sulphoaluminate clinker is prepared from raw materials, wherein the raw materials comprise the following components in parts by weight:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

Technical Field

The invention relates to the technical field of special cement, and particularly provides white sulphoaluminate cement with ultrahigh whiteness and a preparation method thereof

Background

The sulphoaluminate cement is a special cement variety invented in the last 70 th century in China, and the production and application in China are nearly half a century. The sulphoaluminate cement is a special hydraulic cementing material which is prepared by grinding clinker composed of anhydrous calcium sulphoaluminate and dicalcium silicate as main minerals, adding a proper amount of gypsum and limestone and has the characteristics of quick setting, quick hardening, early strength and low alkali, and is mainly applied to construction engineering in winter, preparation of shrinkage-compensating concrete and self-stress concrete, preparation of glass fiber reinforced cement (GRC) products, preparation of terrace mortar and grouting materials and the like.

In recent ten years, due to the characteristics of rapid hardening, early strength and low alkali of the sulphoaluminate cement, the sulphoaluminate cement has the advantages of high early strength, no corrosion to glass fiber and short service cycle of a template when being used for preparing building decoration materials such as GRC wallboards, inorganic artificial stones and urban sculpture products, so that the sulphoaluminate cement is increasingly applied to the building decoration materials. However, the whiteness of the traditional sulphoaluminate cement is low (usually 60-75 degrees), and the whiteness requirement of the decorative material is difficult to meet, so that the improvement of the whiteness of the sulphoaluminate cement becomes a research hotspot in recent years in some special cement enterprises and research institutes in China.

The invention patent applied by the international project of middle materials limited: the white sulphoaluminate cement is prepared by adopting white sulphoaluminate cement clinker, white silicate cement clinker, dolomite and gypsum, and the product is whitened by the dolomite and the white silicate cement, wherein the highest whiteness of the products in three examples introduced by the patent can reach 82 degrees. The invention patent applied by Kawa Special Cement Ltd of Sichuan: a white sulphoaluminate cement and its production method (application publication No. CN109437625A) is prepared from white sulphoaluminate cement clinker, white aluminate clinker, dolomite, limestone and gypsum through whitening the products by aluminate clinker, dolomite and limestone whose whiteness is greater than or equal to 90 deg. to obtain the product whose whiteness is greater than or equal to 87 deg. Invention patent applied by denna university: a white sulphoaluminate cement clinker and a production method thereof (application publication No. CN109369043A) adopt aluminum slag, limestone, quartz sand and gypsum as ingredients, fluorite is used as a mineralizer, the white sulphoaluminate cement clinker is fired by a laboratory high-temperature furnace at the temperature of 1200-1300 ℃, and the whiteness fluctuation of 13 introduced products in examples is 80-89 ℃.

Of the three patents mentioned above concerning white sulphoaluminate cements, the first two are mainly products whitened by incorporating high-whiteness raw materials in the clinker. The third patent is clinker fired in experiments by using dangerous waste aluminum slag as a raw material, and the safety of the clinker is to be investigated. At present, the report that the ultrahigh-whiteness clinker is directly calcined in batches and then ground to prepare the ultrahigh-whiteness (more than or equal to 90 ℃) sulphoaluminate cement does not exist in China.

Disclosure of Invention

The invention aims to provide a preparation method of white sulphoaluminate cement with ultrahigh whiteness, which aims to solve the problem that the prior art can not directly calcine clinker with ultrahigh whiteness in batches and then levigating the clinker to prepare white cement with ultrahigh whiteness.

In order to achieve the purpose, the invention adopts the technical scheme that:

in a first aspect, the present invention provides a method for preparing ultra-high whiteness white sulphoaluminate cement, comprising the steps of:

s1, metering and matching the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator, and then grinding to obtain a raw material;

s2, calcining the raw material at high temperature to obtain laboratory preparation clinker or industrial production clinker;

s3, cooling the clinker prepared in the laboratory or the clinker produced in the industrial production to be below 100 ℃ to obtain sulphoaluminate clinker;

and S4, metering and matching the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent, and then grinding to obtain the white sulphoaluminate cement with ultrahigh whiteness.

The invention has the beneficial effects that: the invention obtains the raw meal by grinding the calcareous raw material, the aluminium raw material, the alumino-silicate raw material, the gypsum and the regulator, the raw meal is calcined at high temperature to obtain the laboratory preparation clinker or the industrial production clinker, then the laboratory preparation clinker or the industrial production clinker is cooled to be below 100 ℃ to obtain the sulphoaluminate clinker, and finally the sulphoaluminate clinker, the gypsum, the mixed material, the retarder and the reinforcing agent are ground to obtain the white sulphoaluminate cement with ultrahigh whiteness.

Preferably, in step S1, the mixture ratio of the calcareous material, the aluminum material, the alumino-silica material, the gypsum and the modifier is as follows:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

Preferably, in step S1, the calcareous material, the aluminum material, the alumino-silicate material, the deleted gypsum and the modifier are weighed, mixed and ground into a 80 μm square-hole sieve with a sieve residue of less than or equal to 10%.

Preferably, in the step S2, the specific method of high-temperature calcination includes: under the condition of a laboratory, the raw material is pressed and molded, and is placed into a high-temperature furnace and calcined under the environment of 1250-1350 ℃ to obtain laboratory preparation clinker, and the calcination time is 30-45 min; under the condition of industrial production, the raw material is directly fed into a rotary kiln and calcined at 1250-1350 ℃ to obtain industrial production clinker, and the calcination time is 30-60 min.

Preferably, under industrial production conditions, the fuel used for high-temperature calcination comprises one or more of petroleum coke, biomass fuel, heavy oil, anthracite and bituminous coal.

Preferably, in step S3, the specific method for cooling the laboratory preparation clinker or the industrial production clinker includes cooling the laboratory preparation clinker or the industrial production clinker by using a cooling machine.

Preferably, in step S4, the mixture ratio of the sulphoaluminate clinker, the gypsum, the admixture, the retarder and the reinforcing agent is as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent;

wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate, boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

Preferably, in the step S4, the sulphoaluminate clinker is mixed with gypsum, the mixture, the retarder and the reinforcing agent, and then the mixture is ground into powder with the specific surface area of 350-500 m²/kg。

In a second aspect, the present application further provides a sulphoaluminate cement prepared by the preparation method of the ultra-high whiteness white sulphoaluminate cement, the sulphoaluminate cement comprises sulphoaluminate clinker, gypsum, a mixed material, a retarder and a reinforcing agent, and the proportions of the sulphoaluminate clinker, the gypsum, the mixed material, the retarder and the reinforcing agent are as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent.

Wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate, boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

The invention has the beneficial effects that: the ultra-high whiteness white sulphoaluminate cement is prepared by adopting the preparation method of the ultra-high whiteness white sulphoaluminate cement, and has ultra-high whiteness (more than or equal to 90 degrees).

Preferably, the sulfoaluminate clinker is prepared from a raw meal, which comprises the following components in the following proportions:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a flow chart of a preparation process of a preparation method of ultra-high whiteness white sulphoaluminate cement provided by an embodiment of the invention;

FIG. 2 is a flow chart of a preparation process of ultra-high whiteness white sulphoaluminate cement under laboratory conditions according to an embodiment of the present invention;

FIG. 3 is a flow chart of a product preparation process of the ultra-high whiteness white sulphoaluminate cement provided by the embodiment of the invention under industrial production conditions.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

In recent ten years, due to the characteristics of rapid hardening, early strength and low alkali of the sulphoaluminate cement, the sulphoaluminate cement has the advantages of high early strength, no corrosion to glass fiber and short service cycle of a template when being used for preparing building decoration materials such as GRC wallboards, inorganic artificial stones and urban sculpture products, so that the sulphoaluminate cement is increasingly applied to the building decoration materials. However, the whiteness of the traditional sulphoaluminate cement is low (usually 60-75 degrees), the whiteness requirement of the decorative material is difficult to meet, and the market urgently needs a cement with ultrahigh whiteness to meet the requirements of various building decorative materials.

Referring to fig. 1 to 3, in order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing ultra-high whiteness white sulphoaluminate cement, the method comprising the steps of:

s1, metering and matching the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator, and then grinding to obtain a raw material;

s2, calcining the raw material at high temperature to obtain laboratory preparation clinker or industrial production clinker;

s3, cooling the clinker prepared in the laboratory or the clinker produced in the industrial production to be below 100 ℃ to obtain sulphoaluminate clinker;

and S4, metering and matching the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent, and then grinding to obtain the white sulphoaluminate cement with ultrahigh whiteness.

The invention obtains the raw meal by grinding the calcareous raw material, the aluminium raw material, the alumino-silicate raw material, the gypsum and the regulator, the raw meal is calcined at high temperature to obtain the laboratory preparation clinker or the industrial production clinker, then the laboratory preparation clinker or the industrial production clinker is cooled to be below 100 ℃ to obtain the sulphoaluminate clinker, and finally the sulphoaluminate clinker, the gypsum, the mixed material, the retarder and the reinforcing agent are ground to obtain the white sulphoaluminate cement with ultrahigh whiteness.

Preferably, in step S1, the mixture ratio of the calcareous material, the aluminum material, the alumino-silica material, the gypsum and the modifier is as follows:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

Preferably, in step S1, the calcareous material, the aluminum material, the alumino-silicate material, the gypsum and the regulator are weighed, mixed and ground into a 80 μm square-hole sieve with a sieve residue of less than or equal to 10%. Wherein, under laboratory conditions, an experimental vibration mill (tungsten carbide bowl) can be adopted; under industrial production conditions, milling can be carried out using ball mills, roller mills, rod mills and extruders.

Preferably, in step S2, the specific method of high-temperature calcination includes pressing and molding the raw material under laboratory conditions, and placing the raw material into a high-temperature furnace to calcine at 1250-1350 ℃ to obtain laboratory-prepared clinker, i.e. high-temperature clinker, wherein the calcination time is 30-45 min. Wherein, the raw materials can be pressed into a cylinder with phi 30mm multiplied by 20mm by a tablet press, and then put into a silicon-molybdenum rod high-temperature furnace for high-temperature calcination.

Under the condition of industrial production, the raw materials are directly fed into a rotary kiln and calcined at 1250-1350 ℃ to obtain industrial production clinker, namely, the clinker taken out of the kiln, wherein the calcination time is 30-60 min.

Preferably, under industrial production conditions, the fuel used for high-temperature calcination includes one or more of petroleum coke, biomass fuel, heavy oil, anthracite coal, and bituminous coal. The petroleum coke and biomass fuel adopted in the fuel has the effects of preventing iron pollution and ensuring the whiteness of the product by utilizing the low-ash characteristic of the petroleum coke, and can provide sulfur element for the raw material. And the biomass fuel can improve the combustion characteristic of petroleum coke.

Preferably, in step S3, the specific method for cooling the laboratory preparation clinker or the industrial production clinker includes cooling the laboratory preparation clinker or the industrial production clinker by using a cooling machine. Specifically, the coolant may be a blower, a single-tube cooler, a grate cooler, or the like for cooling. Under laboratory conditions, the laboratory prepared clinker can be cooled by a blower; under the condition of industrial production, the clinker in industrial production can be cooled by a single-cylinder cooler or a grate cooler.

Preferably, in step S4, the mixture ratio of the sulphoaluminate clinker, the gypsum, the admixture, the retarder and the reinforcing agent is as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent;

wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate (borax), boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

Preferably, in the step S4, the sulphoaluminate clinker is mixed with gypsum, the mixture, the retarder and the reinforcing agent, and then the mixture is ground into powder with the specific surface area of 350-500 m²/kg。

The preparation method of the ultra-high whiteness white sulphoaluminate cement is slightly different from the steps of the preparation method under the laboratory condition and the industrial production condition, and the difference is specifically shown in the combined graph 2 and the graph 3.

In a second aspect, the present application further provides an ultrahigh-whiteness white sulphoaluminate cement prepared by the preparation method of the ultrahigh-whiteness white sulphoaluminate cement, wherein the sulphoaluminate cement comprises sulphoaluminate clinker, gypsum, a mixed material, a retarder and a reinforcing agent, and the proportion of the sulphoaluminate clinker, the gypsum, the mixed material, the retarder and the reinforcing agent is as follows:

80-90% of sulphoaluminate clinker, 5-15% of gypsum, 3-15% of mixed material, 0.1-0.8% of retarder and 0.005-0.8% of reinforcing agent.

Wherein the gypsum comprises one or more of natural anhydrite, natural dihydrate gypsum and mold gypsum;

the retarder comprises sodium borate (borax), boric acid, tartaric acid, sodium gluconate and citric acid;

the reinforcing agent comprises lithium carbonate, calcium nitrite and the like;

the mixed material comprises one or more of limestone powder, dolomite powder, slag powder and lithium slag powder.

The ultra-high whiteness white sulphoaluminate cement is prepared by adopting the preparation method of the ultra-high whiteness white sulphoaluminate cement, and the sulphoaluminate cement has ultra-high whiteness (more than or equal to 90 degrees).

Preferably, the sulfoaluminate clinker is prepared from a raw meal, wherein the raw meal comprises the following components in parts by weight:

30-50% of calcareous raw materials, 7-40% of aluminum raw materials, 3-20% of silicon-aluminum raw materials, 10-20% of gypsum and 1-3% of regulator;

wherein the calcareous raw material comprises one or more of limestone, chalk, shells, carbide slag and quicklime;

the aluminum raw material comprises one or more of aluminum oxide, aluminum hydroxide and aluminum ash;

the silicon-aluminum raw material comprises kaolin and bauxite;

the gypsum comprises one or more of natural dihydrate gypsum, anhydrous gypsum, desulfurized gypsum and mould gypsum;

the modifier comprises barite and/or cryolite.

Example 1

In this embodiment, the present invention provides a preparation method of an ultra-high whiteness white sulphoaluminate cement, the preparation method is performed under laboratory conditions, and the preparation method comprises the following steps:

s1, metering and proportioning the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator according to the following mixing ratio: 40% of limestone, 38.8% of aluminum hydroxide, 15.7% of natural anhydrite and 5.5% of kaolin. After the raw materials are metered and matched, an experimental vibration mill (tungsten carbide material pot) is adopted for grinding until the screen residue of a square-hole sieve with the size of 80 mu m is less than or equal to 10 percent, and the raw material is prepared.

The regulator has the functions of regulating the lowest eutectic temperature of the material under industrial production conditions, expanding the sintering temperature range, reducing ring formation and preventing high temperature escape of sulfur.

S2, pressing the raw materials into cylinders with the diameter of 30mm multiplied by 20mm by a tablet press, putting the cylinders into a silicon-molybdenum rod high-temperature furnace, and calcining for 30min at 1280 ℃ in a high-temperature environment to obtain the laboratory preparation clinker (or called as high-temperature clinker).

And S3, cooling the clinker prepared in the laboratory, and cooling to below 100 ℃ by adopting a blower to obtain the sulphoaluminate clinker.

S4, mixing the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent according to the following mixing ratio: 75.4% of sulphoaluminate clinker, 20% of mould gypsum, 4% of limestone powder, 0.6% of sodium borate and 0.006% of lithium carbonate, and the materials are ground together in an experimental vibration mill until the specific surface area is 450m²And/kg, the ultra-high whiteness sulphoaluminate cement is obtained.

Example 2

In the embodiment, the invention provides a preparation method of ultra-high whiteness white sulphoaluminate cement, which comprises the following steps:

s1, metering and proportioning the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator according to the following mixing ratio: 39.7 percent of limestone, 37.3 percent of aluminum hydroxide, 2 percent of bauxite, 16.3 percent of natural anhydrite and 4.7 percent of kaolin. The raw materials are weighed and matched, and then ground until the screen residue of a square-hole sieve with the size of 80 mu m is less than or equal to 10 percent to prepare raw materials.

And S2, pressing and molding the raw material, and then calcining at high temperature to obtain the laboratory prepared clinker. Wherein, the raw materials are pressed into cylinders with phi 30mm multiplied by 20mm by a tablet press, and are put into a silicon-molybdenum rod high-temperature furnace to be calcined for 30min at 1280 ℃ so as to obtain the laboratory preparation clinker.

And S3, cooling the laboratory preparation clinker, and cooling the laboratory preparation clinker to 100 ℃ by blowing air to obtain the sulphoaluminate clinker.

S4, mixing the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent according to the following mixing ratio: 76.5 percent of sulphoaluminate clinker, 17 percent of mould gypsum, 6 percent of limestone powder, 0.5 percent of sodium borate and 0.004 percent of lithium carbonate, and the materials are ground together in an experimental vibration mill until the specific surface area is 450m²And/kg, the ultra-high whiteness sulphoaluminate cement is obtained.

Example 3

In the embodiment, the invention provides a preparation method of ultra-high whiteness white sulphoaluminate cement, which comprises the following steps:

s1, metering and proportioning the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator according to the following mixing ratio: 40.1 percent of limestone, 32.6 percent of aluminum hydroxide, 5.3 percent of bauxite, 17.2 percent of natural anhydrite and 4.8 percent of kaolin. The raw materials are weighed and matched, and then ground until the screen residue of a square-hole sieve with the size of 80 mu m is less than or equal to 10 percent to prepare raw materials.

And S2, pressing and molding the raw material, and then calcining at high temperature to obtain the laboratory prepared clinker. Wherein, the raw materials are pressed into cylinders with phi 30mm multiplied by 20mm by a tablet press, and are put into a silicon-molybdenum rod high-temperature furnace to be calcined for 30min at 1280 ℃ so as to obtain the laboratory preparation clinker.

And S3, cooling the laboratory preparation clinker, and cooling the laboratory preparation clinker to 100 ℃ by blowing air to obtain the sulphoaluminate clinker.

S4, mixing the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent according to the following mixing ratio: 77.6 percent of sulphoaluminate clinker, 19.7 percent of mould gypsum, 2 percent of limestone powder, 0.7 percent of sodium borate and 0.005 percent of lithium carbonate, which are ground together in an experimental vibration mill until the specific surface area is 450m²And/kg, the ultra-high whiteness sulphoaluminate cement is obtained.

Example 4

In the embodiment, the invention provides a preparation method of ultra-high whiteness white sulphoaluminate cement, which comprises the following steps:

s1, metering and proportioning the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator according to the following mixing ratio: 43.2% of limestone, 20.4% of aluminum hydroxide, 7.7% of alumina powder, 7.0% of bauxite, 16.6% of natural anhydrite and 5.1% of kaolin. The raw materials are weighed and matched, and then ground until the screen residue of 80 mu m is less than or equal to 10 percent to prepare raw materials.

And S2, pressing and molding the raw material, and then calcining at high temperature to obtain the laboratory prepared clinker. Wherein, the raw materials are pressed into cylinders with phi 30mm multiplied by 20mm by a tablet press, and are put into a silicon-molybdenum rod high-temperature furnace to be calcined for 30min at 1280 ℃ so as to obtain the laboratory preparation clinker.

And S3, cooling the laboratory preparation clinker, and cooling the laboratory preparation clinker to 100 ℃ by blowing air to obtain the sulphoaluminate clinker.

S4, mixing the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent according to the following mixing ratio: 77.6 percent of sulphoaluminate clinker, 19.7 percent of mould gypsum, 2 percent of limestone powder, 0.7 percent of sodium borate and 0.005 percent of lithium carbonate, which are ground together in an experimental vibration mill until the specific surface area is 450m²And/kg, the ultra-high whiteness sulphoaluminate cement is obtained.

Example 5

In the embodiment, the invention provides a preparation method of ultra-high whiteness white sulphoaluminate cement, which comprises the following steps:

s1, metering and proportioning the calcareous raw material, the aluminum raw material, the silicon-aluminum raw material, the gypsum and the regulator according to the following mixing ratio: 40.3 percent of limestone, 38.2 percent of aluminum hydroxide, 15.0 percent of natural anhydrite and 6.5 percent of kaolin. The raw materials are fed into a phi 2.2 x 9m ball mill after being metered and matched to be ground until the sieve residue of 80 mu m is less than or equal to 10 percent, and then the raw materials are prepared.

S2, feeding the prepared raw material into a rotary kiln with a phi 2.7 x 42m and a five-stage cyclone preheater to calcine to obtain industrial production clinker, wherein the fuel for calcining the clinker is a composite fuel formed by combining petroleum coke and biomass fuel (rice hull), and the mixing ratio of the two fuels is as follows: 80% of petroleum coke and 20% of rice husk. The temperature of the high-temperature zone is controlled to be 1280 +/-30 ℃, and the rotating speed of the rotary kiln is controlled to be 0.8-1.0 r/min.

And S3, cooling the industrial production clinker, and cooling the industrial production clinker to 100 ℃ by using a single-cylinder cooler to obtain the sulphoaluminate clinker.

S4, mixing the sulphoaluminate clinker with gypsum, a mixed material, a retarder and a reinforcing agent according to the following mixing ratio: 84.0 percent of sulphoaluminate clinker, 4.0 percent of die gypsum, 8.0 percent of anhydrite, 3.5 percent of limestone powder, 0.5 percent of sodium borate and 0.008 percent of lithium carbonate, and the materials are jointly ground in a phi 2.2 x 9m ball mill to the specific surface area of 450m²And/kg, the ultra-high whiteness sulphoaluminate cement is obtained.

The mineral composition of the sulphoaluminate clinker fired in the five examples is quantitatively analyzed by XRD-Rietveld full-spectrum fitting, and the result is shown in Table 1. The performance indexes of the ultra-high whiteness sulphoaluminate cement prepared by the above 5 examples are shown in Table 2.

TABLE 1 mineral composition of sulphoaluminate clinker for each example

TABLE 2 physical and mechanical Properties of the ultra-high whiteness sulphoaluminate cements prepared in the examples

Note: whiteness measurement was measured according to the method specified in appendix A of GB/T2015-2017 and was reported as Hunter whiteness.

The setting time is measured according to the GB/T1346 specification, and the compressive strength is measured according to the GB/T17671 specification.

In conclusion, the sulphoaluminate cement prepared by the preparation method of the ultra-high whiteness white sulphoaluminate cement provided by the invention has whiteness of more than 90 percent, and fills up the domestic blank in the technical aspect of the ultra-high whiteness white sulphoaluminate cement.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.