CN111393047B - High-iron belite cement and preparation method thereof - Google Patents

High-iron belite cement and preparation method thereof Download PDF

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CN111393047B
CN111393047B CN202010232069.2A CN202010232069A CN111393047B CN 111393047 B CN111393047 B CN 111393047B CN 202010232069 A CN202010232069 A CN 202010232069A CN 111393047 B CN111393047 B CN 111393047B
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cement
iron
belite
red mud
bayer process
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CN111393047A (en
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刘松辉
管学茂
王雨利
张海波
朱建平
勾密峰
史才军
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Henan University of Technology
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Henan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
    • C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
    • 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
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • 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
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention provides high-iron belite cement and a preparation method thereof, wherein cement clinker in the high-iron belite cement comprises the following minerals in percentage by mass: c2S：45～60％，C4AF：25～40％，C12A7: 5 to 20 percent. Uniformly mixing 50-60 wt% of Bayer process red mud and 40-50 wt% of limestone, grinding, tabletting to obtain a raw material sheet, calcining the raw material sheet, rapidly cooling to obtain cement clinker, uniformly mixing with gypsum, and grinding to prepare the high-iron belite cement. The cement has high early strength, continuously increased later strength and good mechanical property, the doping amount of the Bayer process red mud in the cement clinker reaches 60 percent, the utilization rate of the Bayer process red mud solid waste is improved to a great extent, the firing temperature of the cement clinker is lower, the production cost of the cement is reduced, and CO is reduced in the production process2And SO2、NOxAnd the like, the amount of the pollutant gas discharged.

Description

High-iron belite cement and preparation method thereof
Technical Field
The invention belongs to the technical field of red mud application, and particularly relates to high-iron belite cement and a preparation method thereof.
Background
The Bayer process red mud is solid waste discharged after alumina is dissolved out of natural bauxite through hot alkali, and about 1 to 2 tons of Bayer process red mud is discharged when 1 ton of alumina is produced. With the annual rise of alumina production capacity in China, the annual emission of Bayer process red mud in China exceeds 1 hundred million tons. At present, due to the lack of economic and feasible technologies for bulk utilization of red mud, the comprehensive utilization rate of the red mud is always at a lower level; according to the statistics of the national statistical bureau and the Chinese industrial solid waste network, the utilization rate of the red mud in China is only about 4 percent at present, so that a large amount of red mud is piled up. The piling up of the red mud not only occupies precious land resources, but also causes serious pollution to surrounding underground water bodies, soil, air and ecological environment, and even has great potential safety hazard of dam break. Therefore, how to realize the large-scale utilization of the red mud and reduce the environmental hazard of the red mud is a difficult problem which needs to be solved urgently by the alumina industry.
On the other hand, cement is the largest building material used in the world at present, but the traditional portland cement clinker is tricalcium silicate (C)3S：50％～65％，C2S: 20-30%) as leading mineral, and the clinker sintering temperature is higher, generally 1450 deg.C. The heat consumption of clinker during firing is from two aspects without considering other heat losses, namely, clinker minerals (mainly C)3S minerals) high temperature formation; another aspect is the decomposition of carbonates in the raw meal, where CaCO3The decomposition heat consumption accounts for about 46 percent of the theoretical heat consumption of the clinker; therefore, the fundamental reason for the high energy consumption of conventional portland cement clinker firing is its high calcium mineral design. In addition, the high calcium mineral design also results in excessive consumption of high quality limestone and high quality coal resources, and greenhouse gas CO2And harmful gas SO2、NOxEtc., thereby increasing energy, resource consumption and environmental load of the cement industry.
Patent CN 104496231B discloses a method for preparing high-iron alite-barium calcium sulphoaluminate cement by utilizing red mud and barium mud, wherein the weight percentages of all mineral phases of the cement are as follows: 5-8% of barium calcium sulphoaluminate, 15-19% of dicalcium silicate, 30-45% of tricalcium silicate, 25-45% of tetracalcium aluminoferrite and 4-8% of tricalcium aluminate. Patent CN 103373826B discloses a method for preparing low-carbon cement clinker from iron tailings, which uses iron tailings and limestone as main raw materials to prepare low-carbon cement clinker fired at a temperature lower than 1400 ℃. The mineral composition of the low-carbon cement clinker comprises 70-85% of dicalcium silicate, 5-15% of tricalcium silicate, 0-5% of tricalcium aluminate and 4-15% of tetracalcium aluminoferrite. In the methods, because cement still contains more high-calcium mineral tricalcium silicate (CaO content is 73.7 percent), the current situations of high pollution, high energy consumption and high emission in the cement industry are not fundamentally improved. The doping amount of the red mud is only 30 percent at most, and the red mud cannot be utilized on a large scale.
Patent CN 103922622B discloses a process for firing sulphoaluminate cement clinker by using aluminum ash, dealkalized red mud, desulfurized gypsum and carbide slag as raw materials. Patent CN 102765893A discloses a method for preparing sulphoaluminate special cement clinker by using waste fluorgypsum and red mud. Patent CN 105060745B discloses a method for preparing belite-sulphoaluminate-ferro-aluminate cement. Patent CN 103964713 a discloses a method for preparing belite sulphoaluminate cement by using fly ash and bayer process red mud. The cement takes low-calcium sulphoaluminate minerals as main minerals, the energy consumption for firing clinker is reduced, and the emission of carbon dioxide is reduced; however, the proportion of fluorine and sulfur raw materials and the calcining conditions need to be strictly controlled in the production process, the clinker is difficult to calcine, the environmental pollution is easy to cause, and the red mud mixing amount is very low, so that the large-scale utilization of the red mud cannot be realized.
Based on energy conservation and emission reduction and new requirements on climate change, the low-calcium silicate cement which takes low-calcium minerals (such as dicalcium silicate and tetracalcium aluminoferrite) as main minerals is produced, so that CO can be reduced2The discharge and the reduction of the calcining temperature can greatly improve the proportion of the solid wastes such as the red mud in the cement production raw materials, and the method has important significance in many aspects.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide high-iron belite cement and a preparation method thereof, which are used for overcoming the problems of serious pollution of red mud piling to surrounding underground water bodies, soil, air and ecological environment in the prior art and the problems of excessive energy consumption and serious environmental pollution caused by the design of high-calcium minerals in the traditional portland cement clinker.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of high-iron belite cement comprises the following steps:
uniformly mixing Bayer process red mud and limestone, wherein the Bayer process red mud accounts for 50-60 wt% and the limestone accounts for 40-50 wt%, grinding into raw material powder, and tabletting to obtain a raw material sheet;
step two, calcining the raw meal slices obtained in the step one, and then cooling to obtain cement clinker;
and step three, uniformly mixing the cement clinker obtained in the step two with gypsum, and grinding to prepare the high-iron belite cement.
According to the preparation method of the high-iron belite cement, as a preferable scheme, the raw material powder comprises the following components in percentage by mass: 50-55 wt% of Bayer process red mud and 45-50 wt% of limestone.
In the preparation method of the high-iron belite cement, as a preferable scheme, the bayer process red mud and the limestone in the first step both comprise the following components: SiO 22、Al2O3、Fe2O3、CaO、MgO、K2O、Na2O and TiO2；
Preferably, SiO in the Bayer process red mud2The content of (A) is 15-30 wt%; al in the Bayer process red mud2O3The content of (A) is 15-25 wt%; fe in Bayer process red mud2O3The content of (A) is 15-20 wt%; the content of CaO in the Bayer process red mud is 5-20 wt%; the content of CaO in the limestone is 45-55 wt%.
In the preparation method of the high-iron belite cement, as a preferable scheme, the fineness of the raw material powder ground in the step one is less than 75 μm.
According to the preparation method of the high-iron belite cement, as a preferable scheme, the calcining temperature in the step two is 1100-1250 ℃, and the calcining time is 1-2 hours.
In the above method for producing high-iron portland cement, the mass ratio of the gypsum to the high-iron portland cement clinker in the third step is preferably 0 to 20%.
According to the preparation method of the high-iron belite cement, as a preferable scheme, the specific surface area of the high-iron belite cement prepared by grinding in the step three is 350-450 m2/kg。
The high-iron belite cement prepared by the preparation method of the high-iron belite cement.
The high-iron belite cement is characterized in that cement clinker in the high-iron belite cement comprises the following minerals in percentage by mass: c2S：45～60％，C4AF：25～40％，C12A7：5～20％。
Preferably, the cement clinker comprises the following minerals in percentage by mass: c2S：50～60％，C4AF：30～40％，C12A7：5～10％。
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the cement clinker in the invention adopts Bayer process red mud and limestone as raw materials, the doping amount of the Bayer process red mud is up to 60%, the utilization rate of Bayer process red mud solid waste is improved to a great extent, the emission reduction pressure of the alumina industry is reduced, and the harm to the environment is reduced.
The firing temperature of the cement clinker in the invention is reduced by 200-350 ℃ compared with the firing temperature of the traditional silicate cement clinker, thereby reducing the production cost of cement, and greatly reducing CO in the production process2And harmful gas SO2、NOxAnd the like, the amount of the pollutant gas discharged.
In the cement clinker of the present invention, C is12A7And C4Early strength of cement provided by hydration of AF mineral, C2The hydration of S mineral provides the later strength of the cement, so that the prepared cement has high early strength and continuously increased later strength, and the mechanical property of the cement is slightly superior to that of common Portland cementIt can be widely used in outdoor building products, rush-repair engineering, underground engineering, etc.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is an XRD pattern of Bayer process red mud used in various examples and comparative examples of the present invention;
FIG. 2 is an XRD pattern of cement clinker prepared in the embodiments 2, 4 and 7 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The high-iron belite cement is prepared by mixing cement clinker with a certain proportion of gypsum and then grinding the mixture, wherein the cement clinker comprises C2S、C4AF、C12A7Minerals, C in cement clinker12A7And C4Early strength of cement provided by hydration of AF mineral, C2The hydration of S mineral provides the later strength of the cement, so that the prepared cement has high early strength and continuously increased later strength, has mechanical properties slightly superior to those of common Portland cement, and can be widely applied to outdoor building products, rush repair engineering, underground engineering and the like.
The cement clinker is prepared by mainly adopting Bayer process red mud and limestone as raw materials through calcining and cooling, and the doping amount of the Bayer process red mud reaches more than 60 percent in the preparation process of the cement clinker, so that the cement clinker is prepared by adopting the Bayer process red mud and the limestone as raw materialsThe utilization rate of the Bayer process red mud solid waste is improved to a certain extent, so that the pollution of red mud stacking to surrounding underground water, soil, air and ecological environment is reduced, and the emission reduction pressure of the alumina industry is reduced; in the production process of the cement clinker, the firing temperature of the cement clinker is reduced by 200-350 ℃ compared with that of the traditional silicate cement clinker, so that the production cost of the cement is reduced, and the CO is greatly reduced2And harmful gas SO2、NOxAnd the like, the amount of the pollutant gas discharged.
The invention provides a preparation method of high-iron belite cement, which comprises the following steps:
step one, uniformly mixing Bayer process red mud and limestone, wherein 50-60 wt% (such as 50wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%) of Bayer process red mud and 40-50 wt% (such as 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%) of limestone are ground into raw material powder, and then tabletting to obtain a raw material tablet.
In the specific embodiment of the invention, as a more preferable scheme, the raw meal powder comprises the following components in percentage by mass: 50-55 wt% (such as 50wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%) of Bayer process red mud, and 45-50 wt% (45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%) of limestone.
In the specific embodiment of the invention, the Bayer process red mud and limestone in the first step comprise the following components: SiO 22、Al2O3、Fe2O3、CaO、MgO、K2O、Na2O and TiO2；
SiO in Bayer process red mud2Is 15 to 30wt% (such as 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%); al in Bayer process red mud2O3Is 15 to 25wt% (e.g. 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20wt%, 21 wt%wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%); fe in Bayer process red mud2O3The content of (a) is 15-20 wt% (e.g. 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%); the content of CaO in the Bayer process red mud is 5-20 wt% (such as 5wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%); the content of MgO in the Bayer process red mud is less than 5wt%, and K in the Bayer process red mud2O and Na2The total content of O is less than 10 wt%, TiO in Bayer process red mud2Is less than 10 wt%.
The CaO content of the limestone is 45-55 wt% (such as 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%). In the embodiment of the invention, the fineness of the raw material powder ground in the first step is less than 75 μm.
In the embodiment of the invention, the purpose of tabletting in the first step is to make the raw material powder closely contact and promote the solid phase reaction of the clinker in the calcining process, a rotary kiln is used for calcining in the actual industrial production process, and tabletting is to press the uniformly mixed raw material powder into compact raw material tablets under the action of pressure and then calcine the raw material tablets in a furnace.
And step two, calcining the raw material slices obtained in the step one, and then cooling to obtain the cement clinker.
In the embodiment of the invention, the temperature of calcination in the second step is 1100-1250 ℃ (such as 1100 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃ and 1250 ℃), and the calcination time is 1-2 h (such as 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h and 2 h).
In the embodiment of the invention, the cooling in the second step is rapid cooling, and the rate of the rapid cooling is more than 100 ℃/min. The rapid cooling is specifically that cold air and the cement clinker after high-temperature calcination are adopted for heat exchange, so as to achieve the purposes of reducing the temperature of the calcined cement clinker and stabilizing the high-temperature crystal form.
And step three, uniformly mixing the cement clinker obtained in the step two with gypsum, and grinding to prepare the high-iron belite cement.
In the embodiment of the invention, the mass ratio of the gypsum to the high-iron belite cement clinker in the third step is 0-20% (e.g., 0, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%).
In the specific embodiment of the invention, the high-iron belite cement prepared by grinding in the step three has the specific surface area of 350-450 m2Kg (e.g. 350 m)2/kg、360m2/kg、370m2/kg、380m2/kg、390m2/kg、400m2/kg、410m2/kg、420m2/kg、430m2/kg、440m2/kg、450m2/kg)。
The invention also provides the high-iron belite cement prepared by the preparation method of the high-iron belite cement.
In a specific embodiment of the invention, the cement clinker in the high-iron belite cement comprises the following minerals in percentage by mass: c2S: 45-60% (such as 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%) C4AF: 25-40% (e.g., 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%) C12A7: 5-20% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%). Wherein, C2S is dicalcium silicate with a molecular formula of 2 CaO. SiO2At C2The CaO content in S is 65.1 wt%; c4AF is tetracalcium aluminoferrite with a molecular formula of 4 CaO. Al2O3·Fe2O3At C4The CaO content in AF was 46.2 wt%; c12A7Is dodecacalcium heptaluminate with a molecular formula of 12CaO 7Al2O3At C12A7The content of CaO in the steel is 48.4 wt%.
In a specific embodiment of the invention, the cement clinker comprises the following minerals in mass percent: c2S: 50-60% (e.g., 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%) C4AF: 30-40% (e.g., 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%) C12A7: 5-10% (e.g., 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%).
Among the raw materials used in the following examples and comparative examples, bayer process red mud was obtained from china, middle, and middle, aluminum, and limestone was obtained from local cement plant limestone, and the chemical composition of the raw materials is shown in table 1 below.
TABLE 1 chemical composition of Bayer process red mud and limestone
Figure BDA0002429575530000071
As shown in FIG. 1, XRD patterns of Bayer process red mud used in the following examples and comparative examples show that the phase of Bayer process red mud comprises 1-Al from XRD phase analysis results2SiO5(OH)5(Kaolin), 2-AlO (OH) (diaspore), 3-Ca3Al2(SiO4)(OH)8(hydrated garnet), 4-SiO2(Quartz), 5-CaCO3(calcite), 6-Na8(SiAlO4)6(H0.33(CO3)1.44)(H2O)2(cancrinite), 7-Fe2O3(hematite).
Example 1
The embodiment of the invention provides a preparation method of high-iron belite cement, which comprises the following steps:
step one, uniformly mixing 60 parts of Bayer process red mud and 40 parts of limestone, grinding the mixture into raw material powder with fineness less than 75 mu m, and tabletting to obtain a raw material sheet;
step two, placing the raw material slices obtained in the step one at 1200 ℃ for calcining for 2h, and then cooling to obtain cement clinker;
and step three, uniformly mixing the cement clinker obtained in the step two with gypsum (the mass of the gypsum is 10 percent of the mass of the cement clinker), and grinding to prepare the high-iron belite cement.
Mineral composition analysis: the mineral components of the high-iron belite cement clinker are determined by adopting an XRD full-spectrum fitting quantitative analysis technology.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：51％，C4AF：32.7％，C12A7: 16.3%, as shown in table 2.
Performance testing
The high-iron belite cement prepared in the examples of the present invention was subjected to a specific surface area test, which was carried out by using a cement boehrlich specific surface area meter with reference to the cement specific surface area measurement method boehrlich method GB/T8074-2008.
The high-iron belite cement prepared in the embodiment of the invention is mixed with water, poured and molded to prepare a 4cm x 4cm test block, the test block is placed in a standard cement concrete curing chamber for curing (the temperature is 20 +/-2 ℃, and the humidity is more than or equal to 95 percent), the curing is carried out for 28 days, and the compressive strength of the test block after the curing is carried out for 3 days and 28 days is measured according to the GB/T17671 and 1999 cement mortar strength test method (ISO method).
The high-iron belite cement prepared in the embodiment of the invention has the specific surface area of 373m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 18.6MPa after 3 d; the compressive strength after 28d was 44.4MPa, as shown in Table 2.
Example 2
In the preparation method of the high-iron belite cement provided by the embodiment of the invention, in the second step, the green sheet is calcined for 2 hours at 1100 ℃; in the third step, no gypsum is added. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：50.3％，C4AF：31.9％，C12A7: 17.8%, as shown in table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 365m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 19.1MPa after 3 d; the compressive strength after 28d was 43.9MPa, as shown in Table 2.
As shown in FIG. 2, the XRD pattern of the cement clinker prepared in this example revealed that the mineral composition C of the cement clinker in the high-iron belite cement prepared in this example was C2S、C4AF and C12A7。
Example 3
In the preparation method of the high-iron belite cement provided by the embodiment of the invention, in the second step, the green sheet is calcined for 2 hours at 1200 ℃; in the third step, the addition amount of the gypsum is 20 percent of the mass of the cement clinker. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：51.3％，C4AF：33.1％，C12A7: 15.6%, as shown in table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 369m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 18.4MPa after 3 d; the compressive strength after 28d was 45.2MPa, as shown in Table 2.
Example 4
In the preparation method of the high-iron belite cement provided in the embodiment of the invention, in the first step, 55 parts of bayer process red mud and 45 parts of limestone are mixed. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：55.4％，C4AF：33％，C12A7: 11.6%, as shown in table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 360m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 26.7MPa after 3 d; the compressive strength after 28d was 54.7MPa, as shown in Table 2.
As shown in FIG. 2, the XRD pattern of the cement clinker prepared in this example shows that the high-iron bainite prepared in this example can be obtained by XRDThe mineral composition of the cement clinker in the Litte cement is C2S、C4AF and C12A7。
Example 5
In the preparation method of the high-iron belite cement provided in the embodiment of the invention, in the second step, the green sheet is calcined at 1100 ℃ for 2 hours. Other methods and steps are the same as embodiment 4, and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：54.4％，C4AF：33.5％，C12A7: 12.1%, as shown in Table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 367m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 27.1MPa after 3 d; the compressive strength after 28d was 52.8MPa, as shown in Table 2.
Example 6
In the preparation method of the high-iron belite cement provided by the embodiment of the invention, in the second step, the green sheet is calcined at 1250 ℃ for 2 hours; in the third step, the addition amount of the gypsum is 20 percent of the mass of the cement clinker. Other methods and steps are the same as embodiment 4, and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：56.1％，C4AF：32.4％，C12A7: 11.5%, as shown in table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 364m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 26.9MPa after 3 d; the compressive strength after 28d was 55.2MPa, as shown in Table 2.
Example 7
In the preparation method of the high-iron belite cement provided in the embodiment of the invention, 50 parts of bayer process red mud and 50 parts of limestone are mixed in the first step; in the third step, the addition amount of the gypsum is 20 percent of the mass of the cement clinker. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：58％，C4AF：33.9％，C12A7: 8.1%, as shown in Table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 370m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention after 3d is 28.1 MPa; the compressive strength after 28d was 64.4MPa, as shown in Table 2.
As shown in FIG. 2, the XRD pattern of the cement clinker prepared in this example revealed that the mineral composition C of the cement clinker in the high-iron belite cement prepared in this example was C2S、C4AF and C12A7. In contrast to the high-iron portland cements prepared in examples 2 and 4, the higher the limestone content in the green powder and the lower the bayer process red mud content, at which point C in the mineral component of the cement clinker in the prepared high-iron portland cement2S、C4The content of AF is increased, and C12A7The content of the high-iron belite cement is reduced, and the compressive strength of the prepared high-iron belite cement is improved after curing for 3 days and curing for 28 days.
Example 8
In the preparation method of the high-iron belite cement provided by the embodiment of the invention, in the second step, the green sheet is calcined for 2 hours at 1100 ℃; in the third step, the addition amount of the gypsum is 10 percent of the mass of the cement clinker. Other methods and steps are the same as those of embodiment 7, and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：57.2％，C4AF：34.0％，C12A7: 8.8%, as shown in Table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 367m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 27.8MPa after 3 d; the compressive strength after 28d was 63.9MPa, as shown in Table 2.
Example 9
In the preparation method of the high-iron belite cement provided by the embodiment of the invention, in the second step, the green sheet is calcined at 1250 ℃ for 2 hours; in the third step, the addition amount of the gypsum is 10 percent of the mass of the cement clinker. Other methods and steps are the same as those of embodiment 7, and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the embodiment of the invention, the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d are carried out, wherein the mineral component analysis method, the specific surface area test standard and method and the compressive strength test standard and method are the same as those in the embodiment 1, and are not repeated herein.
The cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement in the embodiment of the invention comprises the following minerals in percentage by mass: c2S：58.1％，C4AF：34.2％，C12A7: 7.7%, as shown in Table 2.
The specific surface area of the high-iron belite cement prepared in the embodiment of the invention is 361m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the embodiment of the invention is 27.5MPa after 3 d; the compressive strength after 28d was 66.2MPa, as shown in Table 2.
Comparative example 1
In the preparation method of the high-iron belite cement provided in the present comparative example, 80 parts of bayer process red mud and 20 parts of limestone were mixed in the first step. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the comparative example, as well as the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d were performed, wherein the mineral component analysis method, the specific surface area test standard and method, and the compressive strength test standard and method are the same as those in example 1, and are not described herein again.
In the comparative example, the cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement comprises the following minerals in percentage by mass: c2AS：58.6％，C2S：5.6％，Fe2O3：22.3％，CaTiO3: 13.5 percent. Wherein, C2AS is gehlenite; c2S is dicalcium silicate; fe2O3Is hematite; CaTiO3Is a perovskite.
The high-iron belite cement prepared in this comparative example had a specific surface area of 350m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the comparative example after 3d is 0.7 MPa; the compressive strength after 28d was 3.9MPa, as shown in Table 2. In the mineral component of the cement clinker of this comparative example, only C is contained2S has hydration activity, and other minerals have no hydration activity, so the mechanical property of the high-iron belite cement prepared in the comparative example after curing is poor.
Comparative example 2
In the preparation method of the high-iron belite cement provided in the present comparative example, 40 parts of bayer process red mud and 60 parts of limestone were mixed in the first step. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the comparative example, as well as the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d were performed, wherein the mineral component analysis method, the specific surface area test standard and method, and the compressive strength test standard and method are the same as those in example 1, and are not described herein again.
In the comparative example, the cement clinker in the high-iron belite cement prepared by the preparation method of the high-iron belite cement comprises the following minerals in percentage by mass: c3A：50.9％，C2S：22.7％％，C4AF: 17.5%, f-CaO: 9.0 percent. Wherein, C3A is tricalcium aluminate; c2S is dicalcium silicate; c4AF is tetracalcium aluminoferrite; f. ofCaO is free calcium oxide.
The high-iron belite cement prepared in this comparative example had a specific surface area of 361m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the comparative example after 3d is 10.3 MPa; the compressive strength after 28d was 12.5MPa, as shown in Table 2. Due to mineral C in the cement clinker3A and C4The AF early hydration activity is higher, but the gelation property is poorer, so that the cement in the comparison example is hydrated and coagulated quickly, but has poor mechanical property and slow increase of later strength.
Comparative example 3
In the preparation method of the high-iron belite cement provided in the comparative example, the green sheet was calcined at 900 ℃ for 2 hours in the second step. Other methods and steps are the same as embodiment 1 and are not described herein again.
The mineral component analysis of the cement clinker in the high-iron belite cement prepared in the comparative example, as well as the specific surface area of the high-iron belite cement and the compressive strength of the high-iron belite cement after 3d and 28d were performed, wherein the mineral component analysis method, the specific surface area test standard and method, and the compressive strength test standard and method are the same as those in example 1, and are not described herein again.
After the green sheet in the comparative example is calcined at 900 ℃, limestone in the raw material is decomposed to produce calcium oxide, and then the calcium oxide reacts with oxides such as alumina, silica and the like in the Bayer process red mud to produce C2S、C12A7Minerals, but the amount of produced minerals is very small and C cannot be produced4AF。
The high-iron belite cement prepared in this comparative example had a specific surface area of 372m2The values of/kg are shown in Table 2.
The compressive strength of the high-iron belite cement prepared in the comparative example after 3d is 5.2 MPa; the compressive strength after 28d was 7.8MPa, as shown in Table 2.
Table 2 shows the mineral composition of the cement clinker, the specific surface area of the high-iron portland cement and the compressive strength of the high-iron portland cement after 3d and 28d in different examples, and the specific surface area of the high-iron portland cement prepared in different comparative examples and the compressive strength of the high-iron portland cement after 3d and 28 d.
TABLE 2
Figure BDA0002429575530000151
In conclusion, the cement clinker mainly adopts Bayer process red mud and limestone as raw materials, the doping amount of the Bayer process red mud is up to 60wt%, and the utilization rate of Bayer process red mud solid waste is improved to a great extent, so that the pollution to the environment is reduced, and the emission reduction pressure of the alumina industry is reduced; in the production process of the cement clinker, the firing temperature of the cement clinker is reduced by 200-350 ℃ compared with that of the traditional silicate cement clinker, so that the production cost of the cement is reduced, and the CO is greatly reduced2And harmful gas SO2、NOxThe discharge amount of the polluted gas is equal; the mechanical property of the finally prepared high-iron belite cement is slightly better than that of ordinary portland cement and C in cement clinker12A7And C4Early strength of cement provided by hydration of AF mineral, C2The hydration of the S mineral provides the later strength of the cement, so that the prepared cement has high early strength and continuously increased later strength.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.

Claims (6)

1. The preparation method of the high-iron belite cement is characterized by comprising the following steps of:
uniformly mixing Bayer process red mud and limestone, wherein the Bayer process red mud accounts for 50-60 wt% and the limestone accounts for 40-50 wt%, grinding into raw material powder, and tabletting to obtain a raw material sheet;
in the first step, the Bayer process red mud and the limestone comprise the following components: SiO 22、Al2O3、Fe2O3、CaO、MgO、K2O、Na2O and TiO2；
SiO in the Bayer process red mud2The content of (A) is 15-30 wt%; al in the Bayer process red mud2O3The content of (A) is 15-25 wt%; fe in Bayer process red mud2O3The content of (A) is 15-20 wt%; the content of CaO in the Bayer process red mud is 5-20 wt%;
the content of CaO in the limestone is 45-55 wt%;
step two, calcining the raw meal slices obtained in the step one, and then cooling to obtain cement clinker;
in the second step, the calcining temperature is 1100-1210 ℃, and the calcining time is 1-2 h;
step three, uniformly mixing the cement clinker obtained in the step two with gypsum, and grinding to prepare the high-iron belite cement;
in the third step, the mass ratio of the gypsum to the cement clinker is 16-20%;
the cement clinker in the high-iron belite cement consists of the following minerals in percentage by mass: c2S：45~60%，C4AF：25~40%，C12A7：5~20%。
2. The method for preparing high-iron belite cement according to claim 1, wherein the raw meal comprises the following components in percentage by mass: 50-55 wt% of Bayer process red mud and 45-50 wt% of limestone.
3. The method of claim 1, wherein the fineness of the raw material powder pulverized in the first step is less than 75 μm.
4. The method for preparing high-iron belite cement according to claim 1, wherein the specific surface area of the high-iron belite cement prepared by grinding in the third step is 350 to 450m2/kg。
5. A high-iron belite cement produced by the method for producing a high-iron belite cement according to any one of claims 1 to 4.
6. The high-iron belite cement of claim 5, wherein the cement clinker in the high-iron belite cement is comprised of the following minerals in mass percent: c2S：50~60%，C4AF：30~40%，C12A7：5~10%。
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