CN112723763A - Raw material, cement clinker, negative temperature engineering material and method using high-calcium iron tailings - Google Patents
Raw material, cement clinker, negative temperature engineering material and method using high-calcium iron tailings Download PDFInfo
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- CN112723763A CN112723763A CN202011620505.XA CN202011620505A CN112723763A CN 112723763 A CN112723763 A CN 112723763A CN 202011620505 A CN202011620505 A CN 202011620505A CN 112723763 A CN112723763 A CN 112723763A
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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
- C04B7/22—Iron ore cements ; Iron rich cements, e.g. Ferrari cements, Kühl 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention relates to a raw material, a cement clinker, a negative temperature engineering material and a method by utilizing high-calcium iron tailings. The raw material comprises 34-40 parts by weight of CaO and SiO26-12 parts by weight of Al2O320-28 parts by weight of Fe2O35-12 parts by weight of SO312 to 18 weight portions, and the aluminum-sulfur ratio is 1.5 to 2.0. The raw materials are uniformly mixed and homogenized according to a set proportion, and the homogenized raw material is calcined at the temperature of 1220-1250 ℃ for 30-45min to obtain the cement clinker. When used as a negative temperature engineering material, can ensure that the hydration reaction is continuously carried out, and realizes the strength at negative temperatureAnd (4) increasing. The calcining temperature is reduced, and the energy consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of negative temperature engineering materials, and particularly relates to a raw material, cement clinker, a negative temperature engineering material and a method by utilizing high-calcium iron tailings.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, Portland cement is commonly used in winter construction, and measures such as heating and heat preservation, pre-curing or adding early strength agents and antifreezing agents are needed to meet the expected performance requirements, so that the cost and energy consumption in the construction and maintenance process are increased.
The main mineral of the portland cement is tricalcium silicate (3 CaO. SiO)2) Dicalcium silicate (2 CaO. SiO)2) Tricalcium aluminate (3 CaO. Al)2O3) And tetracalcium aluminoferrite (4 CaO. Al)2O3·Fe2O3) The cement has poor performance under the condition of negative temperature and cannot reach the critical freezing resistance strength in time due to long heat release period and low early-stage heat release amount in the hydration reaction process.
In the traditional production of sulphoaluminate cement, high-quality bauxite, limestone and gypsum are used as main raw materials, and sulphoaluminate cement is prepared through a series of links such as raw material selection, batching, crushing, grinding, calcination (1300-. The main mineral phase of the sulphoaluminate cement clinker is anhydrous calcium sulphoaluminate (3 CaO.3Al)2O3·CaSO4) Dicalcium silicate (2 CaO. SiO)2) And iron phase, Al in clinker2O328-40 wt% of the raw materials and in the traditional process, in order to ensure complete solid-phase reaction,The generation of effective ore phase needs to ensure the high CaO content in the raw meal, but the quality requirement on the raw meal is also increased, and the production cost is increased.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a raw material, a cement clinker, a negative temperature engineering material and a method using high-calcium iron tailings.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in the first aspect, the raw material utilizing the high-calcium iron tailings comprises the high-calcium iron tailings, desulfurized gypsum, aluminum ash and limestone, wherein CaO in the raw material accounts for 34-40 parts by weight, and SiO accounts for26-12 parts by weight of Al2O320-28 parts by weight of Fe2O35-12 parts by weight of SO312 to 18 weight portions, and the aluminum-sulfur ratio is 1.5 to 2.0.
The raw materials are reasonable in component proportion, the contents of iron oxide, aluminum oxide, calcium oxide and the like are matched with each other, the effective mineral proportion of the sulphoaluminate cement (negative temperature engineering material) is changed, the early heat release of the sulphoaluminate cement is influenced, the heat of early hydration reaction in a negative temperature environment is provided, the reaction is ensured to be continuously carried out, and the anti-freezing critical strength is reached as early as possible.
The water exists in a pore channel structure of the cement and has hydration reaction with the cement, free water is mainly frozen in a negative temperature environment, the influence on early strength is large, the freezing point of the water in the pore diameter is reduced along with the reduction of the pore diameter, the total porosity of the sulphoaluminate cement stone is lower than 15%, the average pore diameter is small, most of the pore diameters are smaller than 30nm, so that the freezing point of the water in the pore diameter is reduced, most of the pores are ink bottle pores, and the pore structure is a key for forming excellent performances of the sulphoaluminate cement, such as freezing resistance, seepage resistance, corrosion resistance and the like.
Meanwhile, the solid waste cement contains various salts, the addition of the salts also lowers the freezing point of water, free water in the cement paste is not completely frozen in a negative temperature environment, and a part of liquid phase water still reacts with the cement. Therefore, when the negative temperature engineering material is used as a cement material, the hydration reaction can be continuously carried out to generate a material with high hardness, so that the negative temperature engineering material can maintain the performance of the cement in a negative temperature environment.
In the production process of traditional sulphoaluminate cement, if Fe is contained in the cement raw meal2O3When the content of (A) is too high, tetracalcium aluminoferrite with small effect can be generated, and the characteristics of early strength and high strength of the sulphoaluminate cement cannot be maintained. In order to ensure the generation quantity and quality of anhydrous calcium sulphoaluminate, the Fe in the cement raw meal is generally required to be controlled2O3The content of (A) is less than 3 percent, namely, only a small amount of iron-containing minerals can be added into the cement raw meal. However, the calcination temperature is seriously affected by the low Fe content, so that the normal generation of clinker mineral phases is avoided, and the cement performance is reduced.
The raw meal has higher Fe2O3Content, can avoid generating tetracalcium aluminoferrite. While helping to lower the calcination temperature of the raw meal.
Meanwhile, the content of aluminum and calcium in the raw meal is lower than that of the traditional process, and the content of iron and sulfur in the raw meal is obviously higher than that of the traditional process.
The high-calcium iron tailings break through the requirement of alkalinity coefficient in the traditional sulphoaluminate cement production process by controlling key parameters such as raw material chemical composition, aluminum-sulfur ratio and the like, and can be reduced to 0.85-0.95; the alkalinity coefficient is reduced, the content of CaO in the cement raw meal is reduced, and the dependence on high-calcium raw materials such as limestone is further reduced.
The content of aluminum in the raw material is low, and the early strength and high strength performance of the cement cannot be influenced, because the iron element in the calcined clinker partially replaces the aluminum element to generate the calcium sulphoaluminate, and then the iron element and the calcium element are cooperated to generate anhydrous calcium sulphoaluminate, so that the cement has better early strength and high strength performance.
In some embodiments of the present invention, the raw meal comprises high calcium iron tailings, desulfurized gypsum, aluminum ash and limestone, wherein CaO in the raw meal is 34-40 parts by weight, and SiO is211-12 parts by weight of Al2O326-28 parts by weight of Fe2O37-9 parts by weight of SO315-18 parts by weight of aluminum-sulfur ratio of 1.5-2.0.
In some embodiments of the invention, the alkalinity factor of the raw meal is from 0.85 to 0.95; preferably 0.88-0.92.
In some embodiments of the invention, the main component of the high-calcium iron tailings is CaO: 25-32% wt, SiO2：28-35％wt，Al2O3：5-8％wt，Fe2O3：6-9％wt，SO3: 3-8% wt. The high-calcium iron tailings are solid wastes discharged after grinding ores and then selecting useful components, are important sources of environmental pollution in the mineral industry, and mainly comprise oxides such as silicon, calcium, iron, aluminum, magnesium, sulfur and the like. Preferably, the main components of the high-calcium iron tailings are CaO: 30.77% wt, SiO2：31.98％wt，Al2O3：6.49％wt，Fe2O3：8.13％wt，SO3：4.63％wt。
In a second aspect, a cement clinker is prepared from the raw material of the high calcium iron tailings.
In a third aspect, the method for preparing the cement clinker comprises the following steps: and calcining the raw material utilizing the high-calcium iron tailings to obtain the cement clinker.
In some embodiments of the invention, the calcination temperature is 1220-1250 ℃ and the calcination time is 30-45 min. The calcination temperature can be reduced due to the raw material composition in the raw meal compared to the reduction in calcination temperature of portland cement clinker.
In a fourth aspect, a negative temperature engineering material (sulphoaluminate cement) comprises the above cement clinker and gypsum.
In some embodiments of the invention, the sulphate aluminium cement comprises from 3 to 8% by mass of gypsum, the remainder being cement clinker.
In a fifth aspect, the use of the above raw meal, cement clinker, sulphoaluminate cement in the field of construction engineering.
Preferably, the temperature range used is-15 ℃ or higher; further preferably from-15 ℃ to 45 ℃.
In a sixth aspect, a system for producing a sulphoaluminate cement comprises: a drying device, a homogenizing device and a calcining device which are connected in sequence.
In some embodiments of the invention, the drying device is divided into a high-calcium iron tailing drying device, a limestone drying device, a desulfurized gypsum drying device and an aluminum ash drying device, the high-calcium iron tailing drying device and the limestone drying device are respectively connected with the crushing device, and the crushing device is connected with the homogenizing device.
In some embodiments of the present invention, the present invention further comprises a primary grinding device and a secondary grinding device, and the homogenizing device is connected to the primary grinding device, the secondary grinding device and the calcining device in sequence.
One or more technical schemes of the invention have the following beneficial effects:
1. compared with the traditional portland cement and modified portland cement, the ferro-sulphur-aluminium cement produced by the high-calcium iron tailings has better frost resistance and durability. When the temperature is higher than-15 ℃, the compressive strength of the sulpho-aluminoferrite cement produced by the high-calcium-iron tailings can be increased, which indicates that the hydration process of the sulpho-aluminate cement can not be prevented in a negative temperature environment.
2. The ferro-sulphur-aluminium cement produced by adopting the high-calcium iron tailings can realize positive increase of strength without adopting heat preservation measures and adding an early strength agent and an antifreezing agent in an environment with the temperature of above-5 ℃, and the 28d strength can meet the requirement of 425 cement standards.
3. The sulpho-alumino-ferro cement produced by using the high-calcium iron tailings has low requirements on raw materials, the calcination temperature is far lower than that of the traditional sulpho-aluminate cement, and the cost can be reduced by about 20 percent.
Drawings
FIG. 1 is a flow chart of a production system;
FIG. 2 is an X-ray diffraction pattern of the clinker obtained in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Fig. 1 shows a flow chart of a production system, which includes: the device comprises a drying device, a crushing device, a homogenizing device, a primary grinding device, a secondary grinding device and a calcining device which are connected in sequence. Drying device divide into high-calcium iron tailing drying device, lime stone drying device, desulfurization gypsum drying device, aluminium ash drying device, and high-calcium iron tailing drying device, lime stone drying device are connected with breaker respectively, and breaker is connected with the homogenization device. The homogenizing device is connected with the primary grinding device, the secondary grinding device and the calcining device in sequence.
The invention will be further illustrated by the following examples
Example 1
Homogenizing and mixing the high-calcium iron tailings, the desulfurized gypsum, the aluminum ash and the limestone, wherein the alkalinity coefficient of the homogenized cement raw material is 0.91, the CaO accounts for 38 parts by weight, and the SiO accounts for 38 parts by weight211 parts by weight of Al2O326 parts by weight of Fe2O37 weight portions of SO3Accounting for 15 weight portions. And then, conveying the homogenized material to a rotary kiln for calcination, wherein the calcination temperature is 1220 ℃, the calcination time is 30min, and cement clinker is obtained, and the main mineral composition of the cement clinker is shown in table 1. Adding 5% of gypsum into cement clinker, and grinding the cement clinker by a cement grinding machine to obtain sulphoaluminate cement, wherein the main mineral composition of the sulphoaluminate cement is shown in Table 1. And preparing the fired cement into a mortar block and placing the mortar block in a negative temperature environment. The properties of the mortar block prepared are shown in Table 2. The strength test standard is carried out according to GB20472-2006 sulphoaluminate cement.
TABLE 1 composition of main minerals in cement clinker (% by weight)
| Components | Calcium sulphoaluminate | Gehlenite calcium aluminium | Sulphur aluminium calcium ferrite |
| Cement clinker | 65 | 10 | 12 |
TABLE 2 mechanical Properties of mortars at different temperatures
FIG. 2 is an X-ray diffraction pattern of the clinker prepared in example 1, and the main components of the clinker can be seen from FIG. 2, as shown in Table 1.
Example 2
The differences from example 1 are: the calcination temperature is 1250 ℃, the calcination time is 30min, the cement clinker is obtained, and the main mineral composition of the cement clinker is shown in table 3. And preparing the fired cement into a mortar block and placing the mortar block in a negative temperature environment. The properties of the mortar blocks prepared are shown in Table 4. The strength test standard is carried out according to GB20472-2006 sulphoaluminate cement.
TABLE 3 composition of main minerals in cement clinker (% by weight)
| Components | Calcium sulphoaluminate | Gehlenite calcium aluminium | Sulphur aluminium calcium ferrite |
| Cement clinker | 72 | 6 | 9 |
TABLE 4 mechanical Properties of mortars at different temperatures
It can be obtained by the examples 1 and 2 that the calcination temperature is lower, and when the calcination temperature is changed, the mechanical property of the mortar is changed, and the composition of the cement clinker is changed.
Example 3
Homogenizing and mixing the high-calcium iron tailings, the desulfurized gypsum, the aluminum ash and the limestone, wherein the alkalinity coefficient of the homogenized cement raw material is 0.88, 34 parts by weight of CaO and SiO in the homogenized raw material212 weight portions of Al2O328 parts by weight of Fe2O39 parts by weight of SO3Is 18 weight portions. And then, conveying the homogenized material to a rotary kiln for calcination, wherein the calcination temperature is 1220 ℃, the calcination time is 30min, and cement clinker is obtained, and the main mineral composition of the cement clinker is shown in table 1. 7 percent of gypsum is added into the cement clinker, and the cement clinker is ground in a cement grinding machine to obtain the sulphoaluminate cement, wherein the main mineral composition of the sulphoaluminate cement is shown in Table 1. And preparing the fired cement into a mortar block and placing the mortar block in a negative temperature environment. The properties of the mortar block prepared are shown in Table 2. Standard for testing strength is GB20472-2006 sulphoaluminateCement ], etc.
TABLE 5 composition of main minerals in cement clinker (% by weight)
| Components | Calcium sulphoaluminate | Gehlenite calcium aluminium | Sulphur aluminium calcium ferrite |
| Cement clinker | 66 | 9 | 10 |
TABLE 6 mechanical Properties of mortars at different temperatures
It can be seen from a comparison of example 1 and example 3 that when the composition of the raw materials is changed, the mechanical formation of the mortar is changed, i.e. the composition has an influence on the properties.
Example 4
Homogenizing and mixing the high-calcium iron tailings, the desulfurized gypsum, the aluminum ash and the limestone, wherein the alkalinity coefficient of the homogenized cement raw material is 0.91, the CaO accounts for 38 parts by weight, and the SiO accounts for 38 parts by weight211 parts by weight of Al2O326 parts by weight of Fe2O37 weight portions of SO3Accounting for 15 weight portions. Then the homogenized material is conveyed to a rotary kiln for calcination at the temperature ofThe calcination time is 45min at 1220 ℃, and the cement clinker is obtained, and the main mineral composition of the cement clinker is shown in table 1. Adding 5% of gypsum into cement clinker, and grinding the cement clinker by a cement grinding machine to obtain sulphoaluminate cement, wherein the main mineral composition of the sulphoaluminate cement is shown in Table 1. The burnt cement is made into mortar blocks and placed in a low and negative temperature environment. The properties of the mortar block prepared are shown in Table 2. The strength test standard is carried out according to GB20472-2006 sulphoaluminate cement.
TABLE 7 composition of main minerals in cement clinker (% by weight)
| Components | Calcium sulphoaluminate | Gehlenite calcium aluminium | Sulphur aluminium calcium ferrite |
| Cement clinker | 68 | 11 | 6 |
TABLE 8 mechanical Properties of mortars at different temperatures
As can be seen from a comparison of example 4 with example 1, the properties change after a long calcination time, which indicates that the calcination time has an influence on the composition of the individual components of the cement clinker, resulting in a change in the mechanical properties.
Comparative example 1
Compared with example 1, the unreasonable proportion of the high-calcium iron tailings, the limestone, the desulfurized gypsum and the aluminum ash causes that the obtained raw material contains 32 parts by weight of CaO and SiO215 parts by weight of Al2O329 parts by weight of Fe2O34 parts by weight of SO3Is 19 weight portions. The rest of the preparation was the same as in example 1.
TABLE 9 composition of main minerals in cement clinker (% by weight)
| Components | Calcium sulphoaluminate | Gehlenite calcium aluminium | Sulphur aluminium calcium ferrite |
| Cement clinker | 48 | 19 | 9 |
TABLE 10 mechanical Properties of mortars at different temperatures
From example 1 and comparative example 1 it is possible to obtain that, when the composition of the ingredients of the raw meal is not coordinated, a greater variation in the composition of the clinker produced results, leading to a modification in the mechanical properties of the mortar.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The raw meal utilizing the high-calcium iron tailings is characterized in that: comprises high calcium iron tailings, desulfurized gypsum, aluminum ash and limestone, wherein CaO accounts for 34-40 parts by weight in the raw material, and SiO accounts for26-12 parts by weight of Al2O320-28 parts by weight of Fe2O35-12 parts by weight of SO312 to 18 weight portions, and the aluminum-sulfur ratio is 1.5 to 2.0.
2. The raw meal utilizing high-calcium iron tailings of claim 1, wherein: the raw material comprises 34-40 parts by weight of CaO and SiO211-12 parts by weight of Al2O326-28 parts by weight of Fe2O37-9 parts by weight of SO315-18 parts by weight of aluminum-sulfur ratio of 1.5-2.0.
3. The raw meal utilizing high-calcium iron tailings of claim 1, wherein: the alkalinity coefficient of the raw material is 0.85-0.95.
4. The raw meal utilizing high-calcium iron tailings of claim 1, wherein: the main components of the high-calcium iron tailings are CaO: 25-32% wt, SiO2：28-35％wt，Al2O3：5-8％wt，Fe2O3：6-9％wt，SO3：3-8％wt。
5. A cement clinker characterized by: the raw material is the raw material utilizing the high-calcium iron tailings.
6. The method for producing cement clinker according to claim 5, wherein: the method comprises the following steps: and calcining the raw material utilizing the high-calcium iron tailings to obtain the cement clinker.
7. A negative temperature engineering material is characterized in that: comprising the cement clinker of claim 5 and gypsum.
8. The negative temperature engineering material of claim 7, wherein: the mass percentage of the gypsum is 3-8%, and the rest is cement clinker.
9. Use of the raw meal of any of claims 1 to 4, the cement clinker of claim 5, the sulphoaluminate cement of claim 7 in the field of construction engineering;
preferably, the temperature range used is-15 ℃ or higher; further preferably from-15 ℃ to 45 ℃.
10. The production system of sulphoaluminate cement is characterized in that: the method comprises the following steps: the drying device, the homogenizing device and the calcining device are connected in sequence;
preferably, the device also comprises a crushing device, wherein the drying device is divided into a high-calcium iron tailing drying device, a limestone drying device, a desulfurized gypsum drying device and an aluminum ash drying device, the high-calcium iron tailing drying device and the limestone drying device are respectively connected with the crushing device, and the crushing device is connected with the homogenizing device;
preferably, the device also comprises a primary grinding device and a secondary grinding device, and the homogenizing device is sequentially connected with the primary grinding device, the secondary grinding device and the calcining device.
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