CN114014572B - Preparation method of high-activity cement admixture - Google Patents
Preparation method of high-activity cement admixture Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- C04B20/04—Heat treatment
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- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention discloses a preparation method of a high-activity cement admixture, belonging to the technical field of converter steel slag treatment application and industrial solid waste building material resource utilization. The method comprises the steps of mixing converter steel slag serving as a main raw material and carbide slag and blast furnace slag serving as auxiliary materials, heating in a reaction furnace until the temperature of molten converter steel slag reaches, quenching to room temperature after heat preservation treatment, crushing and ball milling to obtain powder, and thus obtaining the high-activity cement admixture. The invention realizes that the high-activity cement admixture with the activity reaching the S95 level is prepared by taking the molten converter steel slag as a main raw material and taking the industrial solid waste as a conditioning agent and utilizing the full solid waste, not only realizes the aim of cooperatively utilizing various industrial solid waste, but also effectively improves the quality level of the subsequent utilization of the converter steel slag; the utilization problem of converter steel slag caused by activity and stability is solved, the iron content of the converter steel slag serving as a cement admixture is effectively reduced, and the substitution proportion of cement is improved to a certain extent.
Description
Technical Field
The invention belongs to the technical fields of converter steel slag treatment application and industrial solid waste building material resource utilization, and relates to a preparation method of a high-activity cement admixture.
Background
The converter steel slag is solid waste in the ferrous metallurgy industry, accounts for about 11-15% of steel yield, and is one of main solid waste in the ferrous industry. The technical problem of recycling the converter steel slag causes that most of the steel slag is temporarily piled up and abandoned as waste, which not only occupies a large amount of land resources, but also brings serious harm to the surrounding environment (damage to soil, vegetation, pollution to air, water source and the like).
At present, one of the main utilization ways of the converter steel slag is to ball mill the magnetically separated converter steel slag tailings to obtain converter steel slag micropowder which is used as a cement admixture to replace part of cement, thereby realizing the utilization of the converter steel slag tailings. However, this method has problems of early strength of concrete due to insufficient activity and stability of concrete mass due to poor stability, and is poor in utilization and low in utilization rate.
Aiming at the problems of low early activity, poor stability and the like in steel slag, a plurality of expert students at home and abroad carry out process and technical improvement from the source of steel slag generation to the end of each process stage of activity excitation and the like of the falling steel slag tailings, modification experiments are carried out on the steel slag, but the grindability of the modified steel slag, the activity of the modified steel slag used as a mineral admixture in concrete, the early strength of the prepared concrete and the stability of the concrete are poor; either replacing the steel slag or adding additives, the replacement rate of the cement admixture is lower than 30%.
For example: chinese patent CN109336437a discloses a limestone micropowder-steel slag powder-slag powder composite admixture and a preparation process thereof, wherein the slag powder performance meets the technical requirement of grade S95 in the standard of GB/T18046-2017 of granulated blast furnace slag powder for cement, mortar and concrete, the slag powder cost is higher, the limestone micropowder cost is higher than that of carbide slag, the utilization rate of converter slag is lower, and the industrial production is not facilitated.
Chinese patent CN104961413a discloses a method for preparing road concrete by using slag micropowder, slag micropowder and fly ash as admixture, wherein the utilization rate of the slag micropowder is also low, the content selection range of the slag micropowder, slag micropowder and fly ash is the same, the effects are the same, and the differences of main and auxiliary materials are avoided.
Chinese patent CN112430005a discloses a cement admixture for inhibiting alkali-aggregate reaction and a preparation method thereof, wherein the composition is as follows, in parts by weight: 30-40 parts of waste glass powder, 15-20 parts of slag, 3 parts of wool, 0.3-0.5 part of gelatin, 3-5 parts of alkyl benzene sulfosulfate and 10-22 parts of lithium sulfate. So the waste glass powder in the cement admixture is used as a main raw material, the utilization rate of slag and slag is low, and the content of replacement cement is also lower than 30 percent.
Chinese patent CN104402266a discloses a preparation method and application of cement admixture, the raw materials of the cement admixture comprise (by weight) carbide slag 1-80%, silica fume 1-80%, nitric acid and/or ammonium nitrate 2-50%, urea 8-50% and water 0-50%; the mixture is placed into a sintering furnace and heated to 300-1200 ℃ to burn; cooling to room temperature after combustion is finished to obtain slag taking dicalcium silicate as a main component, and obtaining the cement admixture. The main raw material combination example in the cement admixture is known as urea, the utilization rate of carbide slag is not high, the cement admixture is not prepared by using converter slag as the main raw material, and the content of replacement cement is also lower than 30%.
Chinese patent CN1792972A discloses a cement admixture with high sulfur resistance and a preparation method thereof, which is mainly prepared from raw materials of blast furnace water floating slag, modifier and shrinkage reduction functional components, wherein the main raw materials in the cement admixture are not converter slag, the auxiliary materials are complex in composition, and the utilization rate of the carbide slag and the converter slag is low.
And the research shows that the level of the cement which is replaced by the converter steel slag as the cement admixture and replaces part of cement is still not more than 30%, otherwise, the early strength of the concrete is difficult to reach the national standard. And the utilization rate of the converter steel slag as a cement admixture is limited by the iron content.
In summary, the prior art has found that although the slag utilization of the cement admixture is very high, the content of the cement admixture replacing part of the cement is still not more than 30%, even for converter steel slag. Because if the replacement cement content exceeds 30%, the early strength of the concrete hardly reaches the national standard; and the iron content in the converter slag further limits the utilization rate of the converter slag as a cement admixture. Thus, to date, there has been no research on a comprehensive industrial production method capable of further improving the utilization rate of converter steel slag as a cement admixture, the level of cement admixture replacing part of cement and the early strength of concrete.
Disclosure of Invention
The invention solves the technical problems that the slag charge utilization mode of the cement admixture in the prior art is many, and the replacement cement content is more than 30 percent although the slag charge utilization mode comprises converter steel slag; if the magnetite in the converter steel slag is removed by magnetic separation, the process is complicated, and if the magnetite is not removed, the iron content is high, so that the utilization rate of the converter steel slag in the preparation of cement admixture is reduced; the prepared cement admixture has low early strength, poor stability, low solid waste utilization rate and high production cost, and is not beneficial to industrial mass production.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method comprises the steps of mixing converter steel slag serving as a main raw material, carbide slag and blast furnace slag serving as auxiliary materials, heating in a reaction furnace until the temperature of molten converter steel slag is reached, quenching to room temperature after heat preservation treatment, crushing and ball milling into powder, and thus obtaining the high-activity cement admixture.
Preferably, the carbide slag is 10-25% of the converter steel slag mass, and the blast furnace slag is 10-25% of the converter steel slag mass.
Preferably, the specific heating process comprises the following steps: the heating rate from 20 ℃ to 200 ℃ is controlled to be 10 ℃/min, and the heating rate from 200 ℃ to 1350 ℃ is controlled to be 15 ℃/min.
Preferably, the quenching mode is fan quenching cooling or water quenching cooling.
Preferably, in the mixing of the converter steel slag, the carbide slag and the blast furnace slag are mixed at the same time, and the mass ratio of the carbide slag to the blast furnace slag is 1:1, the total mass of the carbide slag and the blast furnace slag is 25-40% of that of the converter slag.
Preferably, the powder obtained by crushing and ball milling is more than 200 meshes.
Preferably, the high-activity cement admixture is prepared from full solid waste mainly containing converter steel slag, and the 28-day activity index of the high-activity cement admixture is more than 85 percent and is far higher than 68 percent of the 28-day activity index of the magnetic separation tailings of the converter steel slag which are independently used as the cement admixture.
Preferably, tricalcium silicate which is not contained in the original converter steel slag appears in the high-activity cement admixture, and FeO is converted into magnetite and hematite under the high-temperature condition; mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like also appear.
Preferably, cement mortar is prepared from the prepared high-activity cement admixture and converter steel slag powder according to the national standard GB/T17671-1999, and the cement mortar is obtained by detection: the high-activity cement admixture has a 3-day compressive strength of 12.6-14.9MPa, a 7-day compressive strength of 21.6-23.1MPa and a 28-day compressive strength of 41.9-44.5MPa.
Preferably, the high-activity cement admixture comprises the following components in percentage by mass: caO43.58-43.98%, siO 2 14.97-15.84％，Al 2 O 3 5.21-6.70％，Fe 2 O 3 17.60-19.35％，MgO 7.29-7.73％，P 2 O 5 1.85-2.16％，MnO 2.50-2.76％，C/S 2.97-3.11，S/A 4.01-4.88。
The technical scheme provided by the embodiment of the invention has at least the following beneficial effects:
in the scheme, the invention provides a method for preparing the high-activity cement admixture by taking industrial solid waste carbide slag and blast furnace slag as molten converter slag modifier, mixing and modifying the slag in a molten state according to a certain mass ratio, and then carrying out water quenching/air quenching and ball grinding.
The carbide slag serving as an auxiliary material of the invention is used as solid waste with high calcium content and can be used as a substitute of lime serving as a slag former, thereby adjusting the C/S ratio in the steel slag and promoting the generation of more dicalcium silicate and tricalcium silicate; meanwhile, the auxiliary material blast furnace slag is used as a silicon-aluminum conditioning agent, so that the S/A of a conditioning product is reduced, and the content of minerals such as tricalcium aluminate which are easy to hydrate in early stage is increased; the content of the silicon-calcium potential gel minerals and the silicon-aluminum oxides in the converter steel slag is supplemented and enriched, and the early-onset gel activity of the original converter steel slag is improved.
The invention heats up in the reaction furnace until the temperature of the molten converter steel slag, and does not need frequent magnetic separation process, thus simplifying the original process method, then carrying out heat preservation and quenching, reducing the content of f-CaO by controlling the heat preservation time and the quenching cooling system, and improving the early gelling activity by nearly one time compared with the original converter steel slag.
The invention realizes that the high-activity cement admixture with the activity reaching the S95 level is prepared by taking the molten converter steel slag as a main raw material and taking the industrial solid waste as a conditioning agent and utilizing the full solid waste, not only realizes the aim of cooperatively utilizing various industrial solid wastes, but also effectively improves the quality level of the subsequent utilization of the converter steel slag.
The invention not only solves the utilization problem of converter steel slag caused by activity and stability, but also effectively reduces the iron content of the converter steel slag as a cement admixture and improves the substitution ratio of cement to a certain extent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing a high activity cement admixture of the present invention;
FIG. 2 is a process flow diagram of the method of preparing the high activity cement admixture of example 1 of the present invention;
FIG. 3 is an XRD diffraction pattern of the steel slag of the converter of examples 1-6 of the present invention;
FIG. 4 is an XRD diffraction pattern of the high activity cement admixture prepared in example 1 of the present invention;
FIG. 5 is an XRD diffraction pattern of the high activity cement admixture prepared in example 2 of the present invention;
FIG. 6 is a graph showing the strength comparison of cement mortar prepared from the converter slag and the high-activity cement admixture according to examples 1-2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following table 1 shows the chemical compositions of cement, converter slag, carbide slag, and blast furnace slag in wt%; as shown in fig. 3, the XRD diffractogram of the converter steel slag lists the mineral composition of the converter steel slag.
TABLE 1 chemical composition of converter slag, carbide slag and blast furnace slag, wt%
| Composition of the components | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO |
| Cement and its preparation method | 52.35 | 26.18 | 7.63 | 3.76 | 4.59 | 0.13 | 0.13 |
| Converter steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 |
| Mineral powder | 38.78 | 33.06 | 16.45 | 0.81 | 6.37 | ---- | --- |
| Carbide slag | 84.4 | 4.53 | 4.01 | 0.90 | 1.99 | 0.05 | 0.12 |
As shown in figure 1, the preparation method of the high-activity cement admixture comprises the steps of mixing converter steel slag generated in the production process of a converter as a main raw material, carbide slag and blast furnace slag as auxiliary materials, heating in a reaction furnace until the temperature of the molten converter steel slag reaches, carrying out heat preservation treatment, quenching to a novel mineral at room temperature through water quenching or air quenching, crushing and ball milling into powder, and thus obtaining the high-activity cement admixture. Wherein: the water-quenched slag of the molten blast furnace slag generated in the blast furnace ironmaking process is the blast furnace slag in the auxiliary materials, limestone and oxygen are required to be added in the converter steelmaking process so as to obtain the non-magnetically separated converter slag, and oxygen blowing and stirring are required in the heating process so as to obtain the molten converter slag.
Example 1
320g of converter slag is taken, and the mixing amount is 80 percent; 40g of carbide slag, wherein the mixing amount is 10%; 40g of blast furnace slag, and the mixing amount is 10 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out fan quenching cooling. The cooled sample was crushed and ground to powder by vibration grinding, and XRD and chemical component tests were performed, respectively, with the test results shown in table 2 and fig. 4.
As shown in Table 2, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. As can be obtained from the XRD diffractogram analysis in fig. 4, the prepared high-activity cement admixture exhibited tricalcium silicate diffraction peaks which were not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared.
TABLE 2 chemical composition comparison of raw converter slag with the high-Activity Cement Admixture of example 1, wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 1 | 43.58 | 14.97 | 5.21 | 19.35 | 7.73 | 2.16 | 2.76 | 3.11 | 4.88 |
Example 2
280g of converter slag is taken, and the mixing amount is 70 percent; 60g of carbide slag, wherein the mixing amount is 15%; 60g of blast furnace slag, and the mixing amount is 15 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out water quenching, quenching and cooling. The cooled sample was crushed and pulverized by vibration milling, and XRD and chemical component tests were performed, respectively, and the test results are shown in table 3 and fig. 5.
As shown in Table 3, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. As can be obtained from the XRD diffractogram analysis in fig. 5, the prepared high-activity cement admixture exhibited tricalcium silicate diffraction peaks which were not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared. The highest substitute of the obtained high-activity cement admixture can reach 35% on the basis of reaching the national standard of 42.5 MPa.
TABLE 3 chemical composition comparison of raw converter slag with the high-Activity Cement Admixture in example 2 wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 2 | 43.98 | 15.84 | 6.70 | 17.60 | 7.29 | 1.85 | 2.50 | 2.97 | 4.01 |
Example 3
As shown in fig. 2, 300g of converter slag is taken, and the mixing amount accounts for 75 percent; 50g of carbide slag, wherein the mixing amount is 12.5 percent; 50g of blast furnace slag, and the mixing amount is 12.5 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out fan quenching cooling. The cooled sample was crushed and ground into powder by vibration grinding, and XRD and chemical component tests were performed, respectively, and the test results are shown in table 4.
As shown in Table 4, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. The prepared high-activity cement admixture has a tricalcium silicate diffraction peak which is not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared. The highest substitute of the obtained high-activity cement admixture can reach 33% on the basis of reaching the national standard of 42.5 MPa.
TABLE 4 chemical composition comparison of raw converter slag with the high-Activity Cement Admixture in example 3 wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 3 | 43.78 | 15.23 | 5.92 | 18.23 | 7.45 | 1.93 | 2.63 | 3.01 | 4.43 |
Example 4
290g of converter slag is taken, and the mixing amount is 72.5 percent; 55g of carbide slag, wherein the mixing amount is 13.75 percent; 55g of blast furnace slag, and the mixing amount is 13.75 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out water quenching, quenching and cooling. The cooled sample was crushed and ground into powder by vibration grinding, and XRD and chemical component tests were performed, respectively, and the test results are shown in table 5.
As shown in Table 5, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. The prepared high-activity cement admixture has a tricalcium silicate diffraction peak which is not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared. The highest substitute of the obtained high-activity cement admixture can reach 34% on the basis of reaching the national standard of 42.5 MPa.
TABLE 5 chemical composition comparison of raw converter slag with the high-Activity Cement Admixture in example 4 wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 4 | 43.65 | 15.09 | 5.54 | 17.86 | 7.36 | 1.89 | 2.57 | 2.99 | 4.25 |
Example 5
As shown in fig. 2, taking 310g of converter slag, wherein the mixing amount is 77.5%; 45g of carbide slag, and the mixing amount is 11.25 percent; 45g of blast furnace slag, and the mixing amount is 11.25 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out fan quenching cooling. The cooled samples were crushed and ground to powder by vibration grinding, and XRD and chemical component tests were performed, respectively, with the test results shown in table 6.
As shown in Table 6, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. The prepared high-activity cement admixture has a tricalcium silicate diffraction peak which is not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared. The highest substitute of the obtained high-activity cement admixture can reach 31 percent on the basis of reaching the national standard of 42.5 MPa.
TABLE 6 chemical composition comparison of raw converter slag with high-Activity Cement Admixture in example 5 wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 5 | 43.85 | 15.53 | 6.33 | 18.76 | 7.61 | 2.03 | 2.69 | 3.07 | 4.65 |
Example 6
306g of converter slag is taken, and the mixing amount is 76.5 percent; 47g of carbide slag, and the mixing amount is 11.75 percent; 47g of blast furnace slag, and the mixing amount is 11.75 percent. Mixing the three materials uniformly, then placing the mixture into a crucible, and then placing the crucible into a box-type muffle furnace to heat to 1350 ℃. The specific temperature rising process is as follows: the temperature of 20-200 ℃ is 10 ℃/min, and the temperature of 200-1350 ℃ is 15 ℃/min. And after the heat preservation is finished for 30min, taking out the sample and the crucible, and carrying out water quenching, quenching and cooling. The cooled sample was crushed and ground into powder by vibration grinding, and XRD and chemical component tests were performed, respectively, and the test results are shown in table 7.
As shown in Table 7, the calcium and aluminum contents of the high-activity cement admixture prepared by using the carbide slag and the blast furnace slag as molten converter slag conditioner are simulated to be obviously increased, the iron content is reduced, and the C/S level is already above 3.0 and approaches or even exceeds the C/S of the common cement clinker under the high-temperature condition. And the S/A is greatly reduced compared with the prior S/A. The prepared high-activity cement admixture has a tricalcium silicate diffraction peak which is not found in the original converter steel slag; feO is converted to magnetite and hematite under high temperature conditions. Meanwhile, mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like are also appeared. The highest substitute of the obtained high-activity cement admixture can reach 32% on the basis of reaching the national standard of 42.5 MPa.
TABLE 7 chemical composition comparison of raw converter slag with the high-Activity Cement Admixture in example 6 wt%
| Material | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | P 2 O 5 | MnO | C/S | S/A |
| Steel slag | 41.04 | 15.96 | 2.17 | 20.03 | 7.77 | 2.30 | 6.39 | 2.75 | 12.50 |
| Example 6 | 43.82 | 15.38 | 6.15 | 17.49 | 7.54 | 1.97 | 2.50 | 2.66 | 4.56 |
The high-activity cement admixture prepared in examples 1 and 2 and the raw converter steel slag were prepared into cement mortar according to the national standard GB/T17671-1999 to examine the activity of the three. The specific formulation thereof is shown in Table 4.
Table 4 ratio of raw converter slag to cement mortar prepared from high-activity cement admixture in case 1 and case 2
And curing and detecting the strength of the prepared cement mortar according to the national standard GB/T17671-1999. The pair of compressive strengths is shown in fig. 4.
As shown in the result of FIG. 4, the strength of cement mortar prepared by using the high-activity cement admixture in the method is greatly improved compared with that of the original converter steel slag. In particular, the 3-day intensity was increased by approximately one time in example 2, and the activity index was also increased by one time. The activity index of the original converter steel slag as a cement admixture is 68%, and the activity index of the obtained high-activity cement admixture for 28 days is up to 86%.
In the scheme, the invention provides a method for preparing the high-activity cement admixture by taking industrial solid waste carbide slag and blast furnace slag as molten converter slag modifier, mixing and modifying the slag in a molten state according to a certain mass ratio, and then carrying out water quenching/air quenching and ball grinding.
The carbide slag serving as an auxiliary material of the invention is used as solid waste with high calcium content and can be used as a substitute of lime serving as a slag former, thereby adjusting the C/S ratio in the steel slag and promoting the generation of more dicalcium silicate and tricalcium silicate; meanwhile, the auxiliary material blast furnace slag is used as a silicon-aluminum conditioning agent, so that the S/A of a conditioning product is reduced, and the content of minerals such as tricalcium aluminate which are easy to hydrate in early stage is increased; the content of the silicon-calcium potential gel minerals and the silicon-aluminum oxides in the converter steel slag is supplemented and enriched, and the early-onset gel activity of the original converter steel slag is improved.
The invention heats up in the reaction furnace until the temperature of the molten converter steel slag, and does not need frequent magnetic separation process, thus simplifying the original process method, then carrying out heat preservation and quenching, reducing the content of f-CaO by controlling the heat preservation time and the quenching cooling system, and improving the early gelling activity by nearly one time compared with the original converter steel slag.
The invention realizes that the high-activity cement admixture with the activity reaching the S95 level is prepared by taking the molten converter steel slag as a main raw material and taking the industrial solid waste as a conditioning agent and utilizing the full solid waste, not only realizes the aim of cooperatively utilizing various industrial solid wastes, but also effectively improves the quality level of the subsequent utilization of the converter steel slag.
The invention not only solves the utilization problem of converter steel slag caused by activity and stability, but also effectively reduces the iron content of the converter steel slag as a cement admixture and improves the substitution ratio of cement to a certain extent.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the high-activity cement admixture is characterized in that the method is characterized in that converter slag is used as a main raw material, carbide slag and blast furnace slag are used as auxiliary materials, the mixture is heated in a reaction furnace until the temperature of molten converter slag is reached, the mixture is quenched to room temperature after heat preservation treatment, and crushed and ball-milled into powder, so that the high-activity cement admixture is obtained;
the carbide slag accounts for 10-25% of the converter steel slag, and the blast furnace slag accounts for 10-25% of the converter steel slag;
the specific heating process comprises the following steps: the heating rate from 20 ℃ to 200 ℃ is controlled to be 10 ℃/min, and the heating rate from 200 ℃ to 1350 ℃ is controlled to be 15 ℃/min;
the high-activity cement admixture comprises the following components in percentage by mass: caO43.58-43.98%, siO 2 14.97-15.84％，Al 2 O 3 5.21-6.70％，Fe 2 O 3 17.60-19.35％，MgO7.29-7.73％，P 2 O 5 1.85-2.16％，MnO2.50-2.76％，C/S2.97-3.11，S/A4.01-4.88。
2. The method for preparing the high-activity cement admixture according to claim 1, wherein the quenching mode is fan quenching cooling or water quenching cooling.
3. The method for preparing the high-activity cement admixture according to claim 1, wherein in the mixing of the converter slag, the carbide slag and the blast furnace slag are mixed at the same time, and the mass ratio of the carbide slag to the blast furnace slag is 1:1, the total mass of the carbide slag and the blast furnace slag is 25-40% of that of the converter slag.
4. The method for preparing the high-activity cement admixture according to claim 1, wherein the powder obtained by crushing and ball milling is 200 meshes or more.
5. The preparation method of the high-activity cement admixture according to claim 1, wherein the high-activity cement admixture is prepared from all solid wastes mainly containing converter steel slag, and the 28-day activity index of the high-activity cement admixture is more than 85 percent and is far higher than the 28-day activity index of the magnetic separation tailings of the converter steel slag which are independently used as the cement admixture by 68 percent.
6. The method for preparing a high activity cement admixture according to any one of claims 1 to 5, wherein tricalcium silicate which is not present in raw converter steel slag is present in the high activity cement admixture, feO being converted into magnetite and hematite under high temperature conditions; mineral components with higher hydration activity such as tricalcium aluminate, mullite and the like also appear.
7. The method for preparing the high-activity cement admixture according to any one of claims 1 to 5, wherein cement mortar is prepared from the prepared high-activity cement admixture and converter steel slag powder according to the national standard GB/T17671-1999, and the cement mortar is obtained by detection: the high-activity cement admixture has a 3-day compressive strength of 12.6-14.9MPa, a 7-day compressive strength of 21.6-23.1MPa and a 28-day compressive strength of 41.9-44.5MPa.
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