CN114477805A - Early-strength steel slag cementing material - Google Patents

Early-strength steel slag cementing material Download PDF

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Publication number
CN114477805A
CN114477805A CN202111564493.8A CN202111564493A CN114477805A CN 114477805 A CN114477805 A CN 114477805A CN 202111564493 A CN202111564493 A CN 202111564493A CN 114477805 A CN114477805 A CN 114477805A
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steel slag
parts
cementing material
strength steel
early
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CN114477805B (en
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吴疑
石建红
林培芳
孙章权
张兵成
韦波
罗元威
尹洁
董磊
张胜祥
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Guangdong Huaxin Environmental Protection Technology Co ltd
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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
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • 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
    • C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses an early-strength steel slag cementing material. The early-strength steel slag cementing material comprises the following components in parts by mass: 65-90 parts of steel slag, 5-15 parts of fly ash, 0-10 parts of gypsum, 0-8 parts of sodium silicate, 0-5 parts of mirabilite, 0-5 parts of urea and 0-3 parts of calcium chloride. The steel slag cementing material has high early strength, the 3d compressive strength and the 28d compressive strength of the steel slag cementing material reach the level of common 325 cement, and the problems of low early strength, low application range and the like of the steel slag cementing material are solved.

Description

Early-strength steel slag cementing material
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to an early-strength steel slag cementing material.
Background
The steel industry is a typical resource and energy-intensive industry, and steel production needs to consume a large amount of resources such as iron ore, coal, new water and the like and generate a large amount of three-waste resources. According to statistics, the long-flow steel enterprise consumes about 0.7-0.8 ton of coal, 1.5-1.55 ton of iron ore, a large amount of limestone flux and other raw materials per 1 ton of crude steel, and the solid waste production of 1 ton of steel is about 600 kg. The solid waste mainly comprises blast furnace slag, steel slag, iron-containing dust and mud, environmental dust and mud, waste refractory materials, coal ash of self-prepared power plants, desulfurized gypsum and the like according to different generated interfaces. According to preliminary calculation, the generation amount of the solid waste in the steel industry reaches the level of hundreds of millions of tons every year.
According to statistics, the metallurgical slag produced in 2018 of China reaches 5.56 hundred million tons. Wherein the production of blast furnace slag, steel slag, iron-containing dust and mud and ferroalloy slag are 26987, 13924, 8497 and 6247 ten thousand tons respectively, the comprehensive utilization of the steel slag is about 4.18 hundred million tons, and the comprehensive utilization rate is about 75.04%. However, according to the statistics of the industry, the utilization rate of the steel slag is only about 25%. After most of steel slag is separated from metallic iron, the tailings are in a stockpiling state, so that a large amount of steel slag is accumulated, resources are wasted, land is occupied, and great environmental pollution and potential safety hazards are caused. Steel slag, which is a main waste slag in metallurgical industry, has been a key object of solid waste resource research. Because the solid waste of the steel industry in China is large in production amount, various in solid waste, complex in components, and large in pressure of standardized disposal and resource utilization, the method is popularized in the steel metallurgy industry, the solid waste is not delivered from factories, the full-scale utilization is enhanced, the multi-industry and multi-variety synergistic utilization of the solid waste of the steel industry is promoted according to local conditions, a reproducible and generalizable utilization mode is formed, and the method becomes a necessary trend of green development of the steel industry in China. Therefore, the development of the solid waste recycling technology in the steel industry is urgent.
The steel slag is one of the important ways to realize the reclamation and high value of the industrial waste slag as the cementing material or the concrete admixture. However, the problems of large steel slag crystal particles, compact structure and slow hydration exist. Therefore, if the steel slag is used as a cementing material, the early strength of the steel slag is inevitably low.
Disclosure of Invention
In order to solve the problem of low early strength of the steel slag as a cementing material in the prior art, the invention aims to provide an early strength steel slag cementing material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an early-strength steel slag cementing material comprises the following components in parts by mass: 65-90 parts of steel slag, 5-15 parts of fly ash, 0-10 parts of gypsum, 0-8 parts of sodium silicate, 0-5 parts of mirabilite, 0-5 parts of urea and 0-3 parts of calcium chloride.
Preferably, the early strength steel slag cementing material comprises the following components in parts by mass: 70-85 parts of steel slag, 8-15 parts of fly ash, 1-5 parts of gypsum, 1-5 parts of sodium silicate, 1-5 parts of mirabilite, 1-3 parts of urea and 1-3 parts of calcium chloride.
Preferably, in the early strength steel slag cementing material, the steel slag comprises the following components by mass percent: 30-46% of CaO and 10-18% of SiO2、4-25％FeO、2-15％Fe2O3、2-15％f-CaO、5-8％MgO、1-6％Al2O3、1-4％MnO、 0.1-1.2％P2O5(ii) a Further preferably, the steel slag comprises the following components in percentage by mass: 32-44% of CaO and 10-16% of SiO2、 5-22％FeO、2-12％Fe2O3、2-12％f-CaO、6-7％MgO、2-5％Al2O3、2-3％MnO、0.2-1％P2O5(ii) a Still further preferably, the steel slag comprises the following components in percentage by mass: 34-43% of CaO and 12-15% of SiO2、5-22％FeO、 4-10％Fe2O3、3-10％f-CaO、6-7％MgO、2-5％Al2O3、2-3％MnO、0.2-1％P2O5The rest is the loss due to burning.
Preferably, in the early strength steel slag cementing material, the specific surface area of the steel slag is 400-600m2Per kg; further preferably, the specific surface area of the steel slag is 420-580m2(iv) kg; still more preferably, the specific surface area of the steel slag is 450-550m2/kg。
Preferably, in the early-strength steel slag cementing material, the fly ash is class I F fly ash.
Preferably, in the early-strength steel slag cementing material, the gypsum is desulfurized gypsum, the purity of the gypsum is more than or equal to 90 wt%, the free water content is less than or equal to 10 wt%, the pH value is 6-8, and CaCO3Content is less than or equal to 3wt percent of CaCO3·1/2H2The content of O is less than or equal to 0.35wt percent, and the C dissolved in the gypsum is less than or equal to 10 mg/kg.
Preferably, in the early-strength steel slag cementing material, the particle size of gypsum is 1-250 μm.
Preferably, in the early-strength steel slag cementing material, the d50 particle size of gypsum is 28-45 μm; further preferably, the gypsum has a d50 particle size of 30-42 μm; still more preferably, the d50 particle size of the gypsum is 32-40 μm.
Preferably, in the early-strength steel slag cementing material, the F-content in the gypsum is less than or equal to 100Mg/kg, and the Mg content is less than or equal to 450 Mg/kg.
Preferably, in the early-strength steel slag cementing material, the sodium silicate is d-Na2Si2O5(ii) a The sodium silicate is anhydrous type d-Na2Si2O5。
Preferably, in the early strength steel slag cementing material, the water glass is industrial solid water glass, the soluble solid content of the industrial solid water glass is not less than 98 wt.%, the Fe content of the industrial solid water glass is not more than 0.12 wt.%, and the modulus of the industrial solid water glass is 3.21-4.55.
Preferably, in the early strength steel slag cementing material, the calcium chloride is anhydrous calcium chloride, the anhydrous calcium chloride is industrial I-type anhydrous sodium chloride, the content of the calcium chloride in the anhydrous sodium chloride is more than or equal to 94 wt%, and the alkalinity is (Ca (OH))2Calculated by NaCl is less than or equal to 0.25wt percent, total alkali metal chloride (calculated by NaCl) is less than or equal to 5.0wt percent, the pH value is 7.5-11.0, and the grain diameter is 0.124 mm.
Preferably, in the early-strength steel slag cementing material, mirabilite is national standard industrial mirabilite, wherein Na is sodium chloride2SO4The content is more than or equal to 99 wt%, and the particle size distribution is as follows: 10 wt% of particles with a particle size of < 2.75 μm; 30 wt% of particles with a particle size of less than 5.54 μm; the grain diameter is less than 8.Particles of 61 μm account for 50 wt%; 60 wt% of particles with a particle size of < 13.46 mu m; 90% by weight of particles having a particle size of < 35.94 μm.
Preferably, in the early-strength steel slag cementing material, the urea is national standard industrial grade commercial urea, the content is more than or equal to 46.4 wt%, and the execution standard is Q/371626SZW 006-2017.
The invention also provides a preparation method of the early-strength steel slag cementing material, which comprises the following steps: mixing the components to obtain the early strength steel slag cementing material.
The invention has the beneficial effects that:
the invention provides a steel slag cementing material which has high early strength, the 3d compressive strength and the 28d compressive strength of the steel slag cementing material reach the level of common 325 cement, and the problems of low early strength, low application range and the like of the steel slag cementing material are solved.
The invention fully utilizes solid waste to obtain the steel slag cementing material, consumes a large amount of steel slag, not only saves cost, but also protects natural environment, and creates economic benefit while realizing environmental benefit.
The steel slag cementing material has the steel slag consumption of more than 70 percent, and greatly improves the utilization rate of the steel slag; the early-strength steel slag cementing material not only solves the utilization problem of steel slag, but also solves the influence of cement production on the environment.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion in table 1.
TABLE 1 early Strength Steel slag Binder composition of this example
Raw materials Mass portion of
Steel slag 70
Anhydrous calcium chloride 3
Natrii sulfas 5
Desulfurized gypsum 2
Sodium silicate 3
Fly ash 15
Urea 2
Example 2
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion of table 2.
TABLE 2 early strength steel slag binding material composition of this example
Figure BDA0003421702500000031
Figure BDA0003421702500000041
Example 3
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion in table 3.
TABLE 3 early strength steel slag binding material composition of this example
Raw materials Mass portion of
Steel slag 75
Anhydrous calcium chloride 2
Natrii sulfas 3
Desulfurized gypsum 3
Sodium silicate 4
Fly ash 12
Urea 1
Example 4
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion in table 4.
TABLE 4 early strength steel slag binding material composition of this example
Raw materials Mass portion of
Steel slag 80
Anhydrous calcium chloride 3
Natrii sulfas 2
Desulfurized gypsum 2
Sodium silicate 1
Fly ash 9
Urea 3
Example 5
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion of table 5.
TABLE 5 early strength steel slag binding material composition of this example
Raw materials Mass portion of
Steel slag 82
Anhydrous calcium chloride 1
Natrii sulfas 1
Desulfurized gypsum 1
Sodium silicate 1
Fly ash 13
Urea 1
Example 6
The components of the early strength steel slag cementing material of the embodiment are shown in the mass portion of table 6.
TABLE 6 early strength steel slag binding material composition of this example
Raw materials Mass portion of
Steel slag 85
Anhydrous calcium chloride 1
Natrii sulfas 2
Desulfurized gypsum 2
Sodium silicate 1
Fly ash 8
Urea 1
Comparative example 1
A commercially available ordinary 32.5 type cement was used.
Comparative example 2
Commercially available early strength 32.5R type cement was used.
Performance testing
1. Weighing the raw materials except the steel slag according to the mass parts of the embodiment 1-6, adding the raw materials into a ball milling tank of a planetary ball mill, then carrying out ball milling and stirring in the planetary ball mill at the rotating speed of 300r/min for 30 minutes, and completely and uniformly stirring to obtain the novel early-strength steel slag cementing material precursor.
2. And (3) adding the uniformly mixed early-strength steel slag cementing material precursor and the steel slag into a double-cone mixer in proportion, and stirring for 30min to obtain the early-strength steel slag cementing material.
3. The 3d and 28d compression tests of examples 1-6 and comparative examples 1-2 were tested according to GB/T17671-1999 Cement mortar Strength test method (ISO method), and the specific test results are shown in Table 7:
TABLE 7 results of performance test of examples and comparative examples
3d compressive Strength (MPa) 28d compressive Strength (MPa)
Example 1 19.1 34.9
Example 2 18.6 33.4
Example 3 18.8 35.7
Example 4 19.6 36.8
Example 5 16.5 32.6
Example 6 16.0 31.9
Comparative example 1 11.3 32.5
Comparative example 2 16.2 32.7
The test results show that the 3d and 28d compressive strengths of the early strength steel slag cementing material of the invention basically reach the strength of commercial 32.5R cement, and even exceed the strength of 32.5R cement. Meanwhile, the steel slag cementing material of the invention has the steel slag consumption of more than 70 percent, thereby greatly improving the utilization rate of the steel slag. The early-strength steel slag cementing material not only solves the problem of utilization of steel slag, but also solves the influence of cement production on the environment.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The early-strength steel slag cementing material is characterized by comprising the following components in parts by mass: 65-90 parts of steel slag, 5-15 parts of fly ash, 0-10 parts of gypsum, 0-8 parts of sodium silicate, 0-5 parts of mirabilite, 0-5 parts of urea and 0-3 parts of calcium chloride.
2. The early strength steel slag cementing material of claim 1, which is characterized by comprising the following components in parts by mass: 70-85 parts of steel slag, 8-15 parts of fly ash, 1-5 parts of gypsum, 1-5 parts of sodium silicate, 1-5 parts of mirabilite, 1-3 parts of urea and 1-3 parts of calcium chloride.
3. The early strength steel slag cementing material of claim 1 or 2, wherein the steel slag comprises the following components by mass percent: 30-46% of CaO and 10-18% of SiO2、4-25％FeO、2-15％Fe2O3、2-15％f-CaO、5-8％MgO、1-6％Al2O3、1-4％MnO、0.1-1.2％P2O5。
4. The early strength steel slag cementing material of claim 1 or 2, wherein the specific surface area of said steel slag is 400-600m2/kg。
5. The early strength steel slag cementitious material as claimed in claim 1 or 2, wherein the fly ash is class i class F fly ash.
6. The early strength steel slag cementitious material as claimed in claim 1 or 2, wherein the particle size of the gypsum is 1-250 μm.
7. The early strength steel slag cementitious material as claimed in claim 1 or 2, wherein the d50 particle size of the gypsum is 28-45 μm.
8. The early strength steel slag cementing material of claim 1 or 2, wherein the content of F-in the gypsum is less than or equal to 100Mg/kg, and the content of Mg is less than or equal to 450 Mg/kg.
9. The early strength steel slag cementitious material as claimed in claim 1 or 2, wherein the sodium silicate is d-Na2Si2O5。
10. A method for preparing the early strength steel slag cementing material of any one of the claims 1 to 9, which is characterized by comprising the following steps:
all the components are mixed to obtain the early strength steel slag cementing material.
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CN102491656A (en) * 2011-11-11 2012-06-13 中冶宝钢技术服务有限公司 Pulverized steel slag gelatinization material
CN107555896A (en) * 2017-08-21 2018-01-09 暨南大学 It is a kind of to excite slag and the standby admixture of coal ash for manufacturing and the high-strength concrete prepared using admixture with waterglass
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CN101549977A (en) * 2009-05-14 2009-10-07 吕运征 Composite gelate material and method of producing the same
CN102491656A (en) * 2011-11-11 2012-06-13 中冶宝钢技术服务有限公司 Pulverized steel slag gelatinization material
CN107555896A (en) * 2017-08-21 2018-01-09 暨南大学 It is a kind of to excite slag and the standby admixture of coal ash for manufacturing and the high-strength concrete prepared using admixture with waterglass
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Title
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