CN114163158A - Multi-component waste residue coupling and quality-enhancing composite powder and preparation method and application thereof - Google Patents
Multi-component waste residue coupling and quality-enhancing composite powder and preparation method and application thereof Download PDFInfo
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- CN114163158A CN114163158A CN202111416584.7A CN202111416584A CN114163158A CN 114163158 A CN114163158 A CN 114163158A CN 202111416584 A CN202111416584 A CN 202111416584A CN 114163158 A CN114163158 A CN 114163158A
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- composite powder
- slag
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- furnace slag
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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
- 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
- C04B40/0042—Powdery mixtures
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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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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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
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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
Abstract
The invention discloses a multi-component waste residue coupling quality-enhancing composite powder and a preparation method and application thereof, wherein the composite powder comprises the following components: nano-grade CaCO3Or carbonated steel slag or carbonated waste concrete, blast furnace slag, coal furnace slag, LF furnace refining slag and desulfurized gypsum. The invention utilizes nano-grade CaCO generated by carbonation technology3The granules also develop a new way for utilizing carbonated products of the solid wastes according to the strong coupling effect among the waste residues, improve the problem of difficult utilization of the solid wastes such as LF furnace refining slag, power plant coal-fired furnace slag and the like, and improve the performance of building materials such as cement, concrete and the like.
Description
Technical Field
The invention belongs to the technical field of metallurgical solid waste resource utilization, and particularly relates to multi-component waste residue coupling quality-enhancing composite powder and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The building materials such as cement are generally high in compressive strength and low in flexural strength, and the ratio of the compressive strength to the flexural strength is generally 3-6, so that when the cement and concrete are used for important structural parts, the flexural strength of a cement structure can be improved by adding materials such as reinforcing steel bars or steel fibers, and the improvement of the flexural strength of the cement is one of the application requirements of the cement performance at present.
The LF refining slag is a byproduct generated by adding active lime, bauxite, silica and the like into molten steel in the LF refining process, and is about 1500 ten thousand tons every year around the country because alpha-C exists in the LF refining slag in the cooling process2S to gamma-C2The crystal form of S is changed, the volume expansion is 12%, and certain self-cracking property exists, so that the use of the S in the building material field is limited, a large amount of LF furnace refining slag is stacked, the soil is alkalized, and underground water resources are polluted.
In addition, the amount of slag generated by coal-fired power generation is large, and the slag is mainly applied to road building and other aspects at present and is not comprehensively utilized in a high-value mode.
The current direct carbonation technology and indirect carbonation technology only focus on carbonation, but the influence of products after carbonation on the overall hydration performance of the composite cementing material is lack of attention.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide multi-component waste residue coupling quality-enhancing composite powder and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a multi-component waste residue coupling quality-enhancing composite powder, which comprises the following components: nano-grade CaCO3Or carbonated steel slag or carbonated waste concrete, blast furnace slag, coal furnace slag, LF furnace refining slag and desulfurized gypsum.
In some embodiments, nano-sized CaCO3The mass ratio of blast furnace slag, coal-fired furnace slag, LF furnace refining slag and desulfurization gypsum is as follows: 1-10:50-70:5-20:10-30:5-10.
In some embodiments, the mass ratio of the carbonated steel slag or carbonated waste concrete, blast furnace slag, coal furnace slag, LF furnace refining slag and desulfurized gypsum is 6-25:50-70:5-15:10-20: 5-10.
In some embodiments, the nanoscale CaCO3Is prepared by an indirect carbonation method.
In some embodiments, the specific surface area of the powder in the composite powder is 400-550m2/kg。
In a second aspect, the invention provides a preparation method of the multi-component waste residue coupling quality-enhancing composite powder, which comprises the following steps:
mixing the components according to a set proportion and grinding to obtain the composite powder.
In some embodiments, hot air is introduced for drying during the grinding process.
The raw materials contain certain moisture, so hot air is introduced for drying in the grinding process, the dryness of the powder is improved, and the subsequent powder selection is convenient to carry out.
Furthermore, the method also comprises the step of selecting powder after grinding and drying each component.
Furthermore, after the powder with the specific surface area meeting the requirement is selected, the powder enters a dust collection unit to be collected under the action of wind power and negative pressure.
In a third aspect, the invention provides the use of the composite powder as an auxiliary additive in the preparation of cement or concrete.
In a fourth aspect, the invention provides cement, which comprises the composite powder, wherein the mass percent of the composite powder is 3% -30%, and preferably 5% -20%.
In a fifth aspect, the invention provides a concrete, which comprises the composite powder, wherein the mass percent of the composite powder is 3% -30%, and preferably 5% -20%.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the invention is based on the technical treatment of direct carbonation or indirect carbonation of solid wastes such as calcium-rich steel slag, waste concrete and the like to obtain the nano CaCO3Granular steel slag, waste concrete or nano-grade CaCO directly extracted3The particles are prepared into multi-component waste residue coupling quality-enhancing composite powder through a grinding process with LF furnace refining slag, blast furnace slag, power plant coal-fired furnace slag and power plant desulfurized gypsum, the components of the composite powder generate physical and chemical reactions with strong relevance, the composite powder is added into an inorganic nonmetal composite cementing material system such as cement or concrete, and nano-grade CaCO generated through a carbonation reaction3The particles play a 'crystal nucleus effect', promote the early hydration of the inorganic non-metal cementing material, simultaneously generate hydrated calcium carbonate aluminate, and jointly act with other components in the composite powder to promote the generation and the stability of needle-rod-mounted AFt, thereby improving the bending strength and the compressive strength of inorganic non-metal composite cementing material systems such as cement, concrete and the like.
The invention utilizes nano-grade CaCO generated by carbonation technology3The granules simultaneously open a new way for the utilization of the carbonated product of the solid waste according to the strong coupling effect among the waste residues, improve the problem of difficult utilization of the solid waste such as LF furnace refining slag, power plant coal-fired furnace slag and the like, and simultaneously improve the utilization rate of the solid wasteThe performance of building materials such as cement, concrete and the like is improved, the breaking strength of the cement and the concrete can be improved by more than or equal to 10 percent, and the compressive strength is improved by more than or equal to 10 percent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a nano-grade CaCO produced by carbonation in an embodiment of the present invention3SEM photograph and EDS spectra of the particles;
FIG. 2 is an Aft plot of a needle bar in a cement hardened slurry in accordance with an embodiment of the present invention;
fig. 3 is a schematic flow chart of a preparation method of the composite powder in the embodiment of the invention.
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.
The carbonated steel slag and the carbonated waste concrete are both prepared by adopting a direct carbonation method, and the specific preparation method comprises the following steps:
placing the steel slag powder or the waste concrete powder in a mortar stirrer, spraying water with the mass fraction of 5-19%, stirring and mixing uniformly, immediately placing the mixture in a carbonation reaction kettle, introducing carbon dioxide gas with the concentration of 25-100%, maintaining for 2-24 h at the temperature of 50-120 ℃ and the carbon dioxide pressure of 0.2-1 MPa, immediately taking out, placing in a drying box at the temperature of 100-200 ℃, and drying for 0.5-1 h. Taking out, cooling to room temperature, and grinding the mixture by using a ball mill until the specific surface area is 400-500 m2/kg。
Nano-grade CaCO prepared by indirect carbonation method3The preparation method specifically comprises the following steps:
leaching Ca element in calcium-rich mineral (such as steel slag, waste concrete, etc.) with acetic acid or salicylic acid, introducing CO2Carbonating to obtain nano-grade CaCO3。
The direct carbonation technology and the indirect carbonation technology are based on the patents and research papers that have been published so far.
Separating the resulting CaCO3The SEM photograph and EDS spectrum of the particles are shown in fig. 1.
The mechanism of multi-component waste residue coupling quality enhancement is as follows:
al in blast furnace slag2O3The content reaches more than 16.5 percent, and Al in the coal-fired furnace slag of the power plant2O3The content can reach 18 percent, but Al in the two types of slag2O3The activity of the slag is essentially different, the blast furnace slag is rapidly cooled by large water content, the vitreous body content is high, and Al2O3Is very active and is easy to react in the early stage. Al in the slag of coal-fired furnace in power plant2O3Although the content is high, the reaction activity is very low due to the difference between the generation mode and the cooling mode, and the reaction mainly participates in the hydration reaction at the later stage.
Al rich in blast furnace slag and coal-fired furnace slag of power plant2O3Al is provided in early and late stages of cement hydration2O3And as a supplementary Al element component for forming hydrated calcium carbonate aluminate.
The main component of the power plant desulfurization gypsum is CaSO4·2H2O, mainly plays a role in adjusting the setting time and exciting Al in blast furnace slag and coal-fired furnace slag of a power plant2O3Hydration activity, simultaneously with tricalcium aluminate (C) in cement3A) And Al in blast furnace slag and coal-fired furnace slag of power plant2O3Hydration to generate aluminium-calcium gel (C-A-H) to react and generate paired cement AFt (C)3A·3CaSO4·32H2O), the microstructure of AFt is a long pin-rod structure (see figure 2), which has beneficial effects on the improvement of the flexural strength and the compressive strength of cement, but the AFt structure is unstable and is easy to be converted into AFm (C)3A·CaSO4·12H2O), and the micro-morphology of the AFm is a short sheet-shaped structure, so that the compression strength and the flexural strength of the cement are not beneficial, and the reaction formula is as follows:
C-A-H+CaSO4·2H2O+H2O→C3A·3CaSO4·32H2O；
C3A·3CaSO4·32H2O→C3A·CaSO4·12H2O+2CaSO4·2H2O+8H2O。
the refining slag of the LF furnace is rich in Ca with high water solubility and can easily react with water to generate Ca (OH)2Can provide rich Ca in the hydration environment of cement and concrete2+Increasing Ca content in the initial stage of cement hydration2+Concentration, thereby shortening the induction period of hydration and promoting tricalcium silicate (C) in the cement3S) hydration, stimulating the calcium-silicon gel (C-S-H) gel and Ca (OH)2And (4) generating.
CaCO generated by directly carbonating or indirectly carbonating steel slag or waste concrete3Can reach nanometer level (the length of crystal is about 10-300nm), and the function of the material in cement-based composite gel material is as follows: (1) as C3S and C2The S hydration reaction plays a role in 'crystal nucleus effect', and promotes the early hydration process of the cement. (2) Carbonation of CaCO3Can react with the C-A-H gel in the composite cementing material slurry to generate hydrated calcium carbonate aluminate (C)3A·CaCO3·11H2O), the substance can stabilize AFt, inhibit the conversion of AFm to AFm and improve the flexural strength and the compressive strength of cement.
The main reason is due to AFt (C)3A·3CaSO4·32H2O) and AFm (C)3A·CaSO4·12H2O), AFt is a needle-rod-shaped structure and plays a role in cross reinforcement in hardened slurry, while AFm is a smaller plate-shaped structure and cannot effectively play a role in reinforcement.
The specific reaction formula is as follows:
1.5CaCO3+2C3A+0.5Ca(OH)2+22.5H2O→C3A·0.5CaCO3·0.5Ca(OH)2·11.5H2O+C3A·CaCO3·11H2O；
2C3A·0.5CaCO3·0.5Ca(OH)2·11.5H2O→C3A·CaCO3·11H2O+C3AH6；
3C3A·CaSO4·12H2O+2CaCO3+18H2O→2C3A·CaCO3·11H2O+C3A·3CaSO4·32H2O。
examples
The preparation method of the multi-component waste residue coupling quality-enhancing composite powder comprises the following steps:
as shown in FIG. 1, CaCO produced by indirect carbonation3Or the steel slag and the waste concrete after being treated by the direct carbonation method are mixed with blast furnace slag, LF furnace refining slag, power plant coal-fired furnace slag and power plant desulphurization gypsum according to the mixture ratio in the tables 1 and 2, wherein nano-grade CaCO generated by the indirect carbonation method is used3The production of the particles is marked as composite powder 1, the production of the steel slag or waste concrete after direct carbonation treatment is marked as composite powder 2, the materials are conveyed into a vertical mill grinding unit through a belt and other conveying equipment after passing through a metering and proportioning unit, meanwhile, because each raw material contains certain moisture, part of hot air is provided by a hot blast stove for drying the materials while the materials are ground, the ground powder enters a powder selecting unit under the action of wind power and negative pressure, and the rotating speed of the powder selecting machine is mainly adjusted, so that the specific surface area is 400-550m2And the powder is driven by wind power and negative pressure to enter a dust collection unit, and finished products are collected and put in storage.
Performance of multicomponent waste slag coupling quality-increasing composite powder
The activity index of the multi-component waste residue coupling quality-enhancing composite powder is detected according to GBT18046-2017 for granulated blast furnace slag powder in cement, mortar and concrete, and the detection results of the composite powder 1 and the composite powder 2 are respectively shown in tables 1 and 2.
Table 1 detection results of composite powder 1
Table 2 detection results of composite powder 2
Clinker, limestone, desulfurized gypsum, fly ash, blast furnace slag powder and composite powder are used for preparing 42.5-grade cement, and the cement is prepared by grinding the cement to have the specific surface area of 350-380 m2The flexural and compressive strengths of 3d and 28d were measured as/kg and the results are shown in tables 3 and 4.
TABLE 3 Properties of 42.5-grade Cement formulated with composite powder 1
TABLE 4 Properties of 42.5-grade cements formulated with composite powder 2
As can be seen from the test results in tables 3 and 4, the prepared composite powder 1 and composite powder 2 can improve the flexural strength and compressive strength of 42.5-grade cement.
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. A multi-component waste residue coupling quality-enhancing composite powder is characterized in that: comprises the following components: nano-grade CaCO3Or carbonated steel slag or carbonated waste concrete, blast furnace slag, coal furnace slag, LF furnace refining slag and desulfurized gypsum.
2. The multi-component waste residue coupling and quality-enhancing composite powder according to claim 1, wherein: nano-grade CaCO3The mass ratio of blast furnace slag, coal-fired furnace slag, LF furnace refining slag and desulfurization gypsum is as follows: 1-10:50-70:5-20:10-30:5-10.
3. The multi-component waste residue coupling and quality-enhancing composite powder according to claim 1, wherein: the mass ratio of the carbonated steel slag or carbonated waste concrete, blast furnace slag, coal furnace slag, LF furnace refining slag and desulfurized gypsum is 6-25:50-70:5-15:10-20: 5-10.
4. The multi-component waste residue coupling and quality-enhancing composite powder according to claim 1, wherein: the nano-grade CaCO3Is prepared by an indirect carbonation method.
5. The multi-component waste residue coupling and quality-enhancing composite powder according to claim 1, wherein: the specific surface area of the powder in the composite powder is 400-550m2/kg。
6. The preparation method of the multi-component waste residue coupling quality-enhancing composite powder as claimed in any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
mixing the components according to a set proportion and grinding to obtain the composite powder.
7. The preparation method of the multi-component waste residue coupled quality-enhancing composite powder according to claim 6, characterized by comprising the following steps: in the grinding process, hot air is introduced for drying;
further, after grinding and drying each component, the method also comprises the step of selecting powder;
furthermore, after the powder with the specific surface area meeting the requirement is selected, the powder enters a dust collection unit to be collected under the action of wind power and negative pressure.
8. Use of the composite powder according to any one of claims 1 to 5 as an auxiliary additive for the preparation of cement or concrete.
9. A cement, characterized in that: the composite powder comprises the composite powder of any one of claims 1 to 5, and the mass percentage of the composite powder is 3 to 30 percent, preferably 5 to 20 percent.
10. A concrete characterized by: the composite powder comprises the composite powder of any one of claims 1 to 5, and the mass percentage of the composite powder is 3 to 30 percent, preferably 5 to 20 percent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4324803A1 (en) * | 2022-08-17 | 2024-02-21 | Carbon Upcycling Technologies Inc. | A mechanochemically carbonated slag, methods of its production and uses thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304851A (en) * | 2019-07-19 | 2019-10-08 | 迁安威盛固废环保实业有限公司 | A kind of full solid waste cementitious material and preparation method thereof containing refining slag |
| CN112321180A (en) * | 2020-09-30 | 2021-02-05 | 日照钢铁控股集团有限公司 | Carbonation pretreatment process for refining slag of LF (ladle furnace) |
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- 2021-11-25 CN CN202111416584.7A patent/CN114163158A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304851A (en) * | 2019-07-19 | 2019-10-08 | 迁安威盛固废环保实业有限公司 | A kind of full solid waste cementitious material and preparation method thereof containing refining slag |
| CN112321180A (en) * | 2020-09-30 | 2021-02-05 | 日照钢铁控股集团有限公司 | Carbonation pretreatment process for refining slag of LF (ladle furnace) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4324803A1 (en) * | 2022-08-17 | 2024-02-21 | Carbon Upcycling Technologies Inc. | A mechanochemically carbonated slag, methods of its production and uses thereof |
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