CN110845163A - Copper slag aggregate and preparation method and application thereof - Google Patents
Copper slag aggregate and preparation method and application thereof Download PDFInfo
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- CN110845163A CN110845163A CN201911314674.8A CN201911314674A CN110845163A CN 110845163 A CN110845163 A CN 110845163A CN 201911314674 A CN201911314674 A CN 201911314674A CN 110845163 A CN110845163 A CN 110845163A
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- 239000002893 slag Substances 0.000 title claims abstract description 144
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000010949 copper Substances 0.000 title claims abstract description 134
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000003723 Smelting Methods 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 238000010791 quenching Methods 0.000 claims abstract description 30
- 230000000171 quenching effect Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 18
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 18
- 239000004571 lime Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000004567 concrete Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 41
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 30
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 30
- 239000006148 magnetic separator Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000007885 magnetic separation Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000010220 ion permeability Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 27
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000006004 Quartz sand Substances 0.000 description 11
- 239000004568 cement Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004574 high-performance concrete Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011374 ultra-high-performance concrete Substances 0.000 description 1
Images
Classifications
-
- 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
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/023—Fired or melted materials
- C04B18/026—Melted materials
-
- 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
-
- 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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a copper slag aggregate and a preparation method and application thereof, belonging to the field of comprehensive utilization of non-ferrous metallurgy solid wastes. A preparation method of copper slag aggregate comprises the following steps: mixing 65-80 wt% of converter copper smelting water-quenched slag, 15-25 wt% of ferrosilicon and 5-20 wt% of lime, and grinding to reach a 2mm square-hole sieve passing rate of 80%; melting the ground copper slag mixture at 1120-1150 ℃ by using a submerged arc furnace until the copper slag mixture is completely melted, and keeping the temperature for 3 h; after molten iron is discharged from the melt, performing water quenching treatment on the residual slag to obtain tailings; grinding and magnetically separating the obtained tailings, classifying copper slag aggregates into three grades of copper slag aggregates with the grain sizes of 0.6-1.25 mm, 0.3-0.6 mm and 0.15-0.6 mm by taking square-hole sieves with the grain sizes of 0.15mm, 0.3mm and 0.6mm as key control sieve holes, and magnetically separating and deironing each grade of the aggregates; and obtaining the copper slag aggregate. The invention provides a good way for high-value and large-scale consumption of a large amount of stockpiled copper smelting slag and provides a technical support for wide application of the active powder concrete.
Description
Technical Field
The invention relates to a copper slag aggregate and a preparation method and application thereof, in particular to a preparation method of the copper slag aggregate suitable for preparing Reactive Powder Concrete (RPC), and belongs to the field of comprehensive utilization of solid waste in non-ferrous metal smelting.
Background
The slag of the pyrometallurgical copper smelting is non-ferrous metal smelting slag with high stockpiling amount, and the average smelting of 1 ton of copper can generate 2 tons of slag. The problem of relieving the large amount of stacking of copper smelting slag by a pyrogenic process is urgently needed to be solved.
The converter copper smelting slag is one of the copper smelting slag with a larger proportion, the iron content in the components is up to 40-50%, which is equivalent to the average grade of domestic iron ore, but the iron phase in the copper slag mainly comprises ferric silicate and a small amount of magnetic iron, and the magnetic iron is usually embedded in the ferric silicate phase in the associated state, the intergrowth state and the like, and is difficult to directly recover in a magnetic separation mode. The existence of a large amount of iron silicate phase in the copper slag causes the copper slag to have poor grinding performance, thereby bringing more difficulty to the recovery of copper and iron. Therefore, in recent years, although many enterprises have carried out engineering practices for recovering copper and iron from copper smelting slag, the cost is too high to continue to be deep. Therefore, it is temporarily difficult to industrially apply the valuable metals recovered from the copper slag.
In the aspect of building material production, the copper slag is generally used as an iron correction raw material for cement production, and the consumption is low; but directly used for producing cement clinker, because the content of Ca-containing components is low, the cement clinker can not be directly used. Therefore, the method can be used for large-scale consumption of the solid wastes in mining and metallurgy, namely cement production, and obviously cannot be used for large-scale consumption of copper slag. At present, most of the research results of the resource utilization of the copper slag are the extraction of valuable metals; in the aspect of high-value utilization, the production of copper slag ceramic products, the extraction of chemical raw materials from copper slag and the like are difficult to relieve the problem of mass stockpiling of copper slag.
The active powder concrete is a high-performance concrete which is proposed in the last 90 years, is prepared according to the maximum compactness principle by taking quartz sand or river sand with the particle size range of 0.15-1.25 mm as aggregate, has the characteristics of light weight and high strength, is regarded as third-generation high-performance concrete (UHPC), and is more outstanding in durability and elastic modulus, and the 800-grade PRC elastic modulus and durability exceed those of aluminum alloy materials. The 200-grade RPC with the lowest grade has the compression strength of 100-230 MPa and the bending strength of more than 12MPa, so that the reinforcement can be eliminated due to the high compression strength and bending strength, and the market development prospect in the aspects of high-rise buildings, national defense projects, bridge projects and the like is wide. It is noteworthy, however, that the preparation of a typical RPC requires high temperature steam curing and the incorporation of large amounts of corrosion resistant steel fibers, while also requiring high purity quartz sand to ensure high strength. Therefore, although RPC has excellent use performance, the RPC is not accepted by a large number of construction fields because of high production cost, and is only used in the construction fields with high economic and technical added values, such as high-speed rails, subways, antique buildings, and the like, on a large scale at present.
The fine aggregate accounts for 60% in the RPC component, and compared with natural sand, the quartz sand can better ensure that the RPC obtains higher strength, has higher cost, and cannot ensure long-term, stable and large-scale market supply, thereby further limiting the wide application of the RPC. By using the technical idea of RPC, the aggregate meeting the RPC preparation requirement is prepared by utilizing the characteristics of relatively single mineral component and less harmful components of the water quenching slag in the smelting of the copper in the converter, and the quartz sand in the RPC component is replaced, so that the production cost of the RPC and the components thereof can be greatly reduced. The method has outstanding practical significance for high-value and large-scale utilization of the copper slag.
The invention is especially provided for solving the problems in the prior art and simultaneously consuming the copper slag on a large scale.
Disclosure of Invention
The invention is especially provided for the situation that the converter copper smelting water quenching slag has high Fe content and low CaO content and can not realize RPC composition design.
The invention is realized by the following technical scheme:
the copper slag aggregate comprises the following raw materials in percentage by weight: 75 percent of converter copper smelting water quenching slag, 15 percent of ferrosilicon and 10 percent of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 75 percent of converter copper smelting water quenching slag, 15 percent of ferrosilicon and 10 percent of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 70 percent of converter copper smelting water quenching slag, 23 percent of ferrosilicon and 7 percent of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 75 percent of converter copper smelting water quenching slag, 20 percent of ferrosilicon and 5 percent of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 65 percent of converter copper smelting water quenching slag, 25 percent of ferrosilicon and 10 percent of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 78% of converter copper smelting water quenching slag, 16% of ferrosilicon and 6% of lime.
Preferably, the copper slag aggregate is prepared from the following raw materials in percentage by weight: 73 percent of converter copper smelting water quenching slag, 18 percent of ferrosilicon and 9 percent of lime.
A preparation method of copper slag aggregate comprises the following steps:
(1) mixing 65-75% of converter copper smelting water-quenched slag, 15-25% of ferrosilicon and 5-10% of lime mixed ash, and crushing to obtain a mixed material;
(2) melting the mixed material at 1120-1150 ℃ and preserving heat to obtain a melt;
(3) discharging molten iron from the melt, and performing water quenching treatment on the residual slag to obtain iron-removed tailings;
(4) grinding, magnetically separating and grading the iron-removed tailings to obtain copper slag aggregates with different grades; and then carrying out magnetic separation and iron removal on the copper slag aggregates with different grades respectively to obtain the copper slag aggregates.
Preferably, in the step (1), the raw material is pulverized to have a 2mm square hole passing rate of 80%.
Preferably, in the step (2), the holding time is 3 h.
Preferably, in the step (4), three grades of copper slag aggregates with the thickness of 0.6-1.25 mm, 0.3-0.6 mm and 0.15-0.6 mm are obtained.
Preferably, the copper slag aggregate is used for the preparation of Reactive Powder Concrete (RPC).
Preferably, the Methylene Blue (MB) value of the copper slag aggregate is less than or equal to 0.4 g/kg.
The invention has the beneficial effects that:
(1) the method for preparing the copper slag aggregate can utilize the copper slag in a high-value and large-scale manner.
(2) The copper slag aggregate Reactive Powder Concrete (RPC) prepared by the invention is used for replacing quartz sand aggregates in typical formula RPC compositions, and has a 7d compressive strength representative value of 103-135 MPa, a bending strength representative value of 12.3-15.8 MPa, a chloride ion permeability Q value range of 95-98 and frost resistance of more than F500.
Drawings
FIG. 1 is a process flow diagram for the preparation of copper slag aggregate according to the present invention.
Detailed Description
The invention aims at the preparation of copper slag aggregate suitable for preparing Reactive Powder Concrete (RPC), and the overall thought is as follows:
aiming at the condition that the converter copper smelting water quenching slag has high Fe content and low CaO content and cannot realize RPC composition design, the converter copper smelting water quenching slag with the weight percentage of 65-75%, 15-25% of ferrosilicon and 5-10% of lime are mixed and ground until the passing rate of a 2mm square-hole sieve is 80%, and a raw material mixture is obtained; directly reducing the mixture by using an ore furnace at 1120-1150 ℃, discharging molten iron obtained by reduction, and performing water quenching treatment on residual slag to obtain tailings after iron removal by reduction; grinding and magnetically separating tailings, taking a square-hole sieve of 0.15mm, 0.3mm and 0.6mm as a key control sieve pore, grading copper slag tailings particles to obtain copper slag aggregates of three grades of 0.6-1.25 mm, 0.3-0.6 mm and 0.15-0.6 mm, and magnetically separating and deironing each grade of aggregate to obtain the copper slag aggregate suitable for RPC.
The methylene blue value MB of the copper slag aggregate prepared by the invention needs to be detected. The methylene blue value reflects the content of expansive clay or easily-occurring alkali aggregate reaction components (such as stone powder) in the copper slag aggregate, the content of the expansive clay or easily-occurring alkali aggregate reaction components is reduced to ensure the improvement of the long-term stability and the environmental durability of the PRC prepared from the copper slag aggregate, and although the process is subjected to a high-temperature reduction process, the process cannot ensure that all clay substances introduced by long-term stockpiling are subjected to phase transformation or loss, and a new phase causing the alkali aggregate reaction is possibly formed, so that the MB value of the copper slag aggregate prepared by the process is not more than 0.4 g/kg.
The test and analysis results of the total components of the converter copper smelting water quenching slag used in the invention are shown in the following table 1.
TABLE 1 full ingredient assay analysis result of converter copper smelting water quenching slag
| Serial number | FeO | SiO2 | Fe3O4 | CaO | MgO | Al2O3 | S | Cu |
| 1# | 47.56 | 17.28 | 12.48 | 1.55 | 0.35 | 7.32 | 1.25 | 1.12 |
| 2# | 58.14 | 14.33 | 5.69 | 2.17 | 1.22 | 5.96 | 3.33 | 1.96 |
| 3# | 39.25 | 28.54 | 18.88 | 2.26 | 0.69 | 3.32 | 0.98 | 1.88 |
Analysis results show that the main component of the converter copper smelting water quenching slag is Fe, and the content of CaO providing potential activity is only about 1.0-2.0%, so that the copper slag is inferred to be low-activity slag and basically can not be directly used as a raw material for calcining cement. But ground to be used directly for the preparation of RPC because of SiO therein2The low content can not ensure that Ca and Si hydration reaction under the excitation of RPC cement clinker can generate a large amount of strength contributing substance, ettringite. It is noted that the compositions in the table contain a certain amount of Al2O3Is the gain component of the RPC hydration reaction. Therefore, the Fe in the copper slag is removed to the maximum extent, and the SiO is supplemented2And the CaO content is very favorable for the preparation of RPC.
From the above analysis, copper slag aggregates suitable for RPC were prepared, the steps of which are detailed below:
(1) 65 to 75 percent by weightThe converter copper smelting water quenching slag, 15-25% ferrosilicon and 5-10% lime are mixed and ground until the passing rate of a 2mm square-hole sieve is 80% (namely D)80＝2mm)；
(2) Feeding the mixture into a submerged arc furnace, melting the copper slag mixture at 1120-1150 ℃ until the mixture is completely melted, and keeping the temperature for 3 h;
(3) after the reduced molten iron is discharged, carrying out water quenching treatment on the molten slag to obtain copper slag tailings after the iron is reduced;
(4) grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal;
(5) sieving materials with the particle size of more than 0.6mm, grinding the rest materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization;
(6) sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of the 0.15 square-hole sieve is less than 5%, and feeding into a magnetic separator for deferrization;
(7) screening out materials with the particle size larger than 0.15mm, and feeding the rest materials into a magnetic separator for deferrization;
thus obtaining the copper slag aggregate for RPC with three grades of 0.6-1.25 mm, 0.3-0.6 mm and 0.15-0.6 mm.
Example 1
Firstly, converter copper smelting water quenching slag, ferrosilicon and lime are mixed according to the proportion of 75%: 15%: mixing 10%, grinding to D802 mm; feeding the mixture into a submerged arc furnace, melting the copper slag mixture at 1120-1150 ℃ until the mixture is completely melted, and keeping the temperature for 3 h; after the reduced molten iron is discharged, carrying out water quenching treatment on the molten slag to obtain copper slag tailings after the iron is reduced; grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal; sieving materials with the particle size of more than 0.6mm, grinding the rest materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization; sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of the 0.15 square-hole sieve is less than 5%, and feeding into a magnetic separator for deferrization; and obtaining the copper slag aggregate for the third-grade RPC.
And detecting the methylene blue value MB of the obtained copper slag aggregate, wherein the MB is 0 g/kg.
According to a typical RPC formula, the obtained three-grade copper slag aggregate is used as a fine aggregate, RPC is prepared, and the performance of the RPC is detected, wherein the 7d compressive strength representative value is 125MPa, the flexural strength representative value is 15.8MPa, the chloride ion permeability Q value range is 96, and the frost resistance is greater than F510.
Example 2
Firstly, converter copper smelting water quenching slag, ferrosilicon and lime are mixed according to the proportion of 70%: 23%: 7 percent of the mixture is mixed and ground to D802 mm; feeding the mixture into a submerged arc furnace, melting the copper slag mixture at 1120-1150 ℃ until the mixture is completely melted, and keeping the temperature for 3 h; after the reduced molten iron is discharged, carrying out water quenching treatment on the molten slag to obtain copper slag tailings after the iron is reduced; grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal; sieving materials with the particle size of more than 0.6mm, grinding the rest materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization; sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of the 0.15 square-hole sieve is less than 5%, and feeding into a magnetic separator for deferrization; and obtaining the copper slag aggregate for the third-grade RPC.
And detecting the methylene blue value MB of the obtained copper slag aggregate, wherein the MB is 0.4 g/kg.
According to a typical RPC formula, the obtained three-grade copper slag aggregate is used as a fine aggregate, RPC is prepared, and the performance of the RPC is detected, wherein the 7d compressive strength representative value is 116MPa, the flexural strength representative value is 14.2MPa, the chloride ion permeability Q value range is 97, and the frost resistance is greater than F505.
Example 3
Firstly, converter copper smelting water quenching slag, ferrosilicon and lime are mixed according to the proportion of 75%: 20%: 5 percent of the mixture is mixed and ground to D802 mm; feeding the mixture into a submerged arc furnace, melting the copper slag mixture at 1120-1150 ℃ until the mixture is completely melted, and keeping the temperature for 3 h; after the reduced molten iron is discharged, carrying out water quenching treatment on the molten slag to obtain copper slag tailings after the iron is reduced; grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal; sieving to remove materials with particle size of more than 0.6mm and residuesGrinding the materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization; sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of the 0.15 square-hole sieve is less than 5%, and feeding into a magnetic separator for deferrization; and obtaining the copper slag aggregate for the third-grade RPC.
And detecting the methylene blue value MB of the obtained copper slag aggregate, wherein the MB is 0.6 g/kg.
According to a typical RPC formula, the obtained three-grade copper slag aggregate is used as a fine aggregate, RPC is prepared, and the performance of the RPC is detected, wherein the 7d compressive strength representative value is 103MPa, the flexural strength representative value is 12.3MPa, the chloride ion permeability Q value range is 93, and the frost resistance is higher than F501.
Example 4
Firstly, smelting converter copper by using water quenching slag, ferrosilicon and lime according to the proportion of 65%: 25%: mixing 10%, grinding to D802 mm; feeding the mixture into a submerged arc furnace, melting the copper slag mixture at 1120-1150 ℃ until the mixture is completely melted, and keeping the temperature for 3 h; after the reduced molten iron is discharged, carrying out water quenching treatment on the molten slag to obtain copper slag tailings after the iron is reduced; grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal; sieving materials with the particle size of more than 0.6mm, grinding the rest materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization; sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of the 0.15 square-hole sieve is less than 5%, and feeding into a magnetic separator for deferrization; and obtaining the copper slag aggregate for the third-grade RPC.
And detecting the methylene blue value MB of the obtained copper slag aggregate, wherein the MB is 0 g/kg.
According to a typical RPC formula, the obtained three-grade copper slag aggregate is used as a fine aggregate, RPC is prepared, and the performance of the RPC is detected, wherein the 7d compressive strength representative value is 135MPa, the flexural strength representative value is 13.6MPa, the chloride ion permeability Q value range is 97, and the frost resistance is greater than F510.
Comparative example 1
The comparison of the RPC technical economic performance of quartz sand and the copper slag aggregate prepared by the invention as aggregate under the typical RPC formula condition is shown in Table 2.
TABLE 2 comparison table of economic performance of RPC technique for high-purity quartz sand and copper slag aggregate
The data shown in table 2, based on a typical RPC formulation, was adjusted to an RPC formulation using the copper slag aggregate of the present invention, subject to the maximum theoretical density design rule and the minimum water-to-gel ratio at the optimum fluidity; according to the test method specified in the national standard of the people's republic of China, reactive powder concrete (GB/T31387-.
Compared with the data in the table 2, under the condition of a typical RPC formula, the technical performance of the quartz sand RPC and the copper slag RPC is superior to that of the quartz sand RPC on the basis of meeting the standard GB/T31387-2015; and in the aspect of economy, the copper slag RPC is obviously superior to the quartz sand RPC, and the unit comprehensive cost of the copper slag RPC is 30% lower than that of the quartz sand RPC.
Comparative example 2
The methylene blue value MB has certain influence on the technical performance of the RPC with the copper slag aggregate as the aggregate; the methylene blue value MB of the copper slag aggregate is closely related to the proportion of the copper slag in the raw materials for preparing the copper slag aggregate. The raw material proportion for preparing the copper slag aggregate is not suitable, and the Mg-containing crystal phase is easy to generate in the reduction process, so that the methylene blue value MB is increased. The comparative example is illustrated by comparing the situation of 80% copper slag.
TABLE 3 relationship between copper slag aggregate methylene blue value and copper slag RPC technical performance at different copper slag proportions
As can be seen from the comparison of the data in Table 3, the methylene blue value MB has a great influence on the technical performance, and in comparison, when the MB is less than or equal to 0.4, the copper slag RPC can obtain better technical performance more easily.
Claims (7)
1. The copper slag aggregate is characterized by comprising the following raw materials in percentage by weight: 75 percent of converter copper smelting water quenching slag, 15 percent of ferrosilicon and 10 percent of lime.
2. The preparation method of the copper slag aggregate is characterized by comprising the following steps:
(1) mixing 65-75% of converter copper smelting water-quenched slag, 15-25% of ferrosilicon and 5-10% of lime mixed ash, and crushing to obtain a mixed material;
(2) melting the mixed material at 1120-1150 ℃ and preserving heat to obtain a melt;
(3) discharging molten iron from the melt, and performing water quenching treatment on the residual slag to obtain iron-removed tailings;
(4) grinding, magnetically separating and grading the iron-removed tailings to obtain copper slag aggregates with different grades; and then carrying out magnetic separation and iron removal on the copper slag aggregates with different grades respectively to obtain the copper slag aggregates.
3. The production method according to claim 2, wherein in the step (1), the raw material is pulverized to have a 2mm square hole passage rate of 80%.
4. The method according to claim 2, wherein the holding time in the step (2) is 3 hours.
5. The preparation method according to claim 2, characterized by comprising the following steps:
(1) mixing 65-75 wt% of converter copper smelting water-quenched slag, 15-25 wt% of ferrosilicon and 5-10 wt% of lime, and grinding until the passing rate of a 2mm square-hole sieve is 80% to obtain a mixed material;
(2) the mixed materials are completely melted at 1120-1150 ℃, and the temperature is kept for 3 hours to obtain a melt;
(3) after molten iron is discharged from the melt, water quenching treatment is carried out on the molten slag to obtain copper slag tailings;
(4) grinding the tailings until the passing rate of a square-hole sieve with the diameter of 1.25mm is 100 percent and the passing rate of a sieve with the diameter of 0.6mm is more than 70 percent, and sending the tailings into a magnetic separator for magnetic separation and iron removal; sieving materials with the particle size of more than 0.6mm, grinding the rest materials until the passing rate of a 0.6mm square-hole sieve is 100 percent and the passing rate of a 0.3mm square-hole sieve is more than 40 percent, and sending the materials into a magnetic separator for deferrization; sieving to remove materials with particle size larger than 0.3mm, grinding the rest materials until the passing rate of a square-hole sieve with 0.15mm is less than 5%, and feeding the materials into a magnetic separator for deferrization; and screening out materials with the particle size larger than 0.15mm, and feeding the rest materials into a magnetic separator for deferrization to obtain the copper slag aggregate for RPC with the three grades of 0.6-1.25 mm, 0.3-0.6 mm and 0.15-0.6 mm.
6. The preparation method according to the claims 2-5, characterized in that the copper slag aggregate prepared by the preparation method is used for preparing reactive powder concrete.
7. The preparation method of the copper slag aggregate according to the claims 2-5, wherein the copper slag aggregate prepared by the preparation method has a Methylene Blue (MB) value of less than or equal to 0.4g/kg, a 7d compressive strength representative value of 108-137 MPa, a flexural strength representative value of 14.8-16.5 MPa, a chloride ion permeability Q value range of 95-98 and frost resistance of more than F500.
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