CN112499996A - Preparation method of shrinkage-reducing copper slag concrete - Google Patents
Preparation method of shrinkage-reducing copper slag concrete Download PDFInfo
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- CN112499996A CN112499996A CN202011398858.XA CN202011398858A CN112499996A CN 112499996 A CN112499996 A CN 112499996A CN 202011398858 A CN202011398858 A CN 202011398858A CN 112499996 A CN112499996 A CN 112499996A
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- 239000002893 slag Substances 0.000 title claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 107
- 239000010949 copper Substances 0.000 title claims abstract description 107
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000004568 cement Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000004127 vitreous body Anatomy 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000009466 transformation Effects 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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of shrinkage-reducing copper slag concrete, which comprises the following steps: calcining and activating the copper slag at high temperature; carrying out ultramicro airflow grinding on the copper slag to form copper slag powder; and preparing the concrete by using the copper slag powder as a raw material. The elasticity modulus of the concrete is improved, the shrinkage is reduced, the fracture resistance of the concrete is obviously improved, and the durability grade of the concrete is improved.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of smelting solid waste, in particular to a preparation method of shrinkage-reducing copper slag concrete.
Background
The prior copper slag treatment mainly adopts stacking, not only occupies a large amount of land, but also causes serious environmental pollution to the stacking land due to heavy metal components. At present, in the aspect of resource utilization of building materials, some copper slag has been explored as concrete aggregate and cement raw materials.
The research results in recent years show that the water-quenched copper slag has high vitreous body content and better activity, while the slow-cooling copper slag used by people still has certain activity although the vitreous body content is low. Because of the problems of low activity and high heavy metal content, the influence of the copper slag powder on the workability, mechanical property and durability of the concrete is more complicated than that of common admixtures such as slag, fly ash and the like, and the application of the copper slag powder as the admixture in the concrete is hindered.
Disclosure of Invention
The invention aims to solve the technical problem that the preparation method of the shrinkage-reducing type copper slag concrete is provided aiming at the defects in the prior art, so that the elastic modulus of the concrete is improved, the shrinkage is reduced, the fracture resistance of the concrete is obviously improved, and the durability grade of the concrete is improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of the shrinkage-reducing type copper slag concrete comprises the following steps:
step 1, calcining and activating copper slag at high temperature;
step 2, carrying out superfine airflow grinding on the copper slag to form copper slag powder;
and 3, preparing the concrete by using the copper slag powder as a raw material.
According to the technical scheme, in the step 1, the specific process of calcining and activating the copper slag at high temperature comprises the following steps: and calcining the copper slag in a furnace at 950-1000 ℃ for 30min, cooling the calcined copper slag in water, and drying to constant weight.
According to the technical scheme, in the step 2, the concrete process of carrying out ultrafine airflow grinding on the copper slag comprises the following steps: and grinding the copper slag for 40-50min by using an ultramicro jet mill to ensure that the particle size of the copper slag reaches 0.5-50 um.
According to the technical scheme, in the step 2, the specific surface area of the copper slag is 500-600m by grinding the copper slag2/kg。
According to the technical scheme, in the step 3, the concrete preparation process by using the copper slag powder as a raw material comprises the following steps: firstly, adding sand, stone, cement, active copper slag powder, mineral powder and fly ash into a forced mixer, adding water and a polycarboxylic acid water reducing agent after the mixing time is t1, and discharging after the mixing time is t 2; after the active copper slag powder is added, the hydration of cement is influenced, so that the conversion of the amount of ettringite in the hydration process of the cement is quicker, and the shrinkage reducing effect is achieved.
According to the technical scheme, the time t1 is 15 seconds to 25 seconds, and the time t2 is 100 seconds to 140 seconds.
The invention has the following beneficial effects:
the activation is carried out by calcining the slow-cooling copper slag powder at high temperature by the method, so that the copper slag can improve the elastic modulus of concrete and reduce the shrinkage, the fracture resistance is obviously improved, the number of harmful pores such as capillary pores is reduced, the water absorption rate and the water absorption capacity of the concrete are reduced, and the durability grade is improved.
Drawings
FIG. 1 is a crystal structure of a slowly-cooled copper slag before calcination in an example of the present invention;
FIG. 2 is a crystal structure of the slowly-cooled copper slag after calcination in the example of the present invention;
FIG. 3 is a graph showing the particle size distribution of the material before the ultra-fine air flow in the embodiment of the present invention;
FIG. 4 is a graph showing the particle size distribution of the material after the ultra-fine air flow in the example of the present invention;
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Referring to fig. 1 to 2, a method for preparing a reduction-type copper slag concrete in one embodiment of the present invention includes the following steps:
step 1, calcining and activating copper slag at high temperature;
step 2, carrying out superfine airflow grinding on the copper slag to form copper slag powder;
and 3, preparing the concrete by using the copper slag powder as a raw material.
Further, in the step 1, the specific process of calcining and activating the copper slag at high temperature comprises the following steps: and calcining the copper slag in a furnace at 950-1000 ℃ for 30min, cooling the calcined copper slag in water, and drying to constant weight.
Further, in the step 2, the specific process of performing ultrafine airflow grinding on the copper slag comprises the following steps: and grinding the copper slag for 40-50min by using an ultrafine jet mill to ensure that the particle size of the copper slag is 0.5-50 um.
Further, in the step 2, the copper slag is ground to enable the specific surface area of the copper slag to reach 500-600 square meters per kilogram.
Further, in the step 3, the concrete preparation process of the concrete by using the copper slag powder as the raw material comprises the following steps: firstly, adding sand, stone, cement, active copper slag powder, mineral powder and fly ash into a forced mixer, adding water and a polycarboxylic acid water reducing agent after the mixing time is t1, and discharging after the mixing time is t 2; after the active copper slag powder is added, the hydration of cement is influenced, so that the conversion of the amount of ettringite in the hydration process of the cement is quicker, and the shrinkage reducing effect is achieved.
Further, the time t1 is 15 seconds to 25 seconds, and the time t2 is 100 seconds to 140 seconds.
Further, time t1 is 20 seconds, and time t2 is 120 seconds.
The working principle of the invention is as follows: although the copper slag is smelted in different modes, most research results show that the copper slag powder can play a role in reducing heat release, improving workability and reducing water consumption, and simultaneously, the problem of increasing bleeding rate is also generated. Because the activity is low and the heavy metal component is high, the delayed coagulation effect of the copper slag powder is obvious, but the problem of prolonging the coagulation time caused by using a large mixing amount is controllable in most researches. The early strength of the concrete caused by the copper slag powder is insufficient, and the early strength of the concrete can be relieved and controlled by adding an exciting agent, improving the fineness, reducing the water-cement ratio and the like. The negative influence of the copper slag powder on the strength of the concrete is gradually reduced along with the prolonging of the age, and the copper slag powder is beneficial to the strength even after a period of time.
This patent carries out high temperature calcination to slow-cooling copper slag powder and arouses the activity, makes this copper slag can improve concrete elastic modulus and reduce the shrink, and the resistance to fracture performance also has obvious improvement effect, can impel harmful pore quantity such as capillary hole to reduce, can make the water absorption rate and the water absorption of concrete reduce to make the durability grade improve to some extent.
Step one, copper slag high-temperature calcination and activation: rapidly calcining slow-cooling copper slag in a 25kW high-temperature carbon tube furnace used in a laboratory, and raising the temperature of an empty furnace of the furnace to the set copper slag calcining temperature of 950-; 160g of copper slag is put into a hanging basket woven by molybdenum wires, and when the furnace reaches the set calcining temperature, the hanging basket filled with the copper slag sample is quickly put into the furnace for calcining. After the hanging basket filled with the copper slag sample enters the hearth, the temperature of the hearth fluctuates for a short time, timing is started when the hearth returns to 950 ℃, and the constant-temperature calcination time is set to be 30 min. Taking out the hanging basket immediately after the calcination is finished, and cooling the hanging basket in clean water; then drying to constant weight. When the calcining temperature is more than 950 ℃, the copper slag is subjected to ball milling to find a large amount of glass body content, which is much more than that of the non-calcined copper slag (the slow-cooling copper slag has a crystal phase mainly comprising olivine and is in a strip column shape, and a large amount of glass phase with a smooth surface appears after calcining); since this temperature of 950 ℃ has reached the result of phase transformation, the temperature does not have to continue to increase.
Step two, copper slag ultramicro airflow grinding: and carrying out ultramicro airflow grinding on the copper slag. The change trend of the copper slag under the action of the ultramicro jet mill can be divided into two stages, wherein the first stage is that the particle size of the copper slag is continuously reduced along with the prolonging of the grinding time, and the particle size range is gradually narrowed and is in concentrated distribution; when the particle size is smaller than a certain limit value, the internal crystal lattice of the copper slag is damaged, so that the system is unstable, the particle size of the copper slag is increased, and the activity is slightly influenced. Therefore, tests show that the superfine airflow grinding time of the copper slag is controlled to be 40-50min, the particle size distribution range of the copper slag is 0.5-50um, and the specific surface area can reach 500-600m2The activity of the copper slag can reach 80 percent at most. Proved by experiments, the ultramicro-qiThe longest time for crushing the copper slag in a flowing mode is 50min, the specific surface area of the copper slag continuously crushed is not increased but reduced, and partial agglomeration phenomenon (coarse particles of the copper slag are not reduced, fine particles are reduced, and fine particle agglomeration is indicated) occurs. The superfine airflow grinding has the advantages that the particle size distribution of particles is more uniform, the particle shape is more round and complete, and the excitation effect on the copper slag can be increased by about 20 percent, as shown in figures 3 and 4, the particle size distribution of the copper slag before and after the superfine airflow grinding is used is changed, the particle size distribution of the copper slag is more uniform after the copper slag is used, and the powder is finer. Step three, preparing the reduced copper slag concrete: the concrete mixing proportion of the following table 1 is used for carrying out the trial assembly work of the shrinkage-reducing type copper slag concrete, and the concrete shrinkage test block is formed and the non-contact shrinkage test of the concrete is carried out.
TABLE 1
In Table 1, G5-20 is pebble of 5-20mm, G20-40 is pebble of 20-40 mm.
Table 2 shows different shrinkage reduction effect data of the concrete prepared by adding different amounts of active copper slag powder to 10 groups in table 1.
TABLE 2
| Group of | 3d non-contact shrinkage/10-6 | 7d non-contact shrinkage/10-6 | 28d non-contact shrinkage/10-6 |
| 1 | 957 | 907 | 685 |
| 2 | 344 | 310 | 149 |
| 3 | 302 | 297 | 144 |
| 4 | 300 | 274 | 132 |
| 5 | 245 | 231 | 135 |
| 6 | 1012 | 986 | 691 |
| 7 | 442 | 441 | 201 |
| 8 | 402 | 395 | 187 |
| 9 | 399 | 386 | 175 |
| 10 | 385 | 365 | 166 |
The above is only a preferred embodiment of the present invention, and certainly, the scope of the present invention should not be limited thereby, and therefore, the present invention is not limited by the scope of the claims.
Claims (6)
1. The preparation method of the shrinkage-reducing type copper slag concrete is characterized by comprising the following steps:
step 1, calcining and activating copper slag at high temperature;
step 2, carrying out superfine airflow grinding on the copper slag to form copper slag powder;
and 3, preparing the concrete by using the copper slag powder as a raw material.
2. The preparation method of the reduction-type copper slag concrete according to claim 1, wherein in the step 1, the specific process of calcining and activating the copper slag at high temperature comprises the following steps: and calcining the copper slag in a furnace at 950-1000 ℃ for 30min, cooling the calcined copper slag in water (at the temperature of 20 +/-2 ℃), and drying to constant weight.
3. The preparation method of the reduction-type copper slag concrete according to claim 1, wherein in the step 2, the concrete process of carrying out ultrafine airflow grinding on the copper slag comprises the following steps: and grinding the copper slag for 40-50min by using an ultramicro jet mill to ensure that the particle size of the copper slag reaches 0.5-50 um.
4. The preparation method of the reduction type copper slag concrete according to claim 3, wherein in the step 2, the specific surface area of the copper slag is up to 500-600 square meters per kg by grinding the copper slag.
5. The preparation method of the reduction-type copper slag concrete according to claim 1, wherein in the step 3, the concrete preparation process by using the copper slag powder as a raw material comprises the following specific steps: firstly, adding sand, stone, cement, copper slag powder, mineral powder and fly ash into a stirrer, stirring for t1, adding water and a polycarboxylic acid water reducing agent, stirring for t2, and discharging.
6. The method for preparing the reduction-type copper slag concrete according to claim 1, wherein the time t1 is 15 seconds to 25 seconds, and the time t2 is 100 seconds to 140 seconds.
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| CN202011398858.XA CN112499996A (en) | 2020-12-02 | 2020-12-02 | Preparation method of shrinkage-reducing copper slag concrete |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011398858.XA CN112499996A (en) | 2020-12-02 | 2020-12-02 | Preparation method of shrinkage-reducing copper slag concrete |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213801A (en) * | 2021-06-29 | 2021-08-06 | 江西科技学院 | Activation method of copper slag and application of copper slag in high-performance concrete |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593493A (en) * | 1995-06-26 | 1997-01-14 | Krofchak; David | Method of making concrete from base metal smelter slag |
| CN107365093A (en) * | 2017-06-27 | 2017-11-21 | 紫金铜业有限公司 | A kind of preparation method of the active copper ashes of binder materials |
| CN109095859A (en) * | 2018-09-13 | 2018-12-28 | 湖北工业大学 | A kind of self-healing anti-cracking waterproof root resistance concrete |
| CN110845163A (en) * | 2019-12-19 | 2020-02-28 | 沈阳有色金属研究院有限公司 | Copper slag aggregate and preparation method and application thereof |
-
2020
- 2020-12-02 CN CN202011398858.XA patent/CN112499996A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593493A (en) * | 1995-06-26 | 1997-01-14 | Krofchak; David | Method of making concrete from base metal smelter slag |
| CN107365093A (en) * | 2017-06-27 | 2017-11-21 | 紫金铜业有限公司 | A kind of preparation method of the active copper ashes of binder materials |
| CN109095859A (en) * | 2018-09-13 | 2018-12-28 | 湖北工业大学 | A kind of self-healing anti-cracking waterproof root resistance concrete |
| CN110845163A (en) * | 2019-12-19 | 2020-02-28 | 沈阳有色金属研究院有限公司 | Copper slag aggregate and preparation method and application thereof |
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| Title |
|---|
| 刘维良: "《先进陶瓷工艺学》", 31 August 2004, 武汉理工大学出版社 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213801A (en) * | 2021-06-29 | 2021-08-06 | 江西科技学院 | Activation method of copper slag and application of copper slag in high-performance concrete |
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Application publication date: 20210316 |