CN117303758A - Method for improving pozzolan activity of water quenched copper slag and application thereof - Google Patents
Method for improving pozzolan activity of water quenched copper slag and application thereof Download PDFInfo
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- CN117303758A CN117303758A CN202311371344.9A CN202311371344A CN117303758A CN 117303758 A CN117303758 A CN 117303758A CN 202311371344 A CN202311371344 A CN 202311371344A CN 117303758 A CN117303758 A CN 117303758A
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- copper slag
- slag
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- molten
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- 239000002893 slag Substances 0.000 title claims abstract description 113
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 76
- 239000010949 copper Substances 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000694 effects Effects 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000004568 cement Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000004567 concrete Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006703 hydration reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001691 hercynite Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/144—Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a method for improving the volcanic ash activity of water quenched copper slag and application thereof, which comprises the steps of adding Al into molten copper slag 2 O 3 Modifying copper slag, and carrying out high-temperature mixing reaction. And carrying out water quenching, drying, grinding and the like on the mixture to form the auxiliary cementing material with higher pozzolanic activity. The invention utilizes the slag discharge port to discharge the molten high-temperature copper slag, and directly combines with Al 2 O 3 The mixing is modified, so that the additional cost of secondary calcination is avoided, and the method has the advantage of low energy consumption; copper slag and Al 2 O 3 The chemical reaction for producing tricalcium aluminate, which is one of the main components of cement, is a main source for cement hydration reaction and strength production, and utilizes Al precisely 2 O 3 Exciting potential pozzolanic activity of copper slag; the invention utilizes a simpler methodThe volcanic ash activity of the copper slag is improved, the utilization scene of the copper slag is widened, and the method has the significance of resource circulation and environmental protection.
Description
Technical Field
The invention belongs to the field of industrial solid waste recycling, and particularly relates to a method for improving pozzolan activity of water quenched copper slag.
Background
Energy shortage, resource shortage and environmental deterioration are three challenges facing the world today. Cement is an important basic building material, and the production process is accompanied by huge resource and energy consumption, and the cement is used for amplifying a large amount of dust and harmful gas side by side, so that the cement has serious pollution to the environment. Therefore, it is important for researchers to reduce the consumption of cement and to maintain the effective strength of cement and reduce environmental pollution.
Copper slag is industrial solid waste generated in the copper smelting process. Because the metal content in the copper concentrate is low, a large amount of copper slag is inevitably generated in the high-temperature smelting process; the annual yield of copper slag is about 4000 ten thousand t per 1t copper metal produced, about 2.2 to 3t copper slag. The copper slag is directly piled up or poured, so that precious land resources are occupied, and surrounding atmosphere, soil and groundwater resources are polluted. The water quenched copper slag is a vitreous material formed by melting steel-making slag in water quenching Chi Zhongli, has a brownish black appearance, slightly coarser particles than ordinary sand, hard texture, sharp correction angle and SiO 2 And the glass phase content is higher, a certain volcanic ash characteristic is shown, the combination with hardened cement stone is good, the physical and mechanical properties of the copper slag fine aggregate concrete are better than those of the common concrete, and the copper slag fine aggregate concrete has the potential of being used as an auxiliary cementing material. However, a certain amount of heavy metal elements are also present in the copper slag, and the heavy metals are likely to be brought into cement materials to cause pollution, and the hydration activity of the copper slag is low due to the fact that the iron content in the copper slag is too high and the calcium content is too low, so that the application of the copper slag in the novel cement materials is greatly limited, and therefore, the improvement of the reactivity of the copper slag is particularly important.
Disclosure of Invention
In order to solve the technical problems, the method solves the problem that the water quenched copper slag is difficult to obtain effective application due to low activity, the potential of the water quenched copper slag as an auxiliary cementing material is excavated, and Al is added into the molten copper slag 2 O 3 Further the copper slag is modified,the volcanic ash activity of the copper slag waste material and the utilization rate of the copper slag waste material in the cementing material are improved.
In order to achieve the above object, the present invention firstly provides a method for improving the pozzolan activity of water quenched copper slag, comprising the following steps:
s1, putting molten copper slag into a modulating furnace, and adding Al into the modulating furnace 2 O 3 Fully mixing the two materials, and reacting at high temperature to obtain mixed molten state clinker;
s2, carrying out water cooling treatment on the molten clinker mixed in the step S1, and collecting cooled modified copper slag particles;
and S3, drying the modified copper slag particles, and grinding the dried modified copper slag particles to a powder state to obtain a modified copper slag powder product.
Preferably, the temperature in the modulating furnace in the step S1 is not lower than 1200 ℃.
Preferably, the mixing reaction time in the step S1 is 30min.
Preferably, al in the S1 step 2 O 3 The addition amount is 5-30% of the copper slag mass.
Preferably, the surface area D90 value of the powdery modified copper slag in the step S3 is 350-400 m 2 /kg。
Based on a general inventive concept, the invention also provides application of the modified copper slag powder in preparing the concrete cementing material, and the modified copper slag and the cement material are mixed and stirred to form the concrete cementing material.
Preferably, the addition amount of the modified copper slag powder is 30-50% of the mass of the cement.
The principle that the modified copper slag can be used as a cementing material in the invention is as follows:
Al 2 O 3 is an amphoteric oxide, can act as a network breaker and also can act as a network inoculant, depending on the slag composition. When the content of the basic oxide component is high, al 2 O 3 Which can be expressed as an acidic oxide, the microstructure of the copper slag is transformed into a complex network structure; when the content of the acidic oxide is high, al 2 O 3 Then it is a basic oxygen which damages the gridAnd (3) chemical compounds. Thus, the first and second substrates are bonded together,
during the depletion process, al 2 O 3 Is considered as an acidic substance, and Al is added 2 O 3 High melting point compounds can be formed and the liquidus temperature of the copper slag can be increased, thereby leading to the increase of the viscosity of the copper slag; adding Al into copper slag 2 O 3 High-melting-point hercynite is formed, and is precipitated in a solid phase in slag, so that the viscosity is increased; al (Al) 2 O 3 The addition of the catalyst can increase the polymerization degree of the slag, so that the slag structure tends to be complex, and the viscosity is increased; at the same time, copper slag and Al 2 O 3 The chemical reaction produces tricalcium aluminate, which is one of the main components of cement and is the main source of cement hydration reaction and strength production.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention utilizes the slag discharge port to discharge the molten high-temperature copper slag, and directly combines with Al 2 O 3 The mixing is modified, so that the additional cost of secondary calcination is avoided, and the method has the advantages of low energy consumption.
(2) The invention uses Al 2 O 3 Modification of copper slag can increase the polymerization degree of slag, so that the slag structure tends to be complex, the viscosity is increased, and the preparation of the cementing material is facilitated.
(3) Copper slag and Al of the invention 2 O 3 The chemical reaction for producing tricalcium aluminate, which is one of the main components of cement, is a main source for cement hydration reaction and strength production, and utilizes Al precisely 2 O 3 The potential volcanic ash activity of the copper slag is stimulated, and the income is maximized.
(4) The method improves the volcanic ash activity of the copper slag by using a simpler method, widens the utilization scene of the copper slag, realizes higher utilization rate, and has the significance of resource circulation and environmental protection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of modified water quenched copper slag in example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated; the reagents used in the examples were all commercially available unless otherwise specified.
Example 1
The gel material containing the modified water quenched copper slag is prepared by the specific preparation method:
s1, storing molten copper slag discharged from a slag discharge port into a modulating furnace, and adding Al into the modulating furnace 2 O 3 Fully mixing the two materials for 30 minutes, wherein the temperature in a modulating furnace is 1400 ℃, ensuring that copper slag materials are in a molten state, and Al 2 O 3 The addition amount is 5% of the copper slag mass;
s2, performing water cooling treatment on the mixed molten clinker, and collecting cooled modified copper slag particles;
s3, placing the modified copper slag particles collected in the step S2 into a drying box for drying;
s4, drying the modified copper slag, and grinding until the particles are ground into uniform powder, wherein the D90 value of the powder surface area is 400m 2 And (3) kg, obtaining modified copper slag powder;
s5, mixing and stirring the modified copper slag powder and the cement material to obtain the concrete cementing material, wherein the mixing amount of the modified copper slag is 30% of the mass of the cement.
The preparation flow is shown in figure 1.
Example 2
The gel material containing the modified water quenched copper slag is prepared by the specific preparation method:
s1, storing molten copper slag discharged from a slag discharge port into a modulating furnace, and adding Al into the modulating furnace 2 O 3 Fully mixing the two materials for 30 minutes, wherein the temperature in a modulating furnace is 1400 ℃, ensuring that copper slag materials are in a molten state, and Al 2 O 3 The addition amount is 10% of the copper slag mass;
s2, performing water cooling treatment on the mixed molten clinker, and collecting cooled modified copper slag particles;
s3, placing the modified copper slag particles collected in the step S2 into a drying box for drying;
s4, drying the modified copper slag, and grinding until the particles are ground into uniform powder, wherein the surface area D90 value is 350m 2 /kg；
S5, mixing and stirring the modified copper slag powder and the cement material to obtain the concrete cementing material, wherein the mixing amount of the modified copper slag is 30% of the mass of the cement.
Comparative example 1
The gel material only containing common water quenched copper slag is prepared by the specific preparation method as follows:
s1, storing molten copper slag discharged from a slag discharge port into a modulating furnace, and reacting for 30min at 1400 ℃ in the modulating furnace to ensure that copper slag materials are in a molten state;
s2, performing water cooling treatment on the molten clinker, and collecting cooled copper slag particles;
s3, placing the copper slag particles collected in the step S2 into a drying box for drying;
s4, grinding after the copper slag is dried until the particles are ground into uniform powder, wherein the surface area D90 value is 400m 2 /kg；
S5, mixing and stirring copper slag powder and a cement material, wherein the mixing amount of the copper slag is 30% of the mass of the cement.
Experimental example 1
Examining compressive strength of concrete test blocks prepared from modified water quenched copper slag and common water quenched copper slag at different ages
The water quenched copper slag prepared in the examples 1-2 and the comparative example 1 is prepared into concrete test blocks according to the mass concentration of 70%, and after curing for 7, 28 and 90 days, uniaxial compressive strength experiments are carried out, and the results are shown in the table 1:
table 1 compressive strength of water quenched copper slag of examples 1-2 and comparative example 1
As can be seen from the above table, by comparing example 1 with comparative example 1, it was found that Al was doped in the copper slag 2 O 3 After that, the intensity of different curing ages is enhanced, and the intensity increase rates of 7 days, 28 days and 90 days are respectively 10%, 22% and 14%.
By comparing example 1 with example 2, it was found that as Al in the copper slag 2 O 3 The mixing amount is increased, and the strength of the concrete is gradually increased. Description of proper improvement of Al in copper slag 2 O 3 Can positively influence the early pozzolanic reaction of the copper slag.
The above description is for the purpose of illustrating the embodiments of the present invention and is not to be construed as limiting the invention, but is intended to cover all modifications, equivalents, improvements and alternatives falling within the spirit and principle of the invention.
Claims (7)
1. A method for improving the pozzolanic activity of water quenched copper slag, which is characterized by comprising the following steps:
s1, putting molten copper slag into a modulating furnace, and adding Al into the modulating furnace 2 O 3 Mixing and reacting at high temperature to obtain mixed molten clinker;
s2, carrying out water cooling treatment on the molten clinker mixed in the step S1, and collecting cooled modified copper slag particles;
and S3, drying the modified copper slag particles, and grinding the dried modified copper slag particles to a powder state to obtain a modified copper slag powder product.
2. The method according to claim 1, wherein the temperature in the modulating oven in step S1 is not lower than 1200 ℃.
3. The method according to claim 1, wherein the mixing reaction time in step S1 is 30min.
4. The method according to claim 1, wherein Al in the S1 step 2 O 3 The addition amount is 5-30% of the copper slag mass.
5. The method according to claim 1, wherein the powder modified copper slag in the step S3 has a surface area D90 value of 350 to 400m 2 /kg。
6. Use of a modified copper slag powder prepared by a method for improving pozzolanic activity of water quenched copper slag according to any of claims 1 to 5 for preparing a concrete cementitious material, wherein the modified copper slag is mixed with a cementitious material and stirred to form the concrete cementitious material.
7. The use according to claim 6, wherein the modified copper slag powder is added in an amount of 30-50% of the cement mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311371344.9A CN117303758A (en) | 2023-10-23 | 2023-10-23 | Method for improving pozzolan activity of water quenched copper slag and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311371344.9A CN117303758A (en) | 2023-10-23 | 2023-10-23 | Method for improving pozzolan activity of water quenched copper slag and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117303758A true CN117303758A (en) | 2023-12-29 |
Family
ID=89260261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311371344.9A Pending CN117303758A (en) | 2023-10-23 | 2023-10-23 | Method for improving pozzolan activity of water quenched copper slag and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117303758A (en) |
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2023
- 2023-10-23 CN CN202311371344.9A patent/CN117303758A/en active Pending
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