CN113213801A - Activation method of copper slag and application of copper slag in high-performance concrete - Google Patents
Activation method of copper slag and application of copper slag in high-performance concrete Download PDFInfo
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- CN113213801A CN113213801A CN202110723094.5A CN202110723094A CN113213801A CN 113213801 A CN113213801 A CN 113213801A CN 202110723094 A CN202110723094 A CN 202110723094A CN 113213801 A CN113213801 A CN 113213801A
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- 239000002893 slag Substances 0.000 title claims abstract description 110
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000004574 high-performance concrete Substances 0.000 title claims abstract description 12
- 230000004913 activation Effects 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 118
- 238000000227 grinding Methods 0.000 claims abstract description 99
- 239000000843 powder Substances 0.000 claims abstract description 57
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000012257 stirred material Substances 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 25
- 239000004575 stone Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000004137 mechanical activation Methods 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 14
- 230000036571 hydration Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- 230000003334 potential effect Effects 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000011376 self-consolidating concrete Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
-
- 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
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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides an activation method of copper slag and application of the copper slag in high-performance concrete, wherein the method comprises the following steps: putting the waste copper slag into a crusher for crushing to obtain first grinding powder; sequentially putting the obtained first grinding powder and the slag grinding aid into a ball mill for coarse grinding in sequence to obtain second grinding powder; putting the obtained second grinding powder into a calcining furnace for calcining to obtain a calcined substance; sequentially putting the obtained calcined substance and the slag grinding aid into a ball mill for fine grinding to obtain third grinding powder; sequentially putting the obtained third grinding powder and sodium carbonate into a stirring pot for stirring to obtain a first stirred material; and sequentially adding the obtained first stirring material and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag. According to the invention, the activity in the copper slag can be fully excited by matching the mechanical activation and the chemical activation, and the recycling effect of the copper slag is improved.
Description
Technical Field
The invention relates to the technical field of copper slag recycling, in particular to an activation method of copper slag and application of the copper slag in high-performance concrete.
Background
The slag is waste slag generated in pig iron smelting in steel plants, has high potential activity, and becomes one of raw materials in the cement industry based on utilization of the potential activity of the slag.
According to the self-compacting concrete using copper slag and the preparation method thereof provided by the patent document with the application number of CN201910851303.7, the product comprises the following components: 360-400 parts of cement; 100-120 parts of fly ash; 45-65 parts of copper slag; 750-800 parts of river sand; 770-820 parts of crushed stone; 5.5-8.5 parts of a water reducing agent; 180-210 parts of water; wherein, river sand and gravel are used as aggregate, and cement, fly ash and copper slag are used as powder materials. The product can recycle the copper slag in a recycling way to the largest extent by optimizing the composition and the proportion of the aggregate and the powder material, and the high added value utilization of the copper slag in the self-compacting concrete is realized to the largest extent.
The concrete adopting the copper slag can recycle the copper slag in a resource regeneration manner to the maximum extent by optimizing the composition and the proportion of the aggregate and the powder material, but the recycling of the traditional slag is realized only by mixing the aggregate, the cement and the fly ash, so that the recycling efficiency of the potential activity of the slag is poor. Therefore, how to sufficiently and effectively excite the potential activity of the slag becomes a problem to be paid attention.
Disclosure of Invention
Based on this, the present invention aims to provide a method for activating copper slag and its application in high performance concrete to solve the technical problems of the background art.
The invention provides an activation method of copper slag, which comprises the following steps:
step one, putting waste copper slag into a crusher for crushing to obtain first grinding powder, wherein the crushing pressure is 0.6-0.8 MPa, and the crushing time is 15-30 min;
step two, sequentially putting the first grinding powder and the slag grinding aid obtained in the step one into a ball mill for coarse grinding, and obtaining second grinding powder;
step three, putting the second grinding powder obtained in the step two into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, and the calcining time is 2-5 hours;
step four, sequentially putting the calcined substance and the slag grinding aid obtained in the step three into a ball mill for fine grinding to obtain third grinding powder;
step five, sequentially putting the third grinding powder obtained in the step four and sodium carbonate into a stirring pot for stirring to obtain a first stirring object, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and step six, sequentially putting the first stirred material obtained in the step five and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
Furthermore, in the second step, the proportion of r40, r50, r60 and r70 ball stones in the ball mill during coarse grinding is respectively 30 percent to 20 percent to 25 percent, and the specific gravity of the ball stones is 2.8g/cm3Medium alumina ball stone of (1). It will be appreciated that by using different volumes of pebbles, the grinding effect is improved.
Furthermore, in the fourth step, the r10, r15, r20 and r30 ball stones in the ball mill are respectively in a proportion of 15 percent to 60 percent to 10 percent to 15 percent during fine grinding, and the specific gravity of the ball stones is 3.2g/cm3Alumina spherulites. It will be appreciated that by using different volumes of pebbles, the grinding effect is improved.
Further, the pulverizer comprises a pulverizing box, a vibration assembly for supporting the pulverizing box, and a pulverized powder screen assembly located inside the pulverizing box;
the crushing powder screening assembly comprises crushing rollers which are rotatably connected with the inner wall of the crushing box and are symmetrically arranged, and a first screening plate and a second screening plate which are positioned below the crushing rollers and are sequentially arranged;
the vibration assembly comprises a supporting frame fixed on the outer peripheral surface of the bottom end of the crushing box, a plurality of springs fixed on the lower surface of the supporting frame and a base fixed on the lower surface of the springs.
Furthermore, the vibration assembly further comprises a vibration motor fixed on the lower surface of the supporting frame.
Further, rubbing crusher still includes slay and draws the subassembly, slay draws the subassembly including being fixed in smash the outer surface of the case and draw the section of thick bamboo, and wear to locate carry the inside auger of a section of thick bamboo. It can be understood that the vibration of the crushing box vibration motor is buffered by the spring.
Furthermore, the feed end of ball mill is fixed with the feeder hopper, the feed end of feeder hopper is fixed with oblique auger. It can be understood that when the inclined packing auger is stopped, the feed hopper is sealed to reduce the leakage of dust.
Further, in the fifth step, the third grinding powder and the sodium carbonate obtained in the fourth step are sequentially put into a stirring pot, and after stirring for 5-8 min, the sulfate is put into the stirring pot for stirring.
And further, sequentially adding the third grinding powder obtained in the fourth step and sodium carbonate into a stirring pot, stirring for 9-10 min, and then adding a crystal seed into the stirring pot for stirring, wherein the crystal seed is silicate, and the crystal seed is added into the slag, so that the nucleation barrier of a hydration product when ions are converted into crystals can be reduced, cement is induced to be hydrated more quickly, and the alkalinity of the system is improved.
Further, the slag grinding aid is one or more of gypsum, 20% triethanolamine and sodium silicate, the slag grinding aid formed by matching the gypsum, the 20% triethanolamine and the sodium silicate is used as a cationic surfactant and a nonionic surfactant, and certain substances in the surfactants have an obvious effect on the easy grindability of slag after being synthesized with weak alkali.
Further, in the sixth step, the first stirring material obtained in the fifth step and hydrochloric acid are sequentially added into a stirring pot for stirring to obtain activated copper slag, and then steam curing at 80 ℃ is adopted, so that the reaction rate is faster as the temperature is higher, and the heat release front of the clinker hydration acceleration period coincides with the heat release front of the slag hydration acceleration period through steam curing at 80 ℃.
According to the technical scheme of the activation method of the copper slag, the invention also provides an application method of the copper slag in the high-performance concrete, which comprises the following steps:
step 1, adding a cementing material, lime and activated copper slag into a stirring pot for stirring, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and 2, sequentially putting the nano titanium dioxide, the water and the crushed stone aggregate into a stirring pot, and mixing the nano titanium dioxide, the water and the crushed stone aggregate with the material prepared in the step 1, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
Furthermore, the gravel aggregate comprises 4-8 mm gravel, 8-20 mm gravel and 10-20 mm gravel.
Furthermore, the crystal form of the nano titanium dioxide is an anatase crystal form, and the particle size is 100-200 nm.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the mechanical grinding is formed by the mutual matching of a grinder, a ball mill and other equipment, so that after the solid material is acted by mechanical forces such as impact, shearing, friction, compression, extension and the like, the internal crystal structure can irregularly generate multiphase crystal form transformation, lattice defects, specific surface area increase and surface area increase are caused, the surface area of hydration reaction is enlarged, and the hydration speed of copper slag is correspondingly improved.
Secondly, the invention can destroy the surface structure of the slag glass body by generating alkaline solution through sodium carbonate, so that water permeates and carries out hydration reaction to decompose and disintegrate slag particles, and produce cementitious calcium silicate hydrate and calcium aluminate hydrate.
Thirdly, the multinuclear complex in the copper slag is formed through hydrolysis of hydrochloric acid, so that a high-charge and high-molecular polymer is formed through continuous polycondensation of the complex, and special chemical adsorption and bridging effects are realized between the polymer and the hydrophilic colloid, so that the adsorption of suspended colloid substances in water is facilitated.
Additional features and advantages of the disclosure will be set forth in the description which follows, or in part may be learned by the practice of the above-described techniques of the disclosure, or may be learned by practice of the disclosure.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a schematic view of a ball mill according to the present invention;
FIG. 2 is a schematic view of the crusher of the present invention;
FIG. 3 is a schematic view showing the internal structure of the pulverizer of the present invention.
Description of the main symbols:
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
A first embodiment of the present invention proposes a method of activating copper slag, including the steps of:
step one, putting the waste copper slag into a crusher 20 for crushing to obtain first grinding powder, wherein the crushing pressure is 0.6-0.8 MPa, and the crushing time is 15-30 min.
And step two, sequentially putting the first grinding powder and the slag grinding aid obtained in the step one into the ball mill 10 for coarse grinding, and obtaining second grinding powder.
In the step, the proportion of r40, r50, r60 and r70 ball stones in the ball mill 10 during rough grinding is respectively 30 percent to 20 percent to 25 percent, and the ball stones are medium-alumina ball stones with the specific gravity of 2.8g/cm3, so that the ball stones with different volumes are adopted, and the grinding effect is improved.
And step three, putting the second grinding powder obtained in the step two into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, and the calcining time is 2-5 hours.
In this step, the interface can be improved by calcining the copper slag to decompose the organic matter and most of the light matter in the slag.
And step four, sequentially putting the calcined substance and the slag grinding aid obtained in the step three into a ball mill 10 for fine grinding to obtain third grinding powder.
In the step, mechanical grinding is performed by matching the pulverizer 20, the ball mill 10 and other devices, so that after the solid material is subjected to mechanical force effects such as impact, shearing, friction, compression, extension and the like, the internal crystal structure is irregularly transformed into a multiphase crystal form, lattice defects, specific surface area and surface area are increased, the surface area of a hydration reaction is enlarged, and the hydration speed of copper slag is correspondingly increased.
In the fine grinding process, the proportion of r10, r15, r20 and r30 in the ball mill 10 is respectively 15 percent to 60 percent to 10 percent to 15 percent, and the specific gravity of the ball stones is 3.2g/cm3Alumina spherulites. It will be appreciated that by using different volumes of pebbles, the grinding effect is improved.
And step five, sequentially putting the third grinding powder obtained in the step four and sodium carbonate into a stirring pot for stirring to obtain a first stirring object, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min.
In the step, mechanical grinding is performed by matching the pulverizer 20, the ball mill 10 and other devices, so that after the solid material is subjected to mechanical force effects such as impact, shearing, friction, compression, extension and the like, the internal crystal structure is irregularly transformed into a multiphase crystal form, lattice defects, the specific surface area is increased, and the surface area is increased, so that the surface area of a hydration reaction is enlarged, and the hydration speed of copper slag is correspondingly increased.
In the step, the third grinding powder and the sodium carbonate obtained in the step four are sequentially put into a stirring pot, stirred for 9-10 min, and then the seed crystal is put into the stirring pot for stirring. Specifically, the crystal seeds are silicate, and the crystal seeds added into the slag can reduce the nucleation barrier when hydration products are converted from ions into crystals, induce the cement to accelerate hydration and improve the alkalinity of the system.
As another preferred embodiment, in this step, the third ground powder and sodium carbonate obtained in the fourth step are sequentially put into a stirring pot, stirred for 5-8 min, and then the sulfate is put into the stirring pot and stirred. Because certain alkaline environment is formed in the stirring pot through the sodium carbonate in the fourth step, after the sulfate is subsequently added to workers, the alkaline environment is matched with the sulfate to form a sulfate excitation effect, and the activity in the slag can be well exerted.
And step six, sequentially putting the first stirred material obtained in the step five and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
In the step, the polynuclear complex in the copper slag is formed by hydrolysis of hydrochloric acid, so that a high-charge and high-molecular polymer is formed by continuous condensation of the complex, and special chemical adsorption and bridging effects are realized between the polymer and the hydrophilic colloid, so that the adsorption of suspended colloid substances in water is facilitated.
The slag grinding aid is one or more of gypsum, 20% triethanolamine and sodium silicate. The slag grinding aid formed by matching gypsum, 20% triethanolamine and sodium silicate is used as a cationic surfactant and a nonionic surfactant, and certain substances in the surfactant have an obvious effect on the easy grindability of slag after being synthesized with weak alkali.
And in the sixth step, the first stirring material obtained in the fifth step and hydrochloric acid are sequentially put into a stirring pot for stirring to obtain activated copper slag, and then steam curing at 80 ℃ is adopted, the reaction rate is faster as the temperature is higher, and the heat release front of the clinker hydration acceleration period is coincided with the heat release peak of the slag hydration acceleration period through the steam curing at 80 ℃.
Specifically, referring to fig. 1 and 2, the pulverizer 20 includes a pulverizing box 22, a vibrating assembly 24 for supporting the pulverizing box 22, and a pulverizing sieve assembly 21 located inside the pulverizing box 22.
Crushing powder sieve subassembly 21 include with crushing roller 211 that the inner wall of smashing case 22 rotates to be connected and the symmetry sets up is located first screening board 212 and the second screening board 213 that just sets gradually below crushing roller 211.
The vibration unit 24 includes a support frame 241 fixed to an outer circumferential surface of a bottom end of the pulverization case 22, a plurality of springs 242 fixed to a lower surface of the support frame 241, and a base 243 fixed to a lower surface of the springs 242, and the vibration unit 24 further includes a vibration motor 244 fixed to a lower surface of the support frame 241. Meanwhile, the pulverizer 20 further comprises a slag pulling assembly 23, wherein the slag pulling assembly 23 comprises a pulling cylinder 231 fixed on the outer surface of the pulverizing box 22, and an auger 232 penetrating through the pulling cylinder 231.
It should be noted that, in this embodiment, when the crushing box 22 starts shaking, since the crushing roller 211, the first screening plate 212 and the second screening plate 213 are arranged in the crushing box 22 in sequence from top to bottom, after the copper slag is crushed by the crushing roller 211, the copper slag can be screened by the first screening plate 212 and the second screening plate 213, so that the crushed copper slag can be crushed into different specifications. The particles having a smaller particle size are discharged from the upper surface of the second sieving plate 213, and the particles having a larger particle size are retained on the upper surface of the first sieving plate 212.
In addition, since the auger 232 is provided in the pulling cylinder 231 on the outer surface of the pulverization box 22, the slag having a large particle size on the upper surface of the first classification plate 212 is pulled by the auger 232 and then dropped above the pulverization roller 211 to be pulverized again. Further, the vibration of the vibration motor 244 of the crushing box 22 is buffered by the spring 242.
Please refer to fig. 3 again, a feeding hopper 11 is fixed at the feeding end of the ball mill 10, and an inclined packing auger 12 is fixed at the feeding end of the feeding hopper 11. In this embodiment, the feed hopper 11 seals the feed end of the ball mill 10, and the inclined packing auger 12 feeds the material into the feed hopper 11, and at the same time, when the inclined packing auger 12 stops, the feed hopper 11 is sealed to reduce the leakage of dust.
According to the above embodiment, there is also provided a use of copper slag in high performance concrete, comprising the steps of:
step 1, adding the cementing material, lime and activated copper slag into a stirring pot for stirring, wherein the stirring speed is 120-130 r/min, the stirring time is 20-30 min, and the activated copper slag is mixed with the cementing material and lime because the slag is reused based on potential activity, so that the quality of concrete is improved;
and 2, sequentially putting the nano titanium dioxide, water and crushed stone aggregate into a stirring pot, mixing the nano titanium dioxide, the water and the crushed stone aggregate with the material prepared in the step 1, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min, so that the prepared concrete can absorb nitrides and sulfides in the air through the photocatalysis of the nano titanium dioxide, and the concrete with the purification capacity is formed.
Furthermore, the gravel aggregate comprises 4-8 mm gravel, 8-20 mm gravel and 10-20 mm gravel. The crystal form of the nano titanium dioxide is an anatase crystal form, and the particle size is 100-200 nm.
Example 2
A second embodiment of the present invention provides a method for activating copper slag, which specifically includes the steps of:
step one, putting the waste copper slag into a crusher 20 for crushing to obtain first grinding powder, wherein the crushing pressure is 0.6-0.8 MPa, and the crushing time is 15-30 min;
step two, sequentially putting the first grinding powder and the slag grinding aid obtained in the step one into the ball mill 10 for coarse grinding to obtain second grinding powder;
step three, putting the second grinding powder obtained in the step two into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, and the calcining time is 2-5 hours;
step four, sequentially putting the calcined substance and the slag grinding aid obtained in the step three into a ball mill 10 for fine grinding to obtain third grinding powder;
step five, sequentially putting the third grinding powder obtained in the step four and sodium carbonate into a stirring pot for stirring to obtain a first stirring object, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and step six, sequentially putting the first stirred material obtained in the step five and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
Furthermore, in the second step, the proportion of r40, r50, r60 and r70 pebbles in the ball mill 10 during coarse grinding is respectively 30 percent to 20 percent to 25 percent.
Furthermore, in the fourth step, the r10, r15, r20 and r30 ball stones in the ball mill 10 are respectively 15 percent to 60 percent to 10 percent to 15 percent during fine grinding.
Further, in the fifth step, the third grinding powder obtained in the fourth step and sodium carbonate are sequentially put into a stirring pot, and after stirring for 5-8 min, sulfate is put into the stirring pot to be stirred, wherein the mixing amount of the sodium carbonate is more than 6%.
Further, in the fifth step, the third grinding powder and sodium carbonate obtained in the fourth step are sequentially put into a stirring pot, and after stirring for 9-10 min, crystal seeds are put into the stirring pot to be stirred, wherein the crystal seeds are silicate, and the mixing amount of the crystal seeds is 5%.
Further, the slag grinding aid is one or more of gypsum, 20% triethanolamine and sodium silicate.
Further, in the sixth step, the first stirred material obtained in the fifth step and hydrochloric acid are sequentially put into a stirring pot for stirring to obtain activated copper slag, and then steam curing at the temperature of 80 ℃ is adopted.
The application of a copper slag in high-performance concrete was the same as in example 1.
According to calculation, the activity index of the experimental sample is 85 in 7 days, and the activity index of the experimental sample is 93 in 30 days.
Example 3
A third embodiment of the present invention provides a method for activating copper slag, including the steps of:
step one, putting the waste copper slag into a crusher 20 for crushing to obtain first grinding powder, wherein the crushing pressure is 0.6-0.8 MPa, and the crushing time is 15-30 min;
step two, sequentially putting the first grinding powder and the slag grinding aid obtained in the step one into the ball mill 10 for coarse grinding to obtain second grinding powder;
step three, putting the second grinding powder obtained in the step two into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, and the calcining time is 2-5 hours;
step four, sequentially putting the calcined substance and the slag grinding aid obtained in the step three into a ball mill 10 for fine grinding to obtain third grinding powder;
step five, sequentially putting the third grinding powder obtained in the step four and sodium carbonate into a stirring pot for stirring to obtain a first stirring object, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and step six, sequentially putting the first stirred material obtained in the step five and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
Furthermore, in the second step, the proportion of r40, r50, r60 and r70 pebbles in the ball mill 10 during coarse grinding is respectively 40 percent to 20 percent to 25 percent to 15 percent.
Furthermore, in the fourth step, the proportion of r10, r15, r20 and r30 ball stones in the ball mill 10 during fine grinding is respectively 15 percent to 50 percent to 20 percent to 15 percent.
Further, in the fifth step, the third grinding powder obtained in the fourth step and sodium carbonate are sequentially put into a stirring pot, and after stirring for 5-8 min, sulfate is put into the stirring pot to be stirred, wherein the mixing amount of the sodium carbonate is more than 10%.
Further, in the fifth step, the third grinding powder and sodium carbonate obtained in the fourth step are sequentially put into a stirring pot, and after stirring for 9-10 min, crystal seeds are put into the stirring pot to be stirred, wherein the crystal seeds are silicate, and the doping amount of the crystal seeds is 8%.
Further, the slag grinding aid is gypsum, 20% triethanolamine and sodium silicate.
Further, in the sixth step, the first stirred material obtained in the fifth step and hydrochloric acid are sequentially put into a stirring pot for stirring to obtain activated copper slag, and then steam curing at the temperature of 80 ℃ is adopted.
The application of a copper slag in high-performance concrete was the same as in example 1.
According to calculation, the activity index of the experimental sample is 88 in 7 days, and the activity index of the experimental sample is 93.5 in 30 days.
The specific operation mode of the invention is as follows:
putting the waste copper slag into a pulverizer 20 for pulverizing to obtain first grinding powder, wherein the pulverizing pressure is 0.6-0.8 MPa, the pulverizing time is 15-30 min, and putting the obtained first grinding powder and a slag grinding aid into a ball mill 10 in sequence for coarse grinding to obtain second grinding powder;
putting the obtained second grinding powder into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, the calcining time is 2-5 hours, putting the obtained calcined substance and a slag grinding aid into a ball mill 10 in sequence for fine grinding to obtain third grinding powder, putting the obtained third grinding powder and sodium carbonate into a stirring pot in sequence for stirring to obtain a first stirring substance, and putting the obtained first stirring substance and hydrochloric acid into the stirring pot in sequence for stirring to obtain activated copper slag;
and (2) adding the cementing material, lime and activated copper slag into a stirring pot for stirring, sequentially adding the nano titanium dioxide, water and crushed stone aggregate into the stirring pot, and mixing with the material prepared in the step (1), wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min, so as to prepare the concrete.
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A method for activating copper slag, characterized by comprising the steps of:
step one, putting waste copper slag into a crusher (20) for crushing to obtain first grinding powder, wherein the crushing pressure is 0.6-0.8 MPa, and the crushing time is 15-30 min;
step two, the first grinding powder and the slag grinding aid obtained in the step one are sequentially put into a ball mill (10) for coarse grinding in sequence to obtain second grinding powder;
step three, putting the second grinding powder obtained in the step two into a calcining furnace for calcining to obtain a calcined substance, wherein the calcining temperature is 600-800 ℃, and the calcining time is 2-5 hours;
step four, sequentially putting the calcined substance and the slag grinding aid obtained in the step three into a ball mill (10) for fine grinding to obtain third grinding powder;
step five, sequentially putting the third grinding powder obtained in the step four and sodium carbonate into a stirring pot for stirring to obtain a first stirring object, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and step six, sequentially putting the first stirred material obtained in the step five and hydrochloric acid into a stirring pot for stirring to obtain activated copper slag, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
2. The method of claim 1, wherein in the second step, the r40, rS0, r60 and r70 are used in the ball mill (10) in a ratio of 30% to 20% to 25% in the course of rough grinding, and the specific gravity of the ball is 2.8g/cm3Medium alumina ball stone of (1).
3. The method of claim 1, wherein in the fourth step, the ratio of r10, r15, r20 and r30 in the ball mill (10) is 15% to 60% to 10% to 15% respectively, and the specific gravity of the ball is 3.2g/cm3Alumina spherulites.
4. The activation method of copper slag according to claim 1, wherein the crusher (20) includes a crushing tank (22), a vibrating assembly (24) for supporting the crushing tank (22), and a pulverizate screen assembly (21) located inside the crushing tank (22);
the crushing powder screening assembly (21) comprises crushing rollers (211) which are rotatably connected with the inner wall of the crushing box (22) and symmetrically arranged, and a first screening plate (212) and a second screening plate (213) which are positioned below the crushing rollers (211) and are sequentially arranged;
the vibration component (24) comprises a supporting frame (241) fixed on the outer peripheral surface of the bottom end of the crushing box (22), a plurality of springs (242) fixed on the lower surface of the supporting frame (241), and a base (243) fixed on the lower surface of the springs (242).
5. The activation method of copper slag according to claim 4, wherein in the fifth step, the vibration assembly (24) further includes a vibration motor (244) fixed to a lower surface of the support frame (241).
6. The activation method of copper slag according to claim 1, wherein the crusher (20) further comprises a slag pulling assembly (23), and the slag pulling assembly (23) comprises a pulling cylinder (231) fixed on the outer surface of the crushing box (22), and an auger (232) arranged inside the pulling cylinder (231).
7. The activation method of copper slag according to claim 1, wherein a feed hopper (11) is fixed to the feed end of the ball mill (10), and an inclined auger (12) is fixed to the feed end of the feed hopper (11).
8. The application of copper slag in high-performance concrete is characterized by comprising the following steps:
step 1, adding a cementing material, lime and activated copper slag into a stirring pot for stirring, wherein the stirring speed is 120-130 r/min, and the stirring time is 20-30 min;
and 2, sequentially putting the nano titanium dioxide, the water and the crushed stone aggregate into a stirring pot, and mixing the nano titanium dioxide, the water and the crushed stone aggregate with the material prepared in the step 1, wherein the stirring speed is 130-140 r/min, and the stirring time is 30-40 min.
9. The use of copper slag in high-performance concrete according to claim 8, wherein the crushed stone aggregate comprises crushed stones with a particle size of 4-8 mm, crushed stones with a particle size of 8-20 mm and crushed stones with a particle size of 10-20 mm.
10. The application of copper slag in high-performance concrete according to claim 8, wherein the nano titanium dioxide is in an anatase crystal form, and the particle size is 100-200 nm.
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| CN116081966A (en) * | 2023-01-10 | 2023-05-09 | 三峡大学 | Preparation method of phosphate tailing-based cementing material and application of phosphate tailing-based cementing material in road stabilization base layer |
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