CN118183760A - Silica sol modified ferrochrome slag aggregate and preparation method thereof - Google Patents
Silica sol modified ferrochrome slag aggregate and preparation method thereof Download PDFInfo
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- CN118183760A CN118183760A CN202410392628.4A CN202410392628A CN118183760A CN 118183760 A CN118183760 A CN 118183760A CN 202410392628 A CN202410392628 A CN 202410392628A CN 118183760 A CN118183760 A CN 118183760A
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- silica sol
- ferrochrome slag
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- 239000002893 slag Substances 0.000 title claims abstract description 84
- 229910000604 Ferrochrome Inorganic materials 0.000 title claims abstract description 82
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 12
- 235000009566 rice Nutrition 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- 238000004448 titration Methods 0.000 claims abstract description 4
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical group [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 claims description 17
- 241000209094 Oryza Species 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- JBHQOKOWHGHTOF-UHFFFAOYSA-N aziridin-2-yl propanoate Chemical compound CCC(=O)OC1CN1 JBHQOKOWHGHTOF-UHFFFAOYSA-N 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 239000004567 concrete Substances 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 3
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 239000004574 high-performance concrete Substances 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 238000002791 soaking Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
- 239000004568 cement Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000010903 husk Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 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
- 241000196324 Embryophyta Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
- C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
-
- 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
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Dispersion Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a silica sol modified ferrochrome slag aggregate and a preparation method thereof, comprising the following steps: the rice hull ash is subjected to acid washing treatment by adopting a sol-gel method to remove metal ions, and NaOH solution is added after drying, stirred and filtered to obtain brown sodium silicate solution. Adjusting the pH value of the water glass solution to 8-10 by acid titration, aging and centrifuging to obtain nano silica sol gel, drying and grinding for later use; preparing nano silica sol into silica sol solution with a certain fraction, dispersing the silica sol solution under an ultrasonic cleaning machine, and then immersing ferrochrome slag aggregate into the solution and fully immersing the ferrochrome slag aggregate; adding a modifier and a cross-linking agent into the fully soaked solution to strengthen the aggregate, and adding a small amount of initiator and accelerator to accelerate the reaction; and (3) placing the modified aggregate into a specific environment for curing, and drying and curing for standby. The modification method is green and environment-friendly, and has the advantages of simple process, low cost, safety and innocuity. The surface pores of the obtained modified ferrochrome slag aggregate are obviously reduced, and the crushing value and the water absorption are obviously reduced. The concrete prepared from the modified ferrochrome slag aggregate has more stable and reliable performance, and is expected to realize more excellent permeation resistance, durability and strength performance especially in high-performance concrete application.
Description
Technical Field
The invention relates to a silica sol modified ferrochrome slag aggregate and a preparation method thereof, belonging to the technical field of building materials.
Background
The high-carbon ferrochrome slag is a byproduct generated in ferrochrome smelting. Statistics show that the annual high-carbon ferrochrome smelting waste residue in China exceeds 840 ten thousand tons by the last year. The traditional treatment mode, namely simple landfill or piling, causes great waste on land resources and is also hidden danger in the environment: leachable Cr 6+ in the slag has serious toxicity, affects the growth of animals and plants, and causes skin and respiratory diseases after long-term contact. Therefore, the recycling of ferrochrome slag is imperative.
The ferrochrome slag is an inorganic nonmetallic material, and takes magnesium olivine and spinel as main phases. According to different cooling modes, the cooling mode can be simply divided into water cooling and air cooling of chromium iron slag. The cooling speed of the water-cooling slag is high, the particles are tiny, the pores are numerous, and the strength is influenced by the glass phase in a multi-metastable state; whereas the air-cooled slag is generally large and coarse in particles, forming a majority of crystals in the bulk phase. Because the ferrochrome slag contains a large amount of siliceous and aluminum, the standardized tailings can be widely applied to the fields of metallurgy, ceramics, refractory materials and the like after the component proportion is regulated. In the construction field, ferrochrome slag has been used as a precedent for mineral admixtures and aggregates. By detecting and controlling the leaching amount of Cr 6+, the compliance of the leaching amount with local environmental standards and regulations can be ensured. However, because of the low active siliceous content of ferrochrome slag, the overall inertia is very poor, and its use as an inert fine particle filler and Supplementary Cementitious Materials (SCMs). Currently, there have been examples in practice showing the potential of ferrochrome slag to completely replace natural sand as aggregate. It should be noted that its porous morphology and high water absorption may affect the durability and strength of the material.
The nano silica sol is a colloidal solution of nano SiO 2 stably dispersed in a medium, has excellent adsorptivity and large specific surface area, and the mesoporous structure provides reactive sites. Meanwhile, the silica sol has good permeability to cement-based materials, and the doped colloid particles can play a role in filling. Meanwhile, in consideration of the compatibility of silica sol and ferrochrome slag, ca 2+ in calcium acrylate can be quickly combined with active Si-OH groups of cement-based materials to form C-S-H gel, so that pores are effectively closed, and water absorption is reduced. In addition, the calcium acrylate can form a calcium polyacrylate framework structure under the action of an initiator and a cross-linking agent, so that the compressive strength and the flexural strength of the aggregate are further improved.
Disclosure of Invention
Technical problems: the invention aims to provide a silica sol modified ferrochrome slag aggregate and a preparation method thereof, wherein the method is low in cost, environment-friendly and simple in process, and solves the problem of high coarse porous water absorption rate of ferrochrome slag, so that the surface of the modified ferrochrome slag aggregate is smooth, the porosity and the water absorption rate are obviously reduced, the workability of fresh concrete slurry is optimized, and the mechanical property and durability of concrete are improved.
The technical scheme is as follows: the silica sol modified ferrochrome slag aggregate is prepared by immersing ferrochrome slag aggregate in nano silica sol, fully immersing, adding a modifier, a cross-linking agent, an initiator and an accelerator to react and strengthen the aggregate, and finally curing and drying for later use; the nano silica sol is obtained by acid washing rice hull ash serving as a raw material by adopting a sol-gel method, reacting with NaOH, regulating pH value by acid to 8-10, and aging.
In the pickling process, the pH value is required to be adjusted to 4-5, and the acid is nitric acid or acrylic acid.
The modifier is calcium acrylate, and the addition amount is 10-20 wt% of the nano silica sol solution. The cross-linking agent is tri (3-aziridinyl) propionate (with a molecular formula of C 20H33N3O7), the initiator is potassium persulfate, and the accelerator is triethanolamine.
The mass ratio of the modifier, the cross-linking agent, the accelerator and the initiator is 100:5:1:2.5.
The method for preparing the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Acid washing rice hull ash by adopting a sol-gel method to remove metal ions, drying, adding a NaOH solution, stirring and filtering to obtain a brown sodium silicate solution;
2) Adjusting the water glass solution to pH=8-10 by acid titration, aging and centrifuging to obtain nano silica sol gel, drying and grinding for later use;
3) Preparing nano silica sol into silica sol solution, dispersing the silica sol solution under an ultrasonic cleaning machine, and then immersing ferrochrome slag aggregate into the solution and fully immersing the ferrochrome slag aggregate;
4) Adding a modifier and a cross-linking agent into the fully soaked solution to strengthen aggregate, and adding a small amount of initiator and accelerator to accelerate the reaction;
5) And curing the modified aggregate, and drying and curing for later use.
The amount of NaOH substance in the step 1) is 0.6-0.8 mol.
The aging time required by the aging and centrifuging step in the step 2) is 2-3 d, and the centrifuging speed is 3500-4000 rpm.
The nano silica sol solution with a certain mass fraction after being dispersed under the ultrasonic cleaning machine in the step 3) is dispersed for 20-30min, the ultrasonic frequency is 30-40 KHz, and the nano silica sol solution is 5-10 wt%.
The curing condition in the step 4) is 20+/-2 ℃, the relative humidity is 95%, and the curing time is 3d.
The drying temperature in the steps 1), 2) and 4) is 110-140 ℃ and the time is 12-18 h.
The beneficial effects are that:
1) The method takes rice hull ash as a raw material to prepare the nano silica sol, eliminates the toxicity caused by taking traditional metal alkoxide as a silicon source, effectively relieves the environmental pressure, has low requirements on equipment complexity and precision, and is easy to realize industrial production;
2) Compared with nano SiO 2 powder, the nano silica sol adopted by the method has stronger permeability, and is easier to realize uniform dispersion in a medium, so that the nano silica sol can be fully contacted with the aggregate to be modified. The excessive nano silica sol solution reacts with calcium acrylate, so that not only is the hole sealing effect realized, but also active nano SiO 2 particles are reserved on the surface and inside, and a key effect is exerted on the aspects of interface bonding and microstructure optimization. Meanwhile, under the action of the cross-linking agent, the skeleton structure formed by the calcium acrylate further strengthens the overall mechanical property of the aggregate, so that the strengthening effect of the aggregate in concrete is fully exerted.
3) The porosity and the water absorption of the modified ferrochrome slag aggregate are reduced, the surface is smoother, and the inside is relatively stable. The water demand is obviously reduced and the workability of the fresh slurry is optimized in the process of using the modified aggregate to form concrete. The strength of the concrete is obviously improved, the diffusion coefficient of chloride ions is reduced, the interface structure of aggregate and slurry is optimized, and the mechanical property and durability of the concrete are effectively improved.
Drawings
FIG. 1 shows the diffusion coefficient of 28d chloride ions for the modified ferrochrome slag aggregate concrete of examples 1-5 and the comparative example.
FIG. 2 is a graph showing the depth of carbonization of 28d chloride ions for the modified ferrochrome slag aggregate concrete of examples 1-5 and the comparative example.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The coarse and fine aggregates used in the embodiment of the invention are obtained by crushing and sieving air-cooled high-carbon ferrochrome slag. The grain size range of the coarse aggregate is 5-20 mm; the grain size of the fine aggregate ranges from 0.75 mm to 5mm.
The invention discloses a preparation method of silica sol modified ferrochrome slag aggregate, which comprises the following steps:
1) The rice hull ash is subjected to acid washing treatment by adopting a sol-gel method to remove metal ions, and NaOH solution is added after drying, stirred and filtered to obtain brown sodium silicate solution.
2) Adjusting the water glass solution to pH=8-10 by acid titration, aging and centrifuging to obtain nano silica sol gel, drying and grinding for later use;
3) Preparing nano silica sol into silica sol solution with a certain fraction, dispersing the silica sol solution under an ultrasonic cleaning machine, and then immersing ferrochrome slag aggregate into the solution and fully immersing the ferrochrome slag aggregate;
4) Adding modifier and cross-linking agent into the fully soaked solution to strengthen aggregate, and adding a small amount of initiator and accelerator to accelerate the reaction.
5) And (3) placing the modified aggregate into a specific environment for curing, and drying and curing for standby.
Wherein:
in the pickling treatment process of the step 1), the pH value is required to be adjusted to 4-5, and the acid is nitric acid or acrylic acid.
The amount of NaOH substance in the step 1) is 0.6-0.8 mol.
The aging time required by the aging and centrifuging step in the step 2) is 2-3 d, and the centrifuging speed is 3500-4000 rpm.
The nano silica sol solution with a certain mass fraction after being dispersed under the ultrasonic cleaning machine in the step 3) is dispersed for 20-30min, the ultrasonic frequency is 30-40 KHz, and the nano silica sol solution is 5-10 wt%.
The modifier in the step 4) is calcium acrylate, the addition amount of the modifier is 10-20wt% of the dispersed nano silica sol solution, the cross-linking agent is tris (3-aziridinyl) propionate (with a molecular formula of C 20H33N3O7), the initiator is potassium persulfate, the accelerator is triethanolamine, and the proportion of the modifier, the cross-linking agent, the accelerator and the initiator is 100:5:1:2.5.
The curing condition in the step 4) is 20+/-2 ℃, the relative humidity is 95%, and the curing time is 3d.
The drying temperature of the steps 1), 2) and 4) is 110-140 ℃ and the time is 12-18 h.
Example 1:
the preparation method of the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Preparing nano silica sol particles prepared from rice husk ash into a nano silica sol solution with the mass fraction of 5% by taking water as a solvent, performing ultrasonic dispersion in an ultrasonic cleaner with the frequency of 40KHz for 20min, and putting ferrochrome slag coarse and fine aggregate into the solution subjected to ultrasonic treatment for soaking for 3d;
2) And opening a sealing cover after soaking, and adding 20% of calcium acrylate by mass percent of the soaking solution. Based on the mixing quality of calcium acrylate, adding tri (3-aziridinyl) propionate, triethanolamine and potassium persulfate, wherein the proportion is 100:5:1:2.5, mixing uniformly and standing;
3) Placing the fully infiltrated ferrochrome slag aggregate into a standard curing chamber with the relative humidity of 95% at 20+/-2 ℃ for curing, taking out after 3d, and drying for later use;
4) 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 748 parts of modified ferrochrome slag fine aggregate, 343 parts of 5-10 mm modified ferrochrome slag coarse aggregate, 685 parts of 10-20 mm modified ferrochrome slag coarse aggregate, 151 parts of water and 4.6 parts of water reducer.
Example 2:
the preparation method of the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Preparing nano silica sol particles prepared from rice husk ash into a nano silica sol solution with the mass fraction of 5% by taking water as a solvent, performing ultrasonic dispersion in an ultrasonic cleaner with the frequency of 40KHz for 20min, and putting ferrochrome slag coarse and fine aggregate into the solution subjected to ultrasonic treatment for soaking for 3d;
2) And opening a sealing cover after soaking, and adding 20% of calcium acrylate by mass percent of the soaking solution. Based on the mixing quality of calcium acrylate, adding tri (3-aziridinyl) propionate, triethanolamine and potassium persulfate, wherein the proportion is 100:5:1:2.5, mixing uniformly and standing;
3) Placing the fully infiltrated ferrochrome slag aggregate into a standard curing chamber with the relative humidity of 95% at 20+/-2 ℃ for curing, taking out after 3d, and drying for later use;
4) Taking 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 799 parts of ferrochrome slag fine aggregate, 326 parts of ferrochrome slag coarse aggregate with the thickness of 5-10 mm, 651 parts of ferrochrome slag coarse aggregate with the thickness of 10-20 mm, 151 parts of water and 4.6 parts of water reducer.
Example 3:
the preparation method of the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Preparing nano silica sol particles prepared from rice husk ash into a nano silica sol solution with the mass fraction of 5% by taking water as a solvent, performing ultrasonic dispersion in an ultrasonic cleaner with the frequency of 40KHz for 20min, and putting ferrochrome slag coarse and fine aggregate into the solution subjected to ultrasonic treatment for soaking for 3d;
2) And opening a sealing cover after soaking, and adding 20% of calcium acrylate by mass percent of the soaking solution. Based on the mixing quality of calcium acrylate, adding tri (3-aziridinyl) propionate, triethanolamine and potassium persulfate, wherein the proportion is 100:5:1:2.5, mixing uniformly and standing;
3) Placing the fully infiltrated ferrochrome slag aggregate into a standard curing chamber with the relative humidity of 95% at 20+/-2 ℃ for curing, taking out after 3d, and drying for later use;
4) Taking 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 799 parts of ferrochrome slag fine aggregate, 326 parts of ferrochrome slag coarse aggregate with the thickness of 5-10 mm, 651 parts of ferrochrome slag coarse aggregate with the thickness of 10-20 mm, 151 parts of water and 4.6 parts of water reducer.
Example 4:
the preparation method of the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Preparing nano silica sol particles prepared from rice husk ash into a nano silica sol solution with the mass fraction of 5% by taking water as a solvent, performing ultrasonic dispersion in an ultrasonic cleaner with the frequency of 40KHz for 20min, and putting ferrochrome slag coarse and fine aggregate into the solution subjected to ultrasonic treatment for soaking for 3d;
2) And opening a sealing cover after soaking, and adding 20% of calcium acrylate by mass percent of the soaking solution. Based on the mixing quality of calcium acrylate, adding tri (3-aziridinyl) propionate, triethanolamine and potassium persulfate, wherein the proportion is 100:5:1:2.5, mixing uniformly and standing;
3) Placing the fully infiltrated ferrochrome slag aggregate into a standard curing chamber with the relative humidity of 95% at 20+/-2 ℃ for curing, taking out after 3d, and drying for later use;
4) 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 748 parts of ferrochrome slag fine aggregate, 343 parts of ferrochrome slag coarse aggregate with the thickness of 5-10 mm, 685 parts of ferrochrome slag coarse aggregate with the thickness of 10-20 mm, 151 parts of water and 4.6 parts of water reducer are taken.
Example 5:
the preparation method of the silica sol modified ferrochrome slag aggregate comprises the following steps:
1) Preparing nano silica sol particles prepared from rice husk ash into a nano silica sol solution with the mass fraction of 5% by taking water as a solvent, performing ultrasonic dispersion in an ultrasonic cleaner with the frequency of 40KHz for 20min, and putting ferrochrome slag coarse and fine aggregate into the solution subjected to ultrasonic treatment for soaking for 3d;
2) And opening a sealing cover after soaking, and adding 20% of calcium acrylate by mass percent of the soaking solution. Based on the mixing quality of calcium acrylate, adding tri (3-aziridinyl) propionate, triethanolamine and potassium persulfate, wherein the proportion is 100:5:1:2.5, mixing uniformly and standing;
3) Placing the fully infiltrated ferrochrome slag aggregate into a standard curing chamber with the relative humidity of 95% at 20+/-2 ℃ for curing, taking out after 3d, and drying for later use;
4) Taking 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 799 parts of ferrochrome slag fine aggregate, 326 parts of ferrochrome slag coarse aggregate with the thickness of 5-10 mm, 651 parts of ferrochrome slag coarse aggregate with the thickness of 10-20 mm, 151 parts of water and 4.6 parts of water reducer.
Comparative example
The comparative example is C60 concrete, which is prepared from the following raw materials in parts by weight: 312 parts of P.II 52.5 cement, 156 parts of metakaolin, 799 parts of unmodified ferrochrome slag fine aggregate, 326 parts of 5-10 mm unmodified ferrochrome slag coarse aggregate, 651 parts of 10-20 mm unmodified ferrochrome slag coarse aggregate, 151 parts of water and 4.6 parts of water reducer.
Firstly, the powder materials of cement, metakaolin and the like and ferrochrome slag coarse aggregate in the examples 1-5 and the comparative example are put into a horizontal mixer to be uniformly mixed. Then pouring part of mixing water and stirring for 2min until the slurry is sticky, and slowly pouring the fine aggregate and continuing stirring. And then adding the rest mixing water and the water reducing agent, stirring for 3min, pouring and filling the slurry in layers after the slurry is uniformly mixed, vibrating, coating the film, demoulding after 24h, and putting the mixture into a standard culture room.
The mechanical property and durability of the concrete prepared in the examples 1-5 are better than those of the comparative examples, the compressive strength increasing rate is 3.1% -25.3%, and the flexural strength increasing rate is 3.8% -41.8%; the diffusion coefficient of chloride ions and the depth of a carbonization layer are obviously reduced, and the improvement effect of the modified ferrochrome slag aggregate on the mechanical property and durability of concrete is proved to be obvious.
TABLE 1 workability and mechanical properties of modified ferrochrome slag concrete
The above description is merely an example of the application of the present invention, but the protection scope of the present invention is not limited thereto, and any changes and substitutions that can be easily considered by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (10)
1. The silica sol modified ferrochrome slag aggregate is characterized in that ferrochrome slag aggregate is immersed in nano silica sol and fully immersed, then modifier, cross-linking agent, initiator and accelerator are added to react and strengthen the aggregate, and finally the aggregate is cured and dried and cured for later use; the nano silica sol is obtained by acid washing rice hull ash serving as a raw material by adopting a sol-gel method, reacting with NaOH, regulating pH value by acid to 8-10, and aging.
2. The silica sol modified ferrochrome slag aggregate according to claim 1, wherein the pH value is adjusted to 4-5 in the pickling process, and the acid is nitric acid or acrylic acid.
3. The silica sol modified ferrochrome slag aggregate of claim 1, wherein the modifier is calcium acrylate, and the addition amount is 10-20 wt% of the nano silica sol solution; the cross-linking agent is tri (3-aziridinyl) propionate (with a molecular formula of C 20H33N3O7), the initiator is potassium persulfate, and the accelerator is triethanolamine.
4. The silica sol modified ferrochrome slag aggregate of claim 1, wherein the mass ratio of the modifier, the cross-linking agent, the accelerator and the initiator is 100:5:1:2.5.
5. A method for preparing the silica sol modified ferrochrome slag aggregate according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Acid washing rice hull ash by adopting a sol-gel method to remove metal ions, drying, adding a NaOH solution, stirring and filtering to obtain a brown sodium silicate solution;
2) Adjusting the water glass solution to pH=8-10 by acid titration, aging and centrifuging to obtain nano silica sol gel, drying and grinding for later use;
3) Preparing nano silica sol into silica sol solution, dispersing the silica sol solution under an ultrasonic cleaning machine, and then immersing ferrochrome slag aggregate into the solution and fully immersing the ferrochrome slag aggregate;
4) Adding a modifier and a cross-linking agent into the fully soaked solution to strengthen aggregate, and adding a small amount of initiator and accelerator to accelerate the reaction;
5) And curing the modified aggregate, and drying and curing for later use.
6. The method for preparing silica sol modified ferrochrome slag aggregate according to claim 5, wherein: the amount of NaOH substance in the step 1) is 0.6-0.8 mol.
7. The method for preparing silica sol modified ferrochrome slag aggregate according to claim 5, wherein: the aging time required by the aging and centrifuging step in the step 2) is 2-3 d, and the centrifuging speed is 3500-4000 rpm.
8. The method for preparing silica sol modified ferrochrome slag aggregate according to claim 5, wherein: the nano silica sol solution with a certain mass fraction after being dispersed under the ultrasonic cleaning machine in the step 3) is dispersed for 20-30 min, the ultrasonic frequency is 30-40 KHz, and the nano silica sol solution is 5-10 wt%.
9. The method for preparing silica sol modified ferrochrome slag aggregate according to claim 5, wherein: the curing condition in the step 4) is 20+/-2 ℃, the relative humidity is 95%, and the curing time is 3d.
10. The method for preparing silica sol modified ferrochrome slag aggregate according to claim 5, wherein: the drying temperature in the steps 1), 2) and 4) is 110-140 ℃ and the time is 12-18 h.
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