CN117486576A - High-corrosion-resistance concrete and preparation method and application thereof - Google Patents
High-corrosion-resistance concrete and preparation method and application thereof Download PDFInfo
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- CN117486576A CN117486576A CN202311213327.2A CN202311213327A CN117486576A CN 117486576 A CN117486576 A CN 117486576A CN 202311213327 A CN202311213327 A CN 202311213327A CN 117486576 A CN117486576 A CN 117486576A
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- 239000004567 concrete Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title description 10
- 239000010881 fly ash Substances 0.000 claims abstract description 84
- 239000002893 slag Substances 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 239000004568 cement Substances 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004576 sand Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000000292 calcium oxide Substances 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 31
- 238000005260 corrosion Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 26
- 230000005284 excitation Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000013535 sea water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000005997 Calcium carbide Substances 0.000 abstract description 6
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 41
- 239000000463 material Substances 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 229920000876 geopolymer Polymers 0.000 description 7
- 230000036571 hydration Effects 0.000 description 7
- -1 silver ions Chemical class 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004566 building material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229940069978 calcium supplement Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 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
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229920003041 geopolymer cement Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses high-corrosion-resistance concrete, which comprises the following components in parts by weight: 100 parts of cement, 100-125 parts of modified carbide slag powder, 125-250 parts of III-grade fly ash, 20-50 parts of sodium hydroxide, 250-295 parts of water glass, 600-900 parts of common sand, 700-1200 parts of cobble, 5-30 parts of silver-containing wastewater and 5-50 parts of water; the modified carbide slag powder is obtained by calcining and grinding waste slag taking calcium hydroxide as a main component after calcium carbide is hydrolyzed to obtain acetylene gas; the calcination temperature is 500-600 ℃, and the calcination time is 30-120min; the average particle diameter is 20-50 μm; the chemical components of the modified carbide slag powder comprise 60-90% of CaO, 0-30% of Ca (OH) 2, 1-2% of MgO and SiO 2 5-10% of Fe 2 O 3 0.5% -2.0%, al 2 O 3 0.1% -1.0%; the invention carries out resource utilization on III-level fly ash, carbide slag and silver-containing wastewater, and develops and compensates shrinkage by improving the strength of concreteGreatly improves the anti-chloride ion permeation performance of the concrete.
Description
Technical Field
The invention belongs to the technical field of concrete materials, and particularly relates to high-corrosion-resistance concrete and a preparation method and application thereof.
Background
In recent years, the super-large cooling tower with the hyperbolic thin-wall structure is widely applied to thermal power and nuclear power, along with the development of nuclear power technology, the building of the large-size high-hyperbolic cooling tower is more and more frequent, the wall thickness is thinner, and the cooling tower structure relates to a large-volume structure, an opposite-type structure and a thin-wall structure and has higher working performance and crack resistance requirements so as to meet the requirements of durability and safety design. Meanwhile, the site of the nuclear power plant is often close to the sea, and the current nuclear power project cooling tower is often designed in a seawater cooling mode, so that the requirement on the chloride ion permeation resistance coefficient of the cooling tower concrete is high, and the design requirement is less than 4 multiplied by 10 < -12 > m < 2 >/s (28 d or 56 d).
Fly ash is a common industrial solid waste, wherein class I and class II fly ash has been fully used in the building field, and meanwhile, due to the problem of the activity of low-grade fly ash (class III), the fly ash cannot be used and treated. The continuous piling of the materials also has great influence on the ecological environment. The utilization rate and the application range of the low-grade fly ash (III grade) are improved, and the problems to be solved are solved urgently at present; in addition, the carbide slag is mainly derived from the production of polyvinyl chloride and vinyl acetate by a calcium carbide method. The consumption of the calcium carbide is about 1.45 tons per ton of the produced polyvinyl chloride, and 1 ton of the multi-carbide slag is produced after the hydrolysis of each ton of the calcium carbide, so that 2 tons of the multi-carbide slag are discharged per 1 ton of the produced polyvinyl chloride. The carbide slag has large quantity and high alkali content, contains sulfur, arsenic and other harmful substances, can block a sewer without being discharged through treatment, is accumulated on a river bed, and endangers fishery production.
Finally, the silver-containing wastewater refers to wastewater containing high concentration silver ions in the industrial production process. The treatment of silver-containing wastewater is particularly important because of the strong toxicity and bioaccumulation of silver.
Disclosure of Invention
The strength of the alkali-activated geopolymer of the III-grade fly ash can be improved by 'supplementing calcium', and the CaO content of the modified carbide slag powder is relatively high, and the modified carbide slag powder is higher than Ca (OH) 2 The content can be adjusted by the calcination time. Therefore, the modified carbide slag powder is used as the calcium supplementing substance of the III-level fly ash, and has the following benefits: 1. the use amount of the modified finely ground carbide slag in the composite alkali-activated raw materials (III-level fly ash and carbide slag powder) is adjusted, so that the III-level fly ash has the effect of calcium supplement, the activation effect of the III-level fly ash in the composite alkali-activated raw materials in an alkaline environment can be improved, and the strength and the corrosion resistance of the whole concrete are improved; 2. CaO and Ca (OH) are changed by adjusting the calcination time 2 The content change not only can change the calcium supplementing effect of the III-level fly ash, but also can utilize Ca (OH) in the modified finely ground carbide slag 2 As another alkali activator, the early-stage intermediate activity of the fly ash is excited, the early-stage strength of the III-level fly ash concrete is improved, and the problem of insufficient early-stage strength of the concrete is solved.
The invention provides green high-corrosion-resistance seawater cooling tower concrete taking cement, III-level fly ash and carbide slag powder as main components and a preparation method thereof, which are combined with the problems of difficult utilization and serious waste of III-level fly ash and the characteristics of carbide slag.
In order to achieve the above purpose, the following technical scheme is adopted:
the high-corrosion-resistance concrete comprises the following components in parts by weight:
100 parts of cement, 100-125 parts of modified carbide slag powder, 125-250 parts of III-grade fly ash, 20-60 parts of sodium hydroxide, 250-295 parts of water glass, 600-900 parts of common sand, 700-1200 parts of cobble, 5-30 parts of silver-containing wastewater and 5-50 parts of water.
According to the scheme, the cement adopts P.O42.5 cement, 300m 2 The specific surface area of the catalyst is not more than/kg and not more than 370m 2 /kg。
According to the scheme, the modified carbide slag powder is obtained by calcining and grinding waste slag taking calcium hydroxide as a main component after acetylene gas is obtained by hydrolyzing calcium carbide; the calcination temperature is 500-600 ℃, and the calcination time is 30-120min; the average particle diameter is 20-50 μm.
According to the scheme, the chemical components of the modified carbide slag powder comprise 60-90% of CaO, 0-30% of Ca (OH) 2, 1-2% of MgO and SiO 2 5-10% of Fe 2 O 3 0.5% -2.0%, al 2 O 3 0.1% -1.0%.
According to the scheme, the fineness range of the III-grade fly ash is 30-40%, the loss on ignition range is 3-8%, the CaO content in the chemical components is 4-10%, and K is the same as that of the III-grade fly ash 2 O content is 1-4%, siO 2 The content is 45-55%, fe 2 O 3 3-8% of Al 2 O 3 The content is 25% -35%.
According to the scheme, the silver-containing wastewater is wastewater containing high concentration silver ions in the industrial production process, and Ag + The concentration is 2000-2500mg/L.
According to the scheme, the concentration of the water glass is 40wt percent, and the modulus is 1.4.
According to the scheme, the purity of the sodium hydroxide is more than 99.55 weight percent.
According to the scheme, the common sand is middle sand, and the fineness modulus of the common sand is 2.3-3.0.
The preparation method of the high-corrosion-resistance concrete comprises the following steps:
mixing compound alkaline activator (sodium hydroxide, water glass), water and silver-containing wastewater to prepare an activator solution; mixing cobble, cement, III-level fly ash, modified carbide slag powder and common sand, adding alkali excitation solution, and uniformly mixing and stirring to obtain the high-corrosion-resistance cooling tower concrete.
The high corrosion resistance concrete is applied to the seawater cooling tower.
The inventor finds wide application of the class I and class II fly ash in building materials in the long-term working process, the application of the class III fly ash in the building material field is almost zero, and the reason is that the fineness and the activity of the class III fly ash are much lower than those of the class I and class II fly ash. In addition, in the field of alkali-activated building materials, the strength and the crack resistance of the class I and class II fly ash alkali-activated geopolymer are greatly improved compared with those of common concrete, but the strength and the crack resistance of the class III fly ash alkali-activated geopolymer are far insufficient.
The invention organically combines and utilizes the physical and chemical properties among three industrial wastes, thereby realizing the aim of changing waste into valuables. Firstly, considering that the CaO content in the low-grade fly ash (III grade) is low, the low-grade fly ash (III grade) cannot be directly applied to the preparation of concrete, and meanwhile, the strength requirement of the low-grade fly ash (III grade) polymer cannot be met in an alkali excitation mode. The use level of the modified fine ground carbide slag powder in the composite alkali excitation raw material (III-level fly ash and modified fine ground carbide slag powder) is adjusted, so that the III-level fly ash has the effect of 'supplementing calcium', the CaO content in the overall alkali excitation raw material is improved, and the excitation effect of the III-level fly ash in the composite alkali excitation raw material under an alkaline environment can be improved; in addition, caO and Ca (OH) are changed by adjusting the calcination time 2 The content change can be used for modifying Ca (OH) in the finely ground carbide slag 2 As another alkali excitant, the early-stage inter-activity of the fly ash is excited, the early-stage strength of the III-level fly ash concrete is improved, and the problem of insufficient early-stage strength of the concrete is solved; secondly, due to the physical property of the fly ash, the addition of the III-grade fly ash can effectively improve the chloride ion adsorption capacity of the concrete; then, because the advantages of small alkali excitation water demand, low hydration heat, good thermal stability, high crack resistance, water reduction and the like are outstanding, the crack resistance of the concrete is further optimized by introducing part of alkali excitation materials in the preparation of the concrete. Finally, the addition of the silver-containing wastewater weakens the erosion of chloride ions to the concrete, greatly reduces the concentration of the chloride ions penetrating into the concrete, and ensures that the internal reaction degree of the polymer cementing material of the fly ash can be obtained under the action of low-concentration chloride ionsThe compactness of the concrete is further increased.
The low-grade (III-grade) fly ash not only serves as a raw material of the alkali-activated geopolymer, but also is beneficial to the secondary hydration reaction of the fly ash after being doped into cement. Secondary hydration of fly ash is to absorb Ca (OH) generated by cement hydration in a gelled system 2 The C-S-H gel and the calcium aluminate hydrate are generated, the strength of the whole cementing material is improved, and the calcium aluminate hydrate can be combined with Cl - And CH to generate Friedel salt to solidify CI - Is effective in (1). In addition, the fly ash particles are larger and are in a hollow spherical structure, and complex air holes are formed in the surface and are communicated with the inner cavity, so that the specific surface area of the fly ash is increased, a large amount of free chloride ions can be adsorbed, and the adsorption of the chloride ions is further improved. Finally, the C-S-H gel can absorb and cure partial chloride ions due to the larger surface energy.
The invention uses silver-containing wastewater, which is wastewater containing high concentration silver ions in industrial production process. Adding silver-containing wastewater, wherein Ag + The ions can not only effectively reduce corrosion of chloride ions to the interior of the concrete by producing precipitates through reaction with the chloride ions, but also reduce the concentration of the chloride ions entering the interior of the concrete.
Because the fly ash has the adsorption performance on chloride ions, the internal reaction degree of the polymer of the fly ash can be effectively improved under the action of low chloride ion concentration. The surface layer part of the concrete material near the air is contacted with chloride ions and sulfate radical plasma in the air preferentially and then contacted with Ag + The reaction generates sediment, and reduces the concentration of chloride ions which invade the interior of the concrete. Then, the reaction of the flyash geopolymer in the deeper layer is improved under the action of the low-concentration chloride ions which permeate into the flyash geopolymer, the strength and the compactness of the concrete of the part are enhanced, the impermeability and the corrosion resistance of the part are improved, and further, the invasion of the chloride ions into the deeper layer concrete can be further effectively inhibited, the contact of reinforcing steel bars with the chloride ions, sulfate ions and the like is avoided, and the corrosion resistance of the concrete is improved.
The alkali excitation reaction principle involved in the invention has two kinds: 1. the fly ash generates hydrated sodium aluminosilicate under the excitation of the water glass, and the sodium hydroxide plays a role in adjusting the modulus of the water glass, so that the strength of the concrete can be effectively improved; 2. the fly ash generates hydrated calcium silicate and hydrated calcium aluminate under the excitation of calcium hydroxide, and can also effectively improve the strength of concrete.
Compared with the prior art, the invention has the following beneficial effects:
1. the low-grade (III-grade) fly ash cannot be applied to concrete due to the fineness and activity problems of the low-grade (III-grade) fly ash, and the excitation effect of the low-grade (III-grade) fly ash in an alkaline environment is improved by taking calcium supplementing measures (CaO supplementing the low-grade (III-grade) fly ash) and adjusting the quantity of calcium supplementing, so that the strength and crack resistance of the polymer cementing material excited by the III-grade fly ash alkali are improved, and the application way of the low-grade (III-grade) fly ash in the field of buildings can be realized and improved; in addition, the invention adopts the ground carbide slag powder as the calcium supplementing substance of the low-grade (III-grade) fly ash alkali-activated geopolymer, thereby not only effectively utilizing the characteristic of high CaO content in the ground carbide slag powder, but also improving the utilization way of carbide slag;
2. ca (OH) in the modified finely ground carbide slag can be utilized 2 As another alkali excitant, the early-stage intermediate activity of the fly ash is excited, the early-stage strength of the III-level fly ash concrete is improved, and the problem of insufficient early-stage strength of the concrete is solved;
3. in the invention, the low-grade (III-grade) fly ash is not only used as a raw material of alkali-activated polymer, but also is beneficial to the secondary hydration reaction of the fly ash after being doped into cement. Secondary hydration of fly ash is to absorb Ca (OH) generated by cement hydration in a gelled system 2 The strength of the whole cementing material is improved by generating C-S-H gel and calcium aluminate hydrate, and the C-S-H gel has larger surface energy and can adsorb partial chloride ions; at the same time hydrated calcium aluminate can combine with Cl - And CH to generate Friedel salt to solidify CI - Is effective in (1). In addition, the fly ash particles are larger and are in a hollow spherical structure, and complex air holes are formed in the surface and are communicated with the inner cavity, so that the specific surface area of the fly ash is increased, a large amount of free chloride ions can be adsorbed, and the fly ash is further extractedHigh adsorption of chlorine ions. Therefore, the anti-seepage and anti-corrosion performances of the concrete of the seawater cooling tower can be effectively improved by combining the excitation effect improvement principle and the anti-cracking improvement effect which are exerted by the materials.
4. The silver-containing wastewater is added, ag + Ions can effectively reduce erosion of chloride ions to the interior of concrete by reacting with chloride ions to produce precipitates. In addition, the internal reaction degree of the polymer of the alkali-activated fly ash can be effectively improved under the action of low chloride ion concentration, and the surface layer part of the concrete material close to one side of air is contacted with chloride ions and sulfate radical plasma in the air preferentially to be contacted with Ag + The reaction generates precipitate, so that the concentration of chloride ions which invade the interior of the concrete is greatly reduced, and the alkali excitation reaction degree of the inner side material is effectively improved under the action of low-concentration chloride ions, so that the strength and the compactness of the concrete are further improved, the impermeability and the corrosion resistance of the concrete are improved, the contact of reinforcing steel bars with ions such as chloride ions and sulfate ions is avoided, and the corrosion resistance of the concrete is improved.
5. Because the alkali excitation water demand is small, the hydration heat is low, the heat stability is good, the crack resistance and the water reduction performance are high, and the like, the crack resistance of the concrete is further optimized by introducing part of alkali excitation materials in the preparation of the concrete.
6. The invention uses cement and III-grade fly ash as main raw materials of seawater concrete of the cooling tower with high crack resistance and corrosion resistance, and simultaneously uses ground fine electric slag powder as an external calcium source, a sodium source and the like. Not only solves the problem of insufficient strength of the alkaline-activated III-level fly ash cementing material by taking calcium oxide in the ground carbide slag powder as an external calcium source, changes waste into valuable and harmful into valuable, but also improves the utilization way of carbide slag in the field of building materials and relieves the problem of carbide slag waste; in addition, the addition of the silver-containing wastewater can not only effectively reduce corrosion of chloride ions to concrete and reduce the concentration of chloride ions entering the concrete, but also effectively improve the reaction degree of the polymer cementing material of the fly ash under the action of low-concentration chloride ions, so that the reaction degree and the compactness of the concrete are further improved and the invasion of the chloride ions is further hindered on the basis that the concentration of the chloride ions invaded into the concrete is reduced by the silver ions.
7. The preparation process adopts industrial waste as a main raw material to prepare the alkali-activated material, realizes the replacement of the cement material, reduces the demand on the cement material, can not only relieve the excessively rapid consumption of limestone, clay and energy source in cement production and reduce the problems of high energy consumption and high pollution caused by cement production, but also gradually eliminate the problem of environmental pollution caused by the accumulation of a large amount of industrial solid waste. Meets the requirements of national environmental protection policies, and has great application prospect.
Detailed Description
The following examples further illustrate the technical aspects of the present invention, but are not intended to limit the scope of the present invention.
The concrete with high corrosion resistance comprises the following components in parts by weight:
100 parts of cement, 100-125 parts of modified carbide slag powder, 125-250 parts of III-grade fly ash, 20-60 parts of sodium hydroxide, 250-295 parts of water glass, 600-900 parts of common sand, 700-1200 parts of cobble, 5-30 parts of silver-containing wastewater and 5-50 parts of water.
Specifically, the cement adopts P.O42.5 cement, 300m 2 The specific surface area of the catalyst is not more than/kg and not more than 370m 2 /kg。
Specifically, the modified carbide slag powder is obtained by calcining and grinding waste slag taking calcium hydroxide as a main component after calcium carbide is hydrolyzed to obtain acetylene gas; the calcination temperature is 500-600 ℃, and the calcination time is 30-120min; the average particle diameter is 20-50 μm; 60-90% of CaO, 0-30% of Ca (OH) 2, 1-2% of MgO and 1-2% of SiO in the chemical components of the modified carbide slag powder 2 5-10% of Fe 2 O 3 0.5% -2.0%, al 2 O 3 0.1% -1.0%.
Specifically, the fineness range of the III-level fly ash is 30-40%, the loss on ignition range is 3-8%, the CaO content in the chemical components is 4-10%, and K is the same as that of the III-level fly ash 2 O content is 1-4%, siO 2 The content is 45-55%, fe 2 O 3 The content is as follows3％-8％，Al 2 O 3 The content is 25% -35%.
Specifically, the silver-containing wastewater is wastewater containing high concentration of silver ions in the industrial production process, ag + The concentration is 2000-2500mg/L.
Specifically, the concentration of the water glass is 40wt% and the modulus is 1.4; the purity of the sodium hydroxide is more than 99.55wt%.
Specifically, the common sand is middle sand, and the fineness modulus of the common sand is 2.3-3.0.
The concrete embodiment also provides a preparation method of the high-corrosion-resistance concrete, which comprises the following steps:
mixing compound alkaline activator (sodium hydroxide, water glass), water and silver-containing wastewater to prepare an activator solution; mixing cobble, cement, III-level fly ash, modified carbide slag powder and common sand, adding alkali excitation solution, and uniformly mixing and stirring to obtain the high-corrosion-resistance cooling tower concrete.
The composition design ratios of the specific examples are shown in Table 1.
TABLE 1
The results of the performance characterization of the specific examples are shown in Table 2. The 100mm cube compressive strength is tested according to the test method standard of physical and mechanical properties of concrete (CBT 50081-2019), and the rapid chloride ion diffusion coefficient DRCM and the electric flux of concrete are tested according to the test method standard of long-term performance and durability of common concrete (CB/T50082-2009). According to the soaking corrosion resistance test method (K method) in GB/T1749-2008 "test method for cement erosion resistance sulfate", the test piece of the gum sand is tested in fresh water and SO4 2- Soaking in solution (SO 4) 2- In the etching solutions with the concentrations of 20000mg/L, respectively, an etching simulation test was performed for a period of 12 months). After the soaking is finished, the flexural strength of the test piece is measured, the corrosion resistance coefficient is calculated, and the corrosion resistance coefficient is more than or equal to 0.80 and is qualified for corrosion resistance and is used as a judging standard.
TABLE 2
From test data, the concrete test piece provided by the embodiment of the invention has good performances of resisting chloride ions and sulfate corrosion, and maintains good mechanical properties. Among them, it is known from the observation of example 7 that the calcium supplement (CaO) of class iii fly ash by using carbide slag powder can effectively improve the strength, chloride ion resistance and sulfate corrosion resistance of concrete. The key point of the invention is that the proportion of III-level fly ash and carbide slag powder in the alkali-activated raw material is changed and adjusted, and the carbide slag powder is utilized to supplement calcium (CaO) to III-level fly ash, so that the performances of the III-level fly ash are improved to different degrees; meanwhile, the uniform distribution of the III-level fly ash can absorb corrosive ions such as chloride ions; finally, the fly ash is uniformly dispersed, and the adsorption performance of the fly ash on chloride ions and the internal reaction degree of the polymer of the fly ash can be effectively improved under the action of the chloride ions. The alkali-activated hydration degree of the fly ash in the gel system is improved, the strength and the compactness of the geopolymer concrete are further improved, and the impermeability and the corrosion resistance of the concrete are improved.
Further observation of example 13 shows that the addition of certain silver ion-containing wastewater can further improve the chloride ion resistance of concrete, and the mechanical properties also meet the standard requirements. The surface layer part of the concrete material close to one side of the seawater is preferentially contacted with chloride ions and sulfate ions in the seawater, so that the strength and the compactness of the concrete of the part are also preferentially improved, the impermeability and the corrosion resistance of the part are improved, the contact between the concrete and the reinforcing steel bar at the inner part and the ions such as chloride ions and sulfate ions can be effectively reduced, and the corrosion resistance of the concrete is improved.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (10)
1. The high-corrosion-resistance concrete is characterized by comprising the following components in parts by weight:
100 parts of cement, 100-125 parts of modified carbide slag powder, 125-250 parts of III-grade fly ash, 20-50 parts of sodium hydroxide, 250-295 parts of water glass, 600-900 parts of common sand, 700-1200 parts of cobble, 5-30 parts of silver-containing wastewater and 5-50 parts of water.
2. The high corrosion resistance concrete according to claim 1, wherein the modified carbide slag powder is obtained by calcining and grinding waste slag containing calcium hydroxide as a main component after acetylene gas is obtained by hydrolysis of carbide; the calcination temperature is 500-600 ℃, and the calcination time is 30-120min; the average particle diameter is 20-50 μm.
3. The concrete of claim 1, wherein the modified slag powder has a chemical composition of 60-90% CaO, 0-30% Ca (OH) 2, 1-2% MgO, and SiO 2 5-10% of Fe 2 O 3 0.5% -2.0%, al 2 O 3 0.1% -1.0%.
4. The concrete with high corrosion resistance according to claim 1, wherein the class III fly ash has fineness ranging from 30% to 40%, loss on ignition ranging from 3% to 8%, caO content in chemical components ranging from 4% to 10%, K 2 O content is 1-4%, siO 2 The content is 45-55%, fe 2 O 3 3-8% of Al 2 O 3 The content is 25% -35%.
5. The concrete of claim 1, wherein the silver-containing wastewater is produced in an industrial processWaste water containing high concentration silver ion, ag + The concentration is 2000-2500mg/L.
6. The high corrosion resistant concrete of claim 1 wherein said water glass has a concentration of 40% by weight and a modulus of 1.4.
7. The high corrosion resistant concrete of claim 1 wherein said sodium hydroxide has a purity of 99.55% by weight or more.
8. The high corrosion resistant concrete of claim 1 wherein said normal sand is a medium sand having a fineness modulus of between 2.3 and 3.0.
9. A method for preparing high corrosion resistant concrete according to any one of claims 1 to 8, characterized by comprising the steps of:
mixing sodium hydroxide, sodium silicate, water and silver-containing wastewater to prepare an excitant solution; mixing cobble, cement, III-level fly ash, modified carbide slag powder and common sand, adding alkali excitation solution, and uniformly mixing and stirring to obtain the high-corrosion-resistance cooling tower concrete.
10. Use of the high corrosion resistant concrete of any one of claims 1-8 in a seawater cooling tower.
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