CN106477931B - Modified active phosphorus slag, preparation method and modified active phosphoric slag cement and concrete - Google Patents
Modified active phosphorus slag, preparation method and modified active phosphoric slag cement and concrete Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 217
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000011574 phosphorus Substances 0.000 title claims abstract description 126
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 126
- 239000004568 cement Substances 0.000 title claims abstract description 78
- 239000004567 concrete Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012190 activator Substances 0.000 claims abstract description 17
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 239000010881 fly ash Substances 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000010440 gypsum Substances 0.000 claims abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 8
- 239000013543 active substance Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910001570 bauxite Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims 11
- 239000002440 industrial waste Substances 0.000 claims 7
- 239000005997 Calcium carbide Substances 0.000 claims 3
- 229940024548 aluminum oxide Drugs 0.000 claims 3
- 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 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000007670 refining Methods 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 230000003213 activating effect Effects 0.000 abstract description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract description 12
- 235000011128 aluminium sulphate Nutrition 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- 206010067482 No adverse event Diseases 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000011396 hydraulic cement Substances 0.000 description 2
- 238000004137 mechanical activation Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B20/023—Chemical 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
- 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The present invention relates to a kind of modified active phosphorus slag, preparation method and modified active phosphoric slag cement and concrete, modified active phosphorus slag includes: activating agent and phosphorus slag；Activating agent and phosphorus slag mass ratio are 0.5-1:10；Moisture in phosphorus slag is less than phosphorus slag weight 2%；The weight ratio of active agent component are as follows: 50-70 parts of carbide slag, aluminium sulfate slag: 0-40 parts, red mud: 0-40 parts, aluminous fly-ash: 0-30, gypsum: 20-30 parts, anhydrous calcium sulphoaluminate mineral: 0-30 parts.Modified active phosphorus slag of the present invention, which eliminates harmful components in phosphorus slag, influences cement and concrete performance, and modified active phosphorus slag shortens cement setting time, and intensity improves, while improves each age strength of concrete, and each age contract with dry rate is less than slag powders；Activator used is various industrial residues when the present invention is to phosphorus slag modified active, without chemi-excitation reagent, it has no adverse effects to cement and concrete service performance and endurance quality etc., makes it possible that high-dopant phosphorus slag is applied in cement and concrete, achieve the purpose that turn waste into wealth.
Description
Technical field
The present invention relates to a kind of modified active phosphorus slags, more particularly to a kind of modified active phosphorus slag, preparation method and modification
Activate phosphoric slag cement and concrete.
Background technique
Phosphorus slag is good recycling resource, and chemical component and mine phase composition are similar to slag, is had good latent
In the hydraulicity, and have the characteristics that concrete workability it is good, it is impervious it is strong, later strength growth rate is big.Currently, phosphorus slag is in cement
Sill, sintered hollow block, steam pressure building-block, devitrified glass, non-fired and non-steamed bricks, road surface base layer material, rock wool etc. have
Certain application.But due to P in phosphorus slag2O5Etc. harmful components to cement setting harden and early strength development have larger impact,
Thus its application percentage in cement industry and concrete construction engineering is not high, and most of phosphorus slag air storage is (accumulative to stack
Amount is more than 90,000,000 tons), ecological environment is constituted and is seriously endangered.
It is influenced to improve reactivity of phosphor slag, eliminating harmful components in phosphorus slag, people have conducted extensive research nearly ten years.Mesh
Before, reactivity of phosphor slag exciting method is divided into the three classes such as mechanical activation, chemical activation and multiplicity reactivation.Wherein, mechanical activation is benefit
Phosphorus slag reaction contact area and vitreum fracture bond number are improved with mechanical grinding mode, improves phosphorus slag powder distribution of particles, enhancing
Phosphorus slag hydration reaction activity；Chemical activation, which mainly passes through alkaline condition, makes the disintegration of phosphorus slag vitreum or acceleration of hydration hardening, with
Improve phosphorus slag reactivity；Multiplicity reactivation is that first two method is compound.These activity methods technological means are different, improve to phosphorus slag
Effect is also different.However activation method is less to the concern of the characteristics such as cement service performance, rheological characteristic and drying shrinkage, anti-corrosion at present；
And the use of chemical reagent is not only at high cost, while there is also some shortcomings, such as highly basic, basic salt and villaumite exciting agent, easily
Phenomena such as inducing concrete alkali aggregate reaction, steel bar corrosion；Sulphate activation agent, calcium oxide equal excitation material can also to cement and
Volume stability of concrete brings certain hidden danger；Furthermore excitation material incorporation in phosphorus slag is excessively high, also can be special to phosphorus slag aquation
Property has a negative impact, such as the heat of hydration, impermeability, later strength growth rate.
Summary of the invention
It is a primary object of the present invention to provide the new modified activation phosphorus slag of one kind, preparation method and modified active phosphorus slag
Cement and concrete, the technical problem to be solved is that making it turn waste into wealth, thus more suitable for practical.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of modified active phosphorus slag comprising: the mass ratio of activating agent and phosphorus slag, the activating agent and phosphorus slag be 0.5-1:10；
Wherein, the moisture in the phosphorus slag is less than the 2wt% of phosphorus slag weight；The weight ratio of the component of the activating agent are as follows: carbide slag
50-70 parts, aluminium sulfate slag: 0-40 parts, red mud: 0-40 parts, aluminous fly-ash: 0-30, gypsum: 20-30 parts, anhydrous calcium sulphoaluminate
Mineral: 0-30 parts.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, modified active phosphorus slag above-mentioned, wherein the calcium oxide content in the carbide slag is more than or equal to
65wt%；Dioxide-containing silica in the aluminium sulfate slag is 60%-72wt%, and the content of aluminum oxide is 8wt%-
15wt%；Calcium oxide, alchlor and total silica content in the red mud are greater than 60wt%, K2O or Na2The content of O
For 1wt%-3wt%；Alchlor content in the aluminous fly-ash is greater than 35wt%.
Preferably, modified active phosphorus slag above-mentioned, wherein the carbide slag is the Industry Waste for preparing acetylene gas and obtaining
Slag；The aluminium sulfate slag is the industrial residue for preparing bauxite and obtaining；The red mud is to refine aluminium oxide to obtain industrial residue；Institute
Stating aluminous fly-ash is coal-burning power plant's waste discharge gurry；The anhydrous calcium sulphoaluminate mineral are sulphoaluminate cement clinker, the sulphur
Mineral constituent content in aluminate cement clinker is more than or equal to 55wt%.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of modified active phosphorus slag preparation method comprising following steps: phosphorus slag is dried；By weight, carbide slag 50- is taken
70 parts, aluminium sulfate slag: 0-40 parts, red mud: 0-40 parts, aluminous fly-ash: 0-30, gypsum: 20-30 parts, anhydrous calcium sulphoaluminate mine
Object: it 0-30 parts, is uniformly mixed, obtains activator；Phosphorus slag and the activator after drying is mixed for 0.5-1:10 in mass ratio
It closes uniformly, grinding obtains modified active phosphorus slag.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of modified active phosphorus slag above-mentioned, is less than wherein phosphorus slag is dried to moisture content
2wt%.
Preferably, the preparation method of modified active phosphorus slag above-mentioned, wherein the temperature of the drying is 100-200 DEG C.
Preferably, the preparation method of modified active phosphorus slag above-mentioned, wherein the calcium oxide content in the carbide slag is big
In being equal to 65wt%, to prepare the industrial residue that acetylene gas obtains；Dioxide-containing silica in the aluminium sulfate slag is
The content of 60%-72wt%, aluminum oxide are 8wt%-15wt%, to prepare the industrial residue that bauxite obtains；Described
Calcium oxide, alchlor and total silica content in red mud are greater than 60wt%, K2O or Na2The content of O is 1wt%-
3wt% obtains industrial residue to refine aluminium oxide；Alchlor content in the aluminous fly-ash is greater than 35wt%, is
Coal-burning power plant's waste discharge gurry；The anhydrous calcium sulphoaluminate mineral are sulphoaluminate cement clinker, the sulphoaluminate cement clinker
In mineral constituent content be more than or equal to 55wt%.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of modified active phosphoric slag cement, component (by weight percentage) includes: modified active phosphorus slag of the present invention:
30%-50%, cement base-material: 50%-70%；The sum of the above components are 100%.
Preferably, modified active phosphoric slag cement above-mentioned, wherein its presetting period is 1h:30min-6h:30min, final set
Time is 3h-7h:30min；3d flexural strength is 2.2-4.2MPa, and 28d flexural strength is 6.7-8.6MPa；28d compression strength
For 38.8-53.0MPa, 3d compression strength is 14.8-28.0MPa.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of modified active phosphorus slag concrete, component (by weight percentage) includes: modified active phosphorus slag of the present invention:
10%-30%, concrete base-material: 70%-90%；The sum of the above components are 100%.
By above-mentioned technical proposal, modified active phosphorus slag, preparation method and modified active phosphoric slag cement and coagulation of the present invention
Soil at least has the advantage that
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
1, modified active phosphorus slag of the present invention eliminates P in phosphorus slag2O5Etc. harmful components cement and concrete performance are influenced.
Present invention activator used when being modified activation to phosphorus slag is essentially different types of industrial residue, is free of strong basicity or salt
The chemi-excitations reagent such as class；Modified active phosphorus slag of the invention keeps cement setting time significant compared to the phosphorus slag without overactivation
Shorten, and cement 3 days and 28 days intensity improve a lot, while are improved each age strength of concrete also, each age does
Shrinkage is less than slag powders；Furthermore activator of the invention is to cement and concrete service performance and endurance quality etc. without bad shadow
It rings, makes it possible that high-dopant phosphorus slag is applied in cement and concrete.
2, phosphorus slag of the invention improvement activation method is easy to operate, and without complicated production equipment, economic and reliable is conducive to
Phosphorus slag promotes and applies in cement industry and Concrete Industry, has a extensive future.
3, China is discharged every year carbide slag, aluminium sulfate slag, red mud, aluminous fly-ash, phosphorus slag at 25,000,000 tons or more, this
Invention uses the above industrial residue to prepare modified active phosphorus slag for raw material, has achieved the purpose that turn waste into wealth, save the cost.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to modified active phosphorus slag proposed according to the present invention, preparation method and modified active phosphoric slag cement and concrete
Its specific embodiment, feature and its effect, detailed description is as follows.In the following description, different " embodiment " or " implementation
What example " referred to is not necessarily the same embodiment.In addition, the special characteristic or feature in one or more embodiments can be by any suitable shapes
Formula combination.
A kind of modified active phosphorus slag that one embodiment of the present of invention proposes comprising: activating agent and phosphorus slag, wherein described
Activating agent and phosphorus slag mass ratio be 0.5-1:10 wherein, moisture in the phosphorus slag is less than the 2% of phosphorus slag weight；Described
The weight ratio of the component of activating agent are as follows: 50-70 parts of carbide slag, aluminium sulfate slag: 0-40 parts, red mud: 0-40 parts, aluminous fly-ash:
0-30, gypsum: 20-30 parts, anhydrous calcium sulphoaluminate mineral: 0-30 parts.The present embodiment uses tetra- kinds of model phosphorus slags of A, B, C, D, respectively
The chemical component of the phosphorus slag of model is as shown in table 1；The activating agent of specific embodiment and the mass ratio of phosphorus slag, the weight of moisture in phosphorus slag
Content is measured, activating agent proportion is as shown in table 2.
Preferably, the calcium oxide content in carbide slag described in the modified active phosphorus slag of the embodiment of the present invention is more than or equal to
65wt% is mainly used for improveing in chemical reaction forming precipitated hydroxyapatite with phosphate radical in phosphorus slag, solidifying to shorten cement
Tie the time；Dioxide-containing silica in the aluminium sulfate slag is 60%-72wt%, and the content of aluminum oxide is 8wt%-
15wt% is conducive to shorten cement setting time, provides intensity；Calcium oxide, alchlor and titanium dioxide in the red mud
Silicon total content is greater than 60wt%, K2O or Na2The content of O is 1wt%-3wt%, has hydration activity excitation；The height
Alchlor content in aluminium powder coal ash is greater than 35wt%, and it is insufficient can to make up phosphorus slag aluminium phase content in aquation liquid phase.
Preferably, carbide slag described in the modified active phosphorus slag of the embodiment of the present invention is the industry for preparing acetylene gas and obtaining
Waste residue；The aluminium sulfate slag is the industrial residue for preparing bauxite and obtaining；The red mud is to refine aluminium oxide to obtain industrial residue；
The aluminous fly-ash is coal-burning power plant's waste discharge gurry；The anhydrous calcium sulphoaluminate mineral are sulphoaluminate cement clinker, state sulphur
Mineral constituent content in aluminate cement clinker is more than or equal to 55wt%, effectively shortens cement setting time, it is contemplated that economical
Cost factor, thus it is relatively small in activator use ratio.
Another embodiment of the invention proposes a kind of preparation method of modified active phosphorus slag, mainly comprises the steps that
Phosphorus slag is dried；By weight, 50-70 parts of carbide slag are taken, aluminium sulfate slag: 0-40 parts, red mud: 0-40 parts, aluminous fly-ash:
Gypsum: 0-30 20-30 parts, anhydrous calcium sulphoaluminate mineral: 0-30 parts, is uniformly mixed, obtains activator；Phosphorus slag after drying and
The activator is uniformly mixed in mass ratio for 0.5-1:10, and grinding obtains modified active phosphorus slag.The present embodiment using A, B,
C, tetra- kinds of model phosphorus slags of D, the chemical component of the phosphorus slag of each model are as shown in table 1；The activating agent of specific embodiment and the matter of phosphorus slag
Ratio is measured, activating agent proportion is as shown in table 2.
It is less than preferably, phosphorus slag is dried to moisture in the preparation method of the modified active phosphorus slag of the embodiment of the present invention
2wt%.The weight content of moisture is as shown in table 2 in specific embodiment phosphorus slag.
Preferably, the temperature of drying described in the preparation method of the modified active phosphorus slag of the embodiment of the present invention is 100-200
DEG C, the drying temperature of specific each embodiment is as shown in table 2.
Preferably, the calcium oxide content in carbide slag described in the preparation method of the modified active phosphorus slag of the embodiment of the present invention
More than or equal to 65wt%, to prepare the industrial residue that acetylene gas obtains；Dioxide-containing silica in the aluminium sulfate slag is
The content of 60%-72wt%, aluminum oxide are 8wt%-15wt%, to prepare the industrial residue that bauxite obtains；Described
Calcium oxide, alchlor and total silica content in red mud are greater than 60wt%, K2O or Na2The content of O is 1wt%-
3wt% obtains industrial residue to refine aluminium oxide；Alchlor content in the aluminous fly-ash is greater than 35wt%, is
Coal-burning power plant's waste discharge gurry；The anhydrous calcium sulphoaluminate mineral are sulphoaluminate cement clinker.
Another embodiment of the invention proposes a kind of modified active phosphoric slag cement, component (by weight percentage) packet
It includes:
Modified active phosphorus slag of the present invention: 30%-50%,
Cement base-material: 50%-70%；Wherein, cement base-material is the cement for not adding modified active phosphorus slag.
The sum of the above components are 100%.
Preferably, the modified active phosphoric slag cement of the embodiment of the present invention, presetting period 1h:30min-6h:30min,
Final setting time is 3h-7h:30min；3d flexural strength is 2.2-4.2MPa, and 28d flexural strength is 6.7-8.6MPa；3d pressure resistance
Degree is 38.8-53.0MPa, and 3d compression strength is 14.8-28.0MPa.
Another embodiment of the invention proposes a kind of modified active phosphorus slag concrete, component (by weight percentage)
Include:
Modified active phosphorus slag of the present invention: 10%-30%,
Concrete base-material: 70%-90%；
The sum of the above components are 100%.
The phosphorus slag chemical component (weight percent/%) of 1 different model of table
" Loss " indicates loss on ignition；
" Σ " indicates the summation of several, forefront chemical component, is a small amount of other impurities less than 100% surplus.
The raw material of 2 embodiment 1-4 modified active phosphorus slag of table forms and preparation parameter
Embodiment 5-11 modified active phosphoric slag cement includes modified active phosphorus slag and cement of the invention；Wherein, each to implement
Example modified active phosphoric slag cement component (weight percent meter) as shown in table 3, prepares phosphorus slag model used in modified active phosphorus slag,
Activator and phosphorus slag weight ratio are as shown in table 3；The component of activator in embodiment 5-11 are as follows: 60 parts of carbide slag, aluminum sulfate
10 parts of slag, 10 parts of red mud, 20 parts of gypsum.
Comparative example 1-7 is phosphoric slag cement, including cement base-material and phosphorus slag, the phosphorus slag are not modified activation, phosphorus used
The model of slag, comparative example 1-7 phosphoric slag cement component (weight percent meter) are as shown in table 4.
The specific surface area of embodiment 5-11 modified active phosphoric slag cement and comparative example 1-7 phosphoric slag cement is 350m2/kg。
The embodiment of the present invention is identical with cement base-material used in comparative example, is same cement.
3 5-11 modified active phosphoric slag cement of table composition
4 comparative example 1-7 phosphoric slag cement of table composition
| Phosphorus slag model | Phosphorus slag/% | Cement/% | |
| Comparative example 1 | A | 30 | 7 |
| Comparative example 2 | A | 50 | 50 |
| Comparative example 3 | B | 30 | 70 |
| Comparative example 4 | B | 40 | 60 |
| Comparative example 5 | B | 50 | 50 |
| Comparative example 6 | C | 50 | 50 |
| Comparative example 7 | D | 50 | 50 |
By GB/T 17671 " Test method for strength of hydraulic cement mortar (ISO method) " and " the cement normal consistency water of GB/T 1346
Amount, setting time and the stability method of inspection " method detection embodiment 5-11 modified active phosphoric slag cement and comparative example 1-7
The physical property of phosphoric slag cement, test result are as shown in table 5.
The quantitative measurement result of table 5 embodiment 5-11 modified active phosphoric slag cement and comparative example 1-7 phosphoric slag cement
By table 4 and table 5 it is found that the setting time of the modified active phosphoric slag cement of embodiment 5-11 is compared to comparative example 1-7
Phosphoric slag cement setting time is obviously shortened, and modified active phosphorus slag volume is higher in cement, and improved effect is more obvious；Meanwhile water
Mud early stage and later strength also have different degrees of raising.
The components by weight percent of embodiment 12-26 modified active phosphoric slag cement are as follows: modified active phosphorus slag 50%, cement base-material
50%.Wherein, phosphorus slag model used in the modified active phosphorus slag in embodiment 12-26, activator and phosphorus slag weight ratio, activator
The weight ratio of each component is as shown in table 6.
The composition of 6 embodiment 12-26 modified active phosphoric slag cement of table
By GB/T 17671 " Test method for strength of hydraulic cement mortar (ISO method) " and GB/T 1346 " cement setting time and peace
Qualitative reaction method " method detection embodiment 12-26 modified active phosphoric slag cement physical property, test result such as table 7
It is shown.
7 embodiment 12-26 modified active phosphoric slag cement quantitative measurement of table
By table 7 as it can be seen that changing as activator component matches, the physical property of final modified active phosphoric slag cement has
Change in various degree, the compression strength of finally obtained modified active phosphoric slag cement and setting time meet cement standard, implement
The content of modified active phosphorus slag is 50wt% in example 12-26 modified active phosphoric slag cement, illustrates that industrial phosphorus slag can prepare water
It is largely used when mud, achievees the purpose that turn waste into wealth；Meanwhile modified active agent of the invention swashs reactivity of phosphor slag as shown in Table 7
Send out effect stability.
Embodiment 27
The component (by weight percentage) of the modified active phosphorus slag concrete of the present embodiment are as follows: 10% embodiment 1 changes
Property activation phosphorus slag, 90% concrete base-material.
Embodiment 28
The component (by weight percentage) of the modified active phosphorus slag concrete of the present embodiment are as follows: 30% embodiment 1 changes
Property activation phosphorus slag, 70% concrete base-material.
Comparative example 8
The component (by weight percentage) of the phosphorus slag concrete of this comparative example are as follows: 30%A type phosphorus slag, 70% coagulation soil matrix
Material, wherein phosphorus slag is without modified active.
Comparative example 9
The component (by weight percentage) of the clinker powder concrete of this comparative example are as follows: 30% pulverized slag, 70% concrete
Base-material.
Embodiment 27,28, comparative example 8, the concrete base-material as raw material in comparative example 9 prepared by portland cement and
, the components by weight percent of all concrete base-materials of embodiment and comparative example are as follows: 370 parts of portland cements, 829 parts of sands, 659 parts
10-20mm stone, 355 parts of 5-10mm stones, 4 parts of additives, 175 parts of water.
It is tested by GB/T50082-2009 " Standard for test methods of longterm performance and durability of ordinary concrete standard " shrinkage
Detection method form 100mm × 100mm × 515mm concrete sample, testing example 27,28 modified active phosphorus slag concrete,
8 phosphorus slag concrete of comparative example, 9 clinker powder concrete of comparative example and embodiment 22,28, concrete base-material used in comparative example 8,9
Physical property, test result is as shown in table 8.
The quantitative measurement result of each concrete of table 8
| 7d shrinking percentage | 28d shrinking percentage | 90d shrinking percentage | |
| Embodiment 27 | 3.78×10-5 | 1.80×10-4 | 3.88×10-4 |
| Embodiment 28 | 3.69×10-5 | 1.84×10-4 | 3.69×10-4 |
| Comparative example 8 | 6.99×10-5 | 3.63×10-4 | 6.48×10-4 |
| Comparative example 9 | 4.85×10-5 | 1.98×10-4 | 5.57×10-4 |
| Concrete base-material | 3.5×10-5 | 1.9×10-4 | 4.47×10-4 |
As shown in Table 8, embodiment 27,28 modified active phosphorus slag concrete examination each age contract with dry rate of body compare slag powder concrete
Contract with dry rate is small, and the concrete examination body prepared with neat portland cement is close or even 90 days its contract with dry rate compare neat portland cement
The concrete examination body of preparation is also small；And the concrete shrinkage for adulterating the modified active phosphorus slag of 30wt% is smaller, it follows that preparation
Modified active phosphorus slag of the invention can largely be added when concrete, achieve the purpose that turn waste into wealth.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (8)
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