CN115321898A - High-performance composite mineral admixture and preparation method thereof - Google Patents
High-performance composite mineral admixture and preparation method thereof Download PDFInfo
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- CN115321898A CN115321898A CN202210799258.7A CN202210799258A CN115321898A CN 115321898 A CN115321898 A CN 115321898A CN 202210799258 A CN202210799258 A CN 202210799258A CN 115321898 A CN115321898 A CN 115321898A
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 68
- 239000011707 mineral Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 186
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011574 phosphorus Substances 0.000 claims abstract description 50
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 50
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 39
- 239000010959 steel Substances 0.000 claims abstract description 39
- 238000003723 Smelting Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000004568 cement Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 49
- 238000005286 illumination Methods 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical group [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 6
- 229940044172 calcium formate Drugs 0.000 claims description 6
- 235000019255 calcium formate Nutrition 0.000 claims description 6
- 239000004281 calcium formate Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000007580 dry-mixing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011398 Portland cement Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 24
- 239000004567 concrete Substances 0.000 abstract description 11
- 238000002474 experimental method Methods 0.000 abstract description 9
- 230000005284 excitation Effects 0.000 abstract description 7
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 239000003469 silicate cement Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009436 residential construction Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
Abstract
The invention discloses a preparation method of a high-performance composite mineral admixture, which is characterized in that production raw materials comprise composite industrial smelting slag, and the composite industrial smelting slag comprises the following components in percentage by mass: 45-55 parts of phosphorus slag of the granulating electric furnace, 15-25 parts of lithium slag and 15-25 parts of steel slag. The advantages are that: the invention firstly proposes that composite industrial smelting slag consisting of granulated electric furnace phosphorus slag, lithium slag and steel slag is used as a production raw material of the high-performance composite mineral admixture; experiments show that when the material is used as a cement admixture, the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace can form an obvious synergistic excitation promoting effect, and the activity performance and the flow performance of the concrete material are obviously improved.
Description
Technical Field
The invention relates to the technical field of concrete mineral admixtures, in particular to a concrete composite mineral admixture.
Background
With the increase of national infrastructure, industrial and residential construction, the use amount of cement, granulated blast furnace slag powder, fly ash and other building cementing materials is increased. However, although many areas in China have very large requirements for mineral admixtures, the yields of the representative mineral admixtures such as granulated blast furnace slag powder and fly ash are low, so that the market requirements are difficult to meet, and the mineral admixtures need to be transported from other areas. Although the method meets the requirement of construction engineering on mineral admixture to a certain extent, the method has the problems of raw material impurity, large performance fluctuation, difficult guarantee of supply quantity and supply continuity, high transportation cost and the like.
Although various large industrial smelting slag is produced in many areas, the process is similar to the forming process of granulating blast furnace slag as a typical mineral admixture raw material, and the slag has hydration activity after the processes of high-temperature calcination, quenching and the like, thereby meeting the basic requirements for preparing the concrete mineral admixture. The bulk industrial smelting slag is prepared into mineral admixture, so that the problem of insufficient granulated blast furnace slag powder and fly ash can be effectively solved. However, because of the unique metallurgical slag phase and chemical composition, the powder formed by processing has special properties and partial poor physical and chemical properties, and is difficult to directly form a concrete mineral admixture product.
Therefore, how to overcome the defect of using bulk industrial smelting slag as a mineral admixture and develop a high-performance composite mineral admixture is a technical problem to be solved in the field.
Disclosure of Invention
The invention provides a preparation method of a high-performance composite mineral admixture, which aims to improve the physicochemical property of bulk industrial smelting slag as the mineral admixture.
The technical scheme adopted by the invention is as follows: the preparation method of the high-performance composite mineral admixture is characterized in that production raw materials comprise composite industrial smelting slag, and the composite industrial smelting slag comprises the following components in percentage by mass: 45-55 parts of phosphorus slag of the granulating electric furnace, 15-25 parts of lithium slag and 15-25 parts of steel slag.
As will be readily understood by those skilled in the art, the granulated electric furnace phosphorus slag refers to the slag discharged after yellow phosphorus is produced by an electric furnace method and subjected to water quenching.
As a further improvement of the invention, the production raw material formula comprises the following components in percentage by mass: 90 parts of composite industrial smelting slag, 5-10 parts of cement clinker, 0.5-1 part of early strength agent, 0.08-0.1 part of water reducing agent and 0.03-0.05 part of early strength grinding aid.
As a further improvement of the invention, the granulated electric furnace phosphorus slag meets the following requirements: the maximum particle size is not more than 50mm, the mass fraction of particles with the particle size of 10-50 mm is not more than 5 percent, P 2 O 5 The mass fraction is less than or equal to 2 percent, the mass coefficient K is more than or equal to 1.2, the glass phase in the physical phase is more than or equal to 85 percent, and the internal illumination index I Ra Less than or equal to 1.3, and external illumination index I γ Less than or equal to 1.3. The activity performance of the powder processed by the phosphorus slag of the granulating electric furnace is influenced by the water quenching degree and the physical and chemical composition, the scheme requires that the maximum particle size of the phosphorus slag of the granulating electric furnace is not more than 50mm, the mass fraction of particles with the particle size of 10-50 mm is not more than 5 percent, and the glass phase in the phosphorus slag phase is not less than 85 percent, thereby ensuring the high water quenching degree and the high water-submersible activity of the phosphorus slag. The activity performance of the phosphorus slag of the granulating electric furnace is influenced by active components such as calcium oxide, magnesium oxide, aluminum oxide and the like on the chemical composition, the invention requires that the mass coefficient K of the used phosphorus slag is more than or equal to 1.2, and the hydration activity of the phosphorus slag is effectively ensured on the chemical composition. The soluble phosphorus in the phosphorus slag can greatly prolong the setting time of the cement-based material slurry. The phosphorus slag used in the invention is required to have the phosphorus pentoxide content less than or equal to 2.0, so that the negative effect of the phosphorus slag is effectively controlled. Because the phosphorus slag used as the raw material phosphate rock has high radioactivity generally, the invention requires the phosphorus slag internal radiation index I Ra Less than or equal to 1.3, and external illumination index I γ Less than or equal to 1.3, the prepared composite mineral admixture can meet the requirement of building material radionuclide limitation GB6566-2010 on performance radioactivity, and the phosphorus slag range capable of being recycled is expanded.
Wherein, the mass coefficient K can be calculated according to the following formula:
in the formula, w CaO -mass fraction of calcium oxide in the phosphorous slag,%;
w MgO -mass fraction of magnesium oxide in the phosphorous slag,%;
As a further improvement of the invention, the lithium slag is a byproduct lithium slag of a lithium smelting process by a sulfuric acid method, and the lithium slag meets the following requirements: siO 2 2 +Al 2 O 3 Is more than or equal to 65 percent, SO 3 Mass fraction less than or equal to 7.0%, water requirement less than or equal to 110%, internal contrast index I Ra Not more than 0.8, and external illumination index I γ Less than or equal to 0.8. The lithium slag used in the scheme is the lithium slag by-product of the sulfuric acid process lithium smelting, and the lithium slag has better activity compared with the lithium slag obtained by-product of the alkaline process. SiO of the lithium slag 2 +Al 2 O 3 The content is more than or equal to 65 percent, and SiO is 2 And Al 2 O 3 The content of the active component is required to be the content of the active component of the lithium slag, so that the active performance of the composite mineral admixture is effectively ensured. The invention requires SO 3 The content is less than or equal to 7.0 percent, and on the one hand, SO in the lithium slag can be volatilized 3 The excitation effect on the phosphorus slag and the steel slag, and on the other hand, the SO in the lithium slag can be avoided 3 Too high content of the compound causes stability problem. The invention requires that the water requirement ratio of the lithium slag is less than or equal to 110 percent, and can control the negative influence of the lithium slag on the fluidity of the composite mineral admixture. The invention requires the internal illumination index I of the lithium slag Ra Not more than 0.8, and external illumination index I γ Less than or equal to 0.8, and provides conditions for qualified radioactivity of the composite mineral admixture.
As a further improvement of the invention, the steel slag is obtained by a hot stuffy method treatment process, and meets the following requirements: free calcium oxide mass fraction less than or equal to 4.0%, SO 3 Mass fraction is less than or equal to 4.0 percent, and internal illumination index I Ra Not more than 0.5, and external illumination index I γ Less than or equal to 0.5. The steel slag used in the scheme is treated by a hot disintegration method, free calcium oxide and free magnesium oxide in the steel slag are fully digested, and the stability is higherGood and better steel slag activity. The invention requires that the content of free calcium oxide is less than or equal to 4.0 percent, and SO 3 The content is less than or equal to 4.0 percent, and the risk of poor stability of the steel slag is reduced. The invention requires the internal illumination index I of the lithium slag Ra Not more than 0.5, and external illumination index I γ Less than or equal to 0.5, and provides conditions for qualified radioactivity of the composite mineral admixture.
As a further improvement of the invention, the cement clinker is silicate cement clinker, and satisfies the following conditions: c 3 S mass fraction is more than or equal to 50%, C 3 S+C 2 The mass fraction of S is more than or equal to 66 percent, the 3d compressive strength is more than or equal to 26.0MPa, and the 28d compressive strength is more than or equal to 52.5MPa. The technical scheme adopts the silicate cement clinker as the early strength component and the strength excitation component of the composite mineral admixture. C in clinker 3 S and C 2 The S has hydraulicity, not only can form better strength, but also the calcium hydroxide generated after hydration has alkali excitation effect on the phosphorus slag and the lithium slag, and the addition of the cement clinker is beneficial to better exciting the activity of the phosphorus slag and the lithium slag, promoting the forming strength of the phosphorus slag and the lithium slag and improving the early activity performance of the composite mineral admixture. It C 3 The S content is more than or equal to 50% because of C 3 S is hydrated quickly and can form better strength in the early stage. The invention requires C 3 S+C 2 S is more than or equal to 66 percent, and the cement clinker can form enough calcium hydroxide after hydration.
As a further improvement of the invention, the water reducing agent is a polycarboxylic acid solid powder water reducing agent, the water content is less than or equal to 5 percent, and the water reducing rate is more than or equal to 35 percent; the early strength agent is calcium formate powder with the particle size less than 1 mm; the grinding aid is a Xika early strength grinding aid. The scheme requires that the used water reducing agent is a polycarboxylate water reducing agent, because the polycarboxylate water reducing agent has good compatibility, the problem of poor adaptability caused by the application of the complex mineral admixture is avoided. The invention requires that the polycarboxylate superplasticizer is in a powder state and has the water content of less than or equal to 5 percent, so that the polycarboxylate superplasticizer is more uniformly distributed in the complex mineral admixture in the subsequent process, and the solid polycarboxylate superplasticizer can effectively improve the fluidity of the complex mineral admixture and ensure that the fluidity ratio of the solid polycarboxylate superplasticizer is more than or equal to 105 percent. And the calcium formate is used as an early strength agent of the composite mineral admixture, can play a role in promoting cement hydration and improving early strength, and is beneficial to improving the early activity of the composite mineral admixture. The Xika early-strength grinding aid can effectively improve the grinding efficiency of each raw material and save the production cost.
The preparation method of the high-performance composite mineral admixture can be implemented according to the following steps:
s1, respectively drying phosphorus slag, lithium slag and steel slag of a granulating electric furnace until the water content is less than or equal to 1%;
s2, weighing the raw materials according to the formula of the production raw materials;
s3, mixing the dried granulated electric furnace phosphorus slag with a part of early strength grinding aid, and grinding the mixture until the specific surface area is 500-600 m 2 /kg；
S4, grinding the dried lithium slag to the specific surface area of 450-600 m 2 /kg；
S5, mixing the dried steel slag with a part of early strength grinding aid, and grinding the mixture to a specific surface area of 600-800 m 2 /kg；
S6, mixing the cement clinker with the rest early strength grinding aid, and grinding the mixture to a specific surface area of 500-700 m 2 /kg；
And S7, uniformly mixing the powder obtained by grinding the powder of S3-S6 with an early strength agent and a water reducing agent in a dry mixing manner to obtain the high-performance composite mineral admixture.
The invention also discloses a high-performance complex mineral admixture which is prepared by the preparation method of the high-performance complex mineral admixture.
The invention has the beneficial effects that: the invention firstly proposes that composite industrial smelting slag consisting of granulated electric furnace phosphorus slag, lithium slag and steel slag is used as a production raw material of the high-performance composite mineral admixture; experiments show that when the material is used as a cement admixture, the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace can form an obvious synergistic excitation promoting effect, and the activity performance and the flow performance of the concrete material are obviously improved.
Detailed Description
The present invention is further illustrated by the following examples.
The first embodiment is as follows:
the composite mineral admixture is prepared according to the following steps:
s1, weighing the raw materials according to a production raw material formula in the following mass proportion: 90 portions of composite industrial smelting slag and cement clinker (Portland cement clinker, C) 3 S mass fraction of 60%, C 3 S+C 2 The mass fraction of S is 72%, the 3d compressive strength is 31.0MPa, the 28d compressive strength is 54.5MPa, the early strength agent (calcium formate powder with the particle size less than 1 mm) is 0.5 part, the water reducing agent (polycarboxylic acid solid powder water reducing agent, the water content is 4.2%, the water reducing rate is 41%) is 0.1 part, and the early strength grinding aid (Xika early strength grinding aid) is 0.04 part; the composite industrial smelting slag is prepared from granulated electric furnace phosphorus slag (the maximum particle size is not more than 50mm, the mass fraction of particles with the particle size within the range of 10-50 mm is 4.2 percent, and P 2 O 5 The mass fraction of (1.8%), the mass coefficient K =1.3, the glass phase in the physical phase is 87%, and the internal illumination index I Ra =1.1, external illumination index I γ = 1.0) and lithium slag (lithium slag, siO by-product of sulfuric acid process lithium smelting process 2 +Al 2 O 3 Is 70% of SO 3 6.5 percent of mass fraction, 110 percent of water demand ratio and internal illumination index I Ra 0.6, an external illumination index I γ 0.6) and steel slag (steel slag obtained by a hot-disintegration method treatment process, wherein the mass fraction of free calcium oxide is 3.0 percent, and SO 3 The mass fraction is 0.3 percent, and the internal contrast index I Ra Is 0.2, and has an external illumination index I γ 0.2) according to the mass ratio of 5; the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace are respectively dried until the water contents are respectively 0.7%, 0.4% and 0.8%;
s2, mixing the dried granulated electric furnace phosphorus slag with 0.02 part of early strength grinding aid, and grinding the mixture to a specific surface area of 550m 2 /kg；
S3, grinding the dried lithium slag into powder with the specific surface area of 500m 2 /kg；
S4, mixing the dried steel slag with 0.01 part of early strength grinding aid, and grinding the mixture until the specific surface area is 650m 2 /kg；
S5, mixing the cement clinker with the rest early strength grinding aid, and grinding the mixture until the specific surface area is 550m 2 /kg；
And S6, uniformly mixing the powder obtained by grinding the S2-S5 powder with an early strength agent and a water reducing agent in a dry mixing manner to obtain the composite mineral admixture.
The second embodiment:
the composite mineral admixture is prepared according to the following steps:
s1, weighing the raw materials according to the following mass ratio of a production raw material formula: 90 portions of composite industrial smelting slag and cement clinker (Portland cement clinker, C) 3 S mass fraction of 60%, C 3 S+C 2 The mass fraction of S is 72 percent, the 3d compressive strength is 31.0MPa, the 28d compressive strength is 54.5 MPa) 10 parts, the early strength agent (calcium formate powder with the grain diameter less than 1 mm) is 0.5 part, the water reducing agent (polycarboxylic acid solid powder water reducing agent, the water content is 4.2 percent, the water reducing rate is 41 percent) is 0.1 part, and the early strength grinding aid (Xika early strength grinding aid) is 0.04 part; the composite industrial smelting slag is prepared from granulated electric furnace phosphorus slag (the maximum particle size is not more than 50mm, the mass fraction of particles with the particle size within the range of 10-50 mm is 4.2 percent, and P 2 O 5 The mass fraction of (1.8%), the mass coefficient K =1.3, the glass phase in the phase of matter is 87%, and the internal illumination index I Ra =1.1, external illumination index I γ = 1.0) and lithium slag (SiO, lithium slag by-product of sulfuric acid process lithium smelting process 2 +Al 2 O 3 Is 70% of SO 3 6.5 percent of mass fraction, 110 percent of water demand ratio and internal contrast index I Ra Is 0.6, and has an external illumination index I γ 0.6) and steel slag (steel slag obtained by a hot-disintegration method treatment process, wherein the mass fraction of free calcium oxide is 3.0 percent, and SO 3 The mass fraction is 0.3 percent, and the internal contrast index I Ra Is 0.2, and has an external illumination index I γ 0.2) according to the mass ratio of 50; the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace are respectively dried until the water contents are respectively 0.6%, 0.9% and 0.6%;
s2, mixing the dried granulated electric furnace phosphorus slag with 0.03 part of early strength grinding aid, and grinding the mixture until the specific surface area is 600m 2 /kg；
S3, grinding the dried lithium slag to a specific surface area of 550m 2 /kg；
S4, mixing the dried steel slag with 0.01 part of early strength grinding aid, and grinding the mixture to a specific surfaceProduct of 650m 2 /kg；
S5, mixing the cement clinker with the rest early strength grinding aid, and grinding the mixture to a specific surface area of 550m 2 /kg；
And S6, uniformly mixing the powder obtained by grinding the S2-S5 powder with an early strength agent and a water reducing agent in a dry mixing manner to obtain the composite mineral admixture.
Example three:
the composite mineral admixture is prepared according to the following steps:
s1, weighing the raw materials according to the following mass ratio of a production raw material formula: 90 portions of composite industrial smelting slag and cement clinker (Portland cement clinker, C) 3 S mass fraction of 60%, C 3 S+C 2 The mass fraction of S is 72%, the 3d compressive strength is 31.0MPa, the 28d compressive strength is 54.5 MPa), the early strength agent (calcium formate powder with the particle size less than 1 mm) is 0.5, the water reducing agent (polycarboxylic acid solid powder water reducing agent, the water content is 4.2%, the water reducing rate is 41%) is 0.1, and the early strength grinding aid (Xika early strength grinding aid) is 0.04; the composite industrial smelting slag is prepared from granulated electric furnace phosphorus slag (the maximum particle size is not more than 50mm, the mass fraction of particles with the particle size within the range of 10-50 mm is 4.2 percent, and P 2 O 5 The mass fraction of (1.8%), the mass coefficient K =1.3, the glass phase in the physical phase is 87%, and the internal illumination index I Ra =1.1, external illumination index I γ = 1.0) and lithium slag (SiO, lithium slag by-product of sulfuric acid process lithium smelting process 2 +Al 2 O 3 Is 70% of SO 3 6.5 percent of mass fraction, 110 percent of water demand ratio and internal contrast index I Ra Is 0.6, and has an external illumination index I γ 0.6 percent) and steel slag (the steel slag obtained by the hot disintegration method treatment process contains 3.0 percent of free calcium oxide and SO 3 The mass fraction is 0.3 percent, and the internal contrast index I Ra Is 0.2, and has an external illumination index I γ Is 0.2) comprises the following components in a mass ratio of 55; the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace are respectively dried until the water content is respectively 0.5%, 0.7% and 0.7%;
s2, mixing the dried granulated electric furnace phosphorus slag with 0.03 part of early strength grinding aid, and grinding the mixture until the specific surface area is 600m 2 /kg；
S3, grinding the dried lithium slag into powder with the specific surface area of 500m 2 /kg；
S4, mixing the dried steel slag with 0.01 part of early strength grinding aid, and grinding the mixture until the specific surface area is 600m 2 /kg；
S5, mixing the cement clinker with the rest early strength grinding aid, and grinding the mixture until the specific surface area is 550m 2 /kg；
And S6, uniformly mixing the powder obtained by grinding the S2-S5 powder with an early strength agent and a water reducing agent in a dry mixing manner to obtain the composite mineral admixture.
Comparative example one:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the composite industrial smelting slag only contains one component of granulated electric furnace phosphorus slag. The formula of the production raw materials is as follows: 90 parts of composite industrial smelting slag (all granulated electric furnace phosphorus slag), 10 parts of cement clinker, 0.5 part of early strength agent, 0.1 part of water reducing agent and 0.04 part of early strength grinding aid. All raw materials were in the same batch as in example one.
And collecting the obtained composite mineral admixture to be tested.
Comparative example two:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the composite industrial smelting slag only contains one component of lithium slag. The formula of the production raw materials is as follows: 90 parts of composite industrial smelting slag (all lithium slag), 10 parts of cement clinker, 0.5 part of early strength agent, 0.1 part of water reducing agent and 0.04 part of early strength grinding aid. All raw materials were the same batch as in example one.
And collecting the obtained composite mineral admixture to be tested.
Comparative example three:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the composite industrial smelting slag only contains one component of steel slag. The formula of the production raw materials is as follows: 90 parts of composite industrial smelting slag (all steel slag), 10 parts of cement clinker, 0.5 part of early strength agent, 0.1 part of water reducing agent and 0.04 part of early strength grinding aid. All raw materials were in the same batch as in example one.
And collecting the obtained complex mineral admixture for testing.
Comparative example four:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the granulated electric furnace phosphorous slag P 2 O 5 3.0 percent, the mass coefficient K is 1.0, the content of glass phase is 80 percent, and the internal illumination index I Ra Is 1.6, and has an external illumination index I γ Is 1.3; the lithium slag SiO 2 +Al 2 O 3 The content is 65 percent, and the water demand ratio is 120 percent; the content of free calcium oxide in the steel slag is 4.0 percent, and the content of SO in the steel slag is 4.0 percent 3 Content of 1.0%, internal illumination index I Ra Is 0.5, and has an external illumination index I γ Is 0.5. The cement clinker C 3 S content 50%, C 3 S+C 2 70 percent of S, 28.0MPa of 3d compressive strength and 53.5MPa of 28d compressive strength.
And collecting the obtained composite mineral admixture to be tested.
Comparative example five:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the composite industrial smelting slag comprises granulated electric furnace phosphorus slag, lithium slag and steel slag according to the mass ratio of 50.
And collecting the obtained complex mineral admixture for testing.
Comparative example six:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: the composite industrial smelting slag comprises granulated electric furnace phosphorus slag, lithium slag and steel slag according to the mass ratio of 50.
And collecting the obtained complex mineral admixture for testing.
Comparative example seven:
this comparative example is a control experiment of example one, conducted according to the same procedures, materials and conditions as example one, except that: powder ratio table obtained in steps S3-S6The areas are respectively as follows: 450m 2 /kg、450m 2 /kg、400m 2 /kg、350m 2 /kg。
And collecting the obtained composite mineral admixture to be tested.
Detecting the performance of the composite mineral admixture:
according to appendix A of JG/T486-2015 composite admixture for concrete, the mass ratio of cement to the composite mineral admixture of each example and each comparative example is 7. The results are shown in Table 1.
TABLE 1 table of the test results of the performance of the complex mineral admixtures
As can be seen from the first to third examples in Table 1, the concrete slurry blended with the complex mineral admixture of the present invention has a 7d/28d activity index stabilized at 80%/107% or more and a fluidity ratio stabilized at 105% or more, and thus it is found that it has excellent activity and fluidity and meets the radioactivity requirement.
As can be seen from comparison of example one with comparative example one, comparative example two and comparative example three in Table 1, when the granulated electric furnace phosphorous slag, lithium slag or steel slag is used as the industrial smelting slag, respectively, the 28d activity indexes of the concrete slurry are 94%,106% and 81%, respectively; according to calculation, under the premise that the total usage amount of industrial smelting slag is not changed, the phosphorus slag, the lithium slag and the steel slag of the electric furnace are combined and used according to the proportion of 2 in the first embodiment 5, the theoretical value of the 28d activity index of the concrete slurry is 94%, and the actual value measured in the first embodiment is 109%, so that the actual 28d activity index is far higher than the theoretical value, and the phosphorus slag, the lithium slag and the steel slag of the granulating electric furnace have obvious synergistic effect of improving the activity performance of the concrete slurry when being used in a combined mode, and the reason is related to the mutual excitation effect among the components.
As can be seen from the first example and the fourth comparative example, the raw materials (high phosphorus slag emission and high water demand ratio of lithium slag) which are not in accordance with the requirements of the invention have poorer comprehensive properties when being used for preparing the composite mineral admixture. As can be seen from the first embodiment, the fifth embodiment and the sixth embodiment, the complex mineral admixture which is not prepared according to the mixture ratio of the invention has the problems of low activity index and low fluidity, and may cause insufficient mutual excitation among industrial smelting slags. As can be seen from the first and seventh examples, the mineral composite admixture prepared by using the specific surface area lower than that specified in the present invention has a problem of low activity index.
Claims (10)
1. The preparation method of the high-performance composite mineral admixture is characterized in that production raw materials comprise composite industrial smelting slag, and the composite industrial smelting slag comprises the following components in percentage by mass: 45-55 parts of phosphorus slag of the granulating electric furnace, 15-25 parts of lithium slag and 15-25 parts of steel slag.
2. The method for preparing the high-performance complex mineral admixture according to claim 1, wherein the production raw material formula comprises the following components in percentage by mass: 90 parts of composite industrial smelting slag, 5-10 parts of cement clinker, 0.5-1 part of early strength agent, 0.08-0.1 part of water reducing agent and 0.03-0.05 part of early strength grinding aid.
3. The method for preparing the high-performance complex mineral admixture according to claim 2, wherein the method comprises the following steps: the granulated electric furnace phosphorus slag meets the following requirements: the maximum particle size is not more than 50mm, the mass fraction of particles with the particle size of 10-50 mm is not more than 5 percent, P 2 O 5 The mass fraction is less than or equal to 2 percent, the mass coefficient K is more than or equal to 1.2, the glass phase in the physical phase is more than or equal to 85 percent, and the internal illumination index I Ra Not more than 1.3, external illumination index I γ ≤1.3。
4. The method for preparing the high-performance complex mineral admixture according to claim 3, wherein the method comprises the following steps: the mass coefficient K is calculated according to the following formula:
in the formula, w CaO -mass fraction of calcium oxide in the phosphorous slag,%;
w MgO -mass fraction of magnesium oxide in the phosphorous slag,%;
5. The method of preparing a high performance mineral complex admixture according to claim 2, characterized in that: the lithium slag is a byproduct of a sulfuric acid method lithium smelting process, and meets the following requirements: siO 2 2 +Al 2 O 3 Mass fraction of not less than 65%, SO 3 Mass fraction is less than or equal to 7.0%, water demand ratio is less than or equal to 110%, internal illumination index I Ra Not more than 0.8, and external illumination index I γ ≤0.8。
6. The method for preparing the high-performance complex mineral admixture according to claim 2, wherein the method comprises the following steps: the steel slag is obtained by a hot-disintegrating method treatment process and meets the following requirements: mass fraction of free calcium oxide is less than or equal to 4.0 percent, and SO 3 Mass fraction less than or equal to 4.0%, internal contrast index I Ra Not more than 0.5, and external illumination index I γ ≤0.5。
7. The method for preparing a high-performance complex mineral admixture according to any one of claims 2 to 6, characterized in that: the cement clinker is formed by portland cement clinkerAnd (b) materials, and satisfies: c 3 S mass fraction is more than or equal to 50%, C 3 S+C 2 The mass fraction of S is more than or equal to 66 percent, the 3d compressive strength is more than or equal to 26.0MPa, and the 28d compressive strength is more than or equal to 52.5MPa.
8. The method for preparing a high-performance complex mineral admixture according to any one of claims 2 to 6, characterized in that: the water reducing agent is a polycarboxylic acid solid powder water reducing agent, the water content is less than or equal to 5 percent, and the water reducing rate is more than or equal to 35 percent; the early strength agent is calcium formate powder with the particle size less than 1 mm; the grinding aid is a Xika early strength grinding aid.
9. The process for the preparation of the high performance mineral complex admixture according to any one of claims 2 to 6, characterized in that it comprises the steps of:
s1, respectively drying phosphorus slag, lithium slag and steel slag of a granulating electric furnace until the water content is less than or equal to 1%;
s2, weighing the raw materials according to the formula of the production raw materials;
s3, mixing the dried granulated electric furnace phosphorus slag with a part of early strength grinding aid, and grinding the mixture until the specific surface area is 500-600 m 2 /kg；
S4, grinding the dried lithium slag to a specific surface area of 450-600 m 2 /kg；
S5, mixing the dried steel slag with a part of early strength grinding aid, and grinding the mixture until the specific surface area is 600-800 m 2 /kg；
S6, mixing the cement clinker with the rest early strength grinding aid, and grinding the mixture until the specific surface area is 500-700 m 2 /kg；
And S7, uniformly mixing the powder subjected to grinding processing of S3-S6 with an early strength agent and a water reducing agent in a dry mixing manner to obtain the high-performance composite mineral admixture.
10. A high performance complex mineral admixture obtained by the method of producing a high performance complex mineral admixture according to any one of claims 1 to 9.
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