CN115093150A - Modifier for improving setting and hardening performance and carbonization resistance of phosphogypsum-based cementing material - Google Patents
Modifier for improving setting and hardening performance and carbonization resistance of phosphogypsum-based cementing material Download PDFInfo
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- CN115093150A CN115093150A CN202210803781.2A CN202210803781A CN115093150A CN 115093150 A CN115093150 A CN 115093150A CN 202210803781 A CN202210803781 A CN 202210803781A CN 115093150 A CN115093150 A CN 115093150A
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- Prior art keywords
- phosphogypsum
- modifier
- mineral
- magnesium
- cementing material
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- 239000000463 material Substances 0.000 title claims abstract description 95
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 94
- 239000003607 modifier Substances 0.000 title claims abstract description 65
- 238000003763 carbonization Methods 0.000 title claims abstract description 37
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 58
- 239000011707 mineral Substances 0.000 claims abstract description 58
- 238000006703 hydration reaction Methods 0.000 claims abstract description 34
- 230000036571 hydration Effects 0.000 claims abstract description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000001238 wet grinding Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000010755 mineral Nutrition 0.000 claims description 56
- 239000004568 cement Substances 0.000 claims description 29
- 239000011083 cement mortar Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011398 Portland cement Substances 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- -1 modified phosphogypsum powder/modified phosphogypsum Chemical class 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000003469 silicate cement Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 12
- 229910001653 ettringite Inorganic materials 0.000 abstract description 8
- 230000015271 coagulation Effects 0.000 abstract description 7
- 238000005345 coagulation Methods 0.000 abstract description 7
- 229910052599 brucite Inorganic materials 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 5
- 229910003023 Mg-Al Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 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
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- 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)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a phosphogypsum-based gelling material modifier, which comprises an Mg-Al double hydroxide radical hydration phase (brucite) formed in situ by promoting self hydration of a gelling material. The modifier is prepared from a calcium-based alkali activator, an active calcium siliceous mineral admixture, an active aluminum siliceous mineral admixture, a magnesium raw material and an early strength agent by a mixing wet milling method, and can be used for replacing the alkali activator part of the common phosphogypsum-based cementing material. The modifier can improve the carbonization resistance of the matrix by promoting the matrix to generate brucite in situ; meanwhile, the combined action of the magnesium raw material and the active silica-alumina raw material promotes the generation of non-expansive ettringite and the improvement of the polymerization degree of C-A-S-H gel, and is beneficial to improving the coagulation hardening performance of the matrix.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a modifier for improving the setting and hardening performance and the carbonization resistance of a phosphogypsum-based cementing material by promoting the cementing material to hydrate to form brucite.
Background
The phosphogypsum as the solid waste generated by producing the phosphoric acid by the wet method has higher impurity content and application performance far inferior to that of other byproduct gypsum, so the utilization rate is lower, and the total accumulation amount worldwide exceeds 40 hundred million tons. In order to reduce land resources occupied by large accumulation of phosphogypsum and the maintenance cost of a storage yard, reduce the risk of polluting soil and underground water by impurity release and realize low-cost, large-dosage and high-performance application of the phosphogypsum, the application of the phosphogypsum has become a research hotspot at home and abroad.
In a plurality of application fields, the technology of replacing portland cement with the over-sulfur phosphogypsum cementing material and applying the over-sulfur phosphogypsum cementing material to partial infrastructure and cement products is highly emphasized, and the carbon emission and energy consumption brought by the traditional portland cement production are greatly reduced while the phosphogypsum is utilized in a large amount. The phosphogypsum-based cementing material is based on the design idea of a full-solid waste cementing material, and the proportion of each component can be adjusted according to different application environments so as to achieve the purpose of regulating and controlling the strength development of the phosphogypsum-based cementing material. By taking the cementing material with the design label of 42.5 as an example, the mass proportion of the phosphogypsum can be improved to 40 percent or more by adjusting the phase proportion of each phase. However, because the impurities of fluorine and phosphorus in the phosphogypsum are high, the phosphogypsum can be dissolved out in a hydration stage to cause serious delayed coagulation, and the setting time and the strength development of a matrix can be greatly different according to the difference of the impurity content in the phosphogypsum of each batch and the difference of the doping amount of the phosphogypsum designed by a cementing material; in addition, because the phosphogypsum-based cementing material is an ettringite-based cementing material, the system has low alkalinity and is easy to carbonize, and the surface is easy to generate ash in natural environment, thereby seriously limiting the application range of the phosphogypsum-based cementing material.
CN102745924A discloses a phosphogypsum modification method for shortening the setting time of phosphogypsum-based cement concrete, i.e. the aim of precipitating impurities is achieved by adding a small amount of steel slag, mineral powder and phosphogypsum for mixing and wet grinding, however, the over-sulfur phosphogypsum cementing material prepared by the method still shows longer setting time. CN114230301A discloses a phosphogypsum hardener, a preparation method and an application thereof, wherein the hardener is only suitable for engineering environments with lower requirements on the strength grade of a cementing material, such as road base layers and the like, and the application space is limited. CN107056115A discloses a set accelerating type early strength agent for phosphogypsum-based cementing material and a preparation method thereof, the early strength agent is prepared by calcining and other processes, the process is complicated, and compared with the hydration of mineral admixtures, the early strength agent is easy to influence the later strength development when the early performance is regulated and controlled by an inorganic admixture, i.e. the later strength growth rate is slowed down or even reversed, and the mixing amount needs to be accurately controlled. CN102249580A discloses a method for improving the carbonization resistance of phosphogypsum-based cement, which improves the carbonization resistance of a matrix by directly introducing magnesium hydroxide, shows better carbonization resistance, but the simple addition of a magnesium raw material can affect the coagulation hardening of the matrix in the early stage of hydration, and the development of early strength is poor; in addition, for the over-sulfur phosphogypsum cementing material, namely the low-alkalinity cementing material, if the content of the magnesium hydroxide is too high, the calcium hydroxide in the pore solution is lack, and the calcium hydroxide directly reacts with the silicate to generate magnesium gel, so that the gel structure of the matrix is damaged. Therefore, how to improve the carbonization resistance and the strength development through a simple and effective means needs to be further explored.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modifier for a phosphogypsum-based cementing material, which accelerates the setting and hardening of the phosphogypsum-based cementing material and improves the carbonization resistance by promoting the self-hydration of the cementing material to form brucite. The modifier can effectively shorten the setting time of the phosphogypsum-based cementing material and improve the strength development and self carbonization resistance of each age.
The technical scheme adopted by the invention for solving the problems is as follows:
a modifier for improving the setting and hardening performance and the carbonization resistance of a phosphogypsum-based cementing material consists of mineral components and a hydration accelerator; the mineral components comprise, by mass, 50-80% of a calcium-based alkali excitant, 10-30% of an active calcium siliceous mineral admixture and 10-20% of an active aluminum siliceous mineral admixture; the hydration promoter comprises a magnesium raw material and an early strength agent; wherein, the magnesium raw material is divided into I type and II type.
In the scheme, the I-type magnesium raw material mainly exists in the form of solid powder, and comprises one or more of magnesium hydroxide, dead-burned magnesium oxide, light-burned magnesium oxide and the like; the class II magnesium raw material exists in the solution mainly in the form of magnesium ions and is introduced by mixing the solution with a cement-based material, and comprises magnesium salt solution (such as magnesium nitrate solution), seawater, brine and the like.
In the scheme, when the I-type magnesium raw material is used, the I-type magnesium raw material and the early strength agent in the hydration accelerator are respectively 12-30% and 1-3% of the total mass of the mineral components.
In the scheme, when the II-type magnesium raw material is used, magnesium salt solutions such as magnesium nitrate solution and the like can be directly adopted or brine, seawater and the like can be directly obtained, wherein the concentration of magnesium ions is not more than 0.2 mol/L. The II-class magnesium raw material directly replaces tap water to be used in the preparation process of the phosphogypsum-based cementitious material cement mortar, and the I-class magnesium raw material does not need to be added.
In the scheme, the early strength agent comprises triethanolamine, triisopropanolamine and the like, and is chemically pure.
In the scheme, the calcium-based alkali activator comprises ordinary portland cement, portland cement or cement clinker, is calcined, dehydrated and the like, and has the strength grade of 42.5 or 52.5.
In the scheme, the active calcium-aluminum admixture comprises S95-grade and above mineral powder, I-grade fly ash and the like, and the specific surface area is 400-500 m 2 /kg。
In the scheme, the active silica-alumina admixture comprises metakaolin, calcined coal gangue, red mud and the like, wherein the oxide component (SiO) is 2 +Al 2 O 3 +Fe 2 O 3 ) Is more than 70 percent.
According to the preparation method of the phosphogypsum-based cementing material modifier, the mineral components and the hydration promoter are mixed according to the proportion, and are subjected to wet grinding for 10-20 min for direct use, or can be dried for use and stored. Wherein the recommended water-solid ratio value in the wet grinding process is between 0.3 and 0.5.
On the basis of the phosphogypsum-based cementing material modifier, the invention also provides phosphogypsum-based cementing material cement mortar which comprises a cementing material, water and quartz sand, wherein the weight ratio of the quartz sand to the cementing material is within the range of 2-4, and the weight ratio of the water to the cementing material is within the range of 0.3-0.5; the cementing material comprises 30-50% of modified phosphogypsum, 35-60% of mineral admixture and 5-15% of phosphogypsum-based cementing material modifier according to the mass percentage, and the sum of the weight percentages of the modified phosphogypsum, the mineral admixture and the phosphogypsum-based cementing material modifier is 100%. The 28-day compressive strength range of the phosphogypsum-based cementitious material cement mortar is 20-60 MPa.
According to the preparation method of the phosphogypsum-based cementing material cement mortar, modified phosphogypsum, mineral admixture (preferably mineral powder and the like), modifier, quartz sand and water are respectively weighed according to the formula amount of the phosphogypsum-based cementing material cement mortar, and are poured into a planetary mortar stirrer to be stirred for 2-5 minutes and then are uniformly mixed. Wherein, if the modified phosphogypsum and the modifier are both slurry-like substances obtained after wet grinding, the water consumption in the wet grinding process needs to be deducted according to the designed water-cement ratio in the stirring process. In areas with proper conditions, the magnesium material in the modifier can be introduced by II magnesium raw materials such as seawater or brine, and the preparation of the modifier and the preparation of cement and mortar are mixed by seawater (or brine) without adding I magnesium raw materials.
In the scheme, the preparation method of the modified phosphogypsum comprises the following steps: according to the mass percentage, uniformly mixing or wet grinding 94-96% of phosphogypsum and 4-6% of precipitator for 20-40 min, and aging for 8-24 h to obtain the modified phosphogypsum powder/modified phosphogypsum slurry. Wherein, the precipitator can be selected from common silicate or silicate cement and clinker, calcined dehydration phase, quicklime, steel slag, carbide slag and the like.
The main technical concept of the invention is as follows:
1) compared with the modifier obtained by compounding one or more of cement, clinker, quick lime, steel slag, sodium hydroxide, sodium silicate and the like, the modifier provided by the invention is added with an active alumino-silicate mineral admixture, namely metakaolin, coal gangue or red mud, and under the double effects of wet grinding and an early strength agent, the active alumino-silicate mineral admixture is quickly dissolved in the early stage of hydration to provide aluminate and silicate, the cement hydration is promoted, the formation of early ettringite and gel is accelerated, and the setting time is effectively shortened; the hydration promoting effect is continuously promoted, aluminate is transferred into the gel, the polymerization degree of the gel is improved, the impermeability of the matrix is enhanced, and more ettringite is generated. The generation of ettringite and gel can further optimize the pore size distribution of the matrix and increase the compactness, which is also beneficial to delaying the invasion of carbon dioxide. The phosphogypsum-based cementing material prepared by the modifier can effectively promote early coagulation and hardening of a matrix.
2) The magnesium raw material in the modifier consumes a part of hydroxide radicals in the early hydration stage of the phosphogypsum cementing material, improves the content of calcium ions in a pore solution, and inhibits the phosphogypsum from further dissolving in a hydration induction period, thereby delaying the redissolution of impurities in the phosphogypsum and accelerating the occurrence of a hydration acceleration period. The generation of a Mg-Al double hydroxide radical structure hydration phase (brucite) in the phosphogypsum-based gelling material is promoted by inducing hydration reactions of cement, mineral admixtures and magnesium raw materials, the layered structure has a 'caging effect' on carbonate ions thermodynamically, on one hand, impurities such as free phosphorus, fluorine and the like which hinder coagulation hardening can be contained in a layer, on the other hand, carbonate which causes carbonization can be filled in the interlayer 'cage', the concentration of carbonate in a pore solution is effectively reduced, the aim of improving the carbonization resistance of the phosphogypsum-based gelling material is fulfilled, the coagulation hardening of the phosphogypsum-based gelling material is accelerated, and the risk of carbonization of the hardened gelling material is reduced. In addition, the hydration of the magnesium ions participating in the cementing material can improve the hydration degree of the mineral powder and promote the generation of ettringite.
3) The modified phosphogypsum, the mineral admixture and the cementing material prepared by the modifier take ettringite as a main hydration product, and have the characteristics of micro-expansion performance and small shrinkage; the matrix with high phosphogypsum content has good sulfate corrosion resistance, and expansion ettringite can not be generated to cause matrix cracking. The phosphogypsum-based cementing material not only maintains the advantages of a gypsum cementing material, but also has high strength, impermeability and water resistance, and mortar prepared by the cementing material has low density, excellent sound insulation performance, easy construction, good fireproof performance and high strength.
Compared with the prior art, the invention has the following advantages:
1) the modifier can effectively reduce the delayed coagulation effect of the cementing material caused by soluble fluorine and phosphorus in the phosphogypsum, shortens the initial setting time and the final setting time, and can regulate and control the setting time and the strength development of each age by regulating the proportion of the active silicon-aluminum phase admixture in the modifier and the proportion of the modifier in the cementing material.
2) The introduction of the magnesium raw material in the modifier can effectively increase the development of the strength in the later stage of hydration, the 28d strength can even reach about 50MPa, brucite is generated by guiding the self-hydration form of the cementing material to improve the carbonization resistance of the low-alkalinity phosphogypsum cementing material, and the cost is lower.
3) The modifier can improve the water resistance and chemical stability of the phosphogypsum-based cementing material.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the present invention are described below in conjunction with the following examples, which are included merely to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention.
In the following examples, the active calcium-aluminum admixture is mineral powder of S95 grade or above, and the specific surface area is 400-500 m 2 Per kg; the active silica-alumina admixture is one of metakaolin and calcined gangue and an oxide component (SiO) 2 +Al 2 O 3 +Fe 2 O 3 ) Is more than 70 percent.
Example 1
An ardealite-based gelling material modifier consists of mineral components and a hydration accelerator; the hydration accelerator comprises magnesium nitrate and triethanolamine; wherein, the consumption of the magnesium raw material and the triethanolamine is respectively 20 percent and 1 percent of the total mass of the mineral components; the mineral components comprise 60% of P.II.42.5 cement, 22% of mineral powder and 18% of coal gangue in percentage by mass.
The preparation method of the phosphogypsum-based cementing material modifier comprises the following steps: placing cement, mineral powder, coal gangue and magnesium nitrate into a horizontal ceramic ball milling tank according to the mass ratio of 50:18:15:17, adjusting the water-solid ratio and the ball-material ratio to be 1/2 and 6/1 respectively, then adding triethanolamine, wherein the mass of the triethanolamine accounts for 1 percent of the total mass of the mineral components (namely the cement, the mineral powder and the coal gangue), and carrying out mixing wet milling for 20min to obtain the phosphogypsum-based cementing material modifier.
The modified phosphogypsum slurry is obtained by the following steps: undisturbed phosphogypsum; mineral powder: the steel slag is placed in a horizontal ceramic ball milling tank according to the mass ratio of 94:2:4, the water-solid ratio and the ball material ratio are respectively adjusted to 1/2 and 6/1, and the steel slag is mixed, wetly milled for 30min and aged for 12 h.
The common phosphogypsum-based cementing material consists of modified phosphogypsum slurry, mineral powder and an alkali activator, and the modifier prepared in example 1 is adopted in the embodiment to mainly replace the alkali activator. Therefore, this example provides a phosphogypsum-based cementitious material cement mortar, which is obtained by the following steps: modified phosphogypsum slurry, mineral powder, alkali activator (modifier prepared in example 1), water and standard sand are mixed according to the mixing ratio in the table 2, and the water-to-gel ratio and the gel-to-sand ratio are respectively 0.5 and 1/3. And carrying out a comparison test on the alkali activator in the phosphogypsum-based cementing material cement mortar by adopting cement, and mixing according to the mixing ratio shown in the table 1.
Measuring the standard consistency of the cementitious material cement mortar according to GB/T1346-2011 'inspection method for water consumption, setting time and stability of cement standard consistency', and testing the setting time of the cementitious material cement mortar under standard curing conditions; forming according to GB 17671-1999 method for detecting cement mortar strength, and testing the mortar strength after curing under standard conditions; baking the 28 d-cured mortar sample at 60 ℃ for 48 hours according to T0581-2020 Cement concrete carbonization test method, and then placing at 20 ℃ and CO 2 The strength was measured after carbonization for 7 days in a carbonization chamber with a concentration of 20% and a relative humidity of 70%.
TABLE 1 influence of cement mixing amount on setting hardening and anti-carbonization properties of cementitious materials cement mortar
TABLE 2 EXAMPLE 1 Effect of modifier loading on setting hardening and carbonation resistance of cementitious materials Cement mortars
Example 2
An ardealite-based gelling material modifier consists of mineral components and a hydration accelerator; the hydration accelerator comprises light burned magnesium oxide and triethanolamine; wherein the consumption of the magnesium raw material and the triethanolamine is respectively 13.6 percent and 1 percent of the total mass of the mineral components; the mineral components comprise 68.2% of P.II.42.5 cement, 20.4% of mineral powder and 11.4% of metakaolin in percentage by mass.
The preparation method of the phosphogypsum-based cementing material modifier comprises the following steps: placing cement, mineral powder, metakaolin and light-burned magnesium oxide in a horizontal ceramic ball milling tank according to the mass ratio of 60:18:10:12, adjusting the water-solid ratio and the ball-material ratio to be 1/2 and 6/1 respectively, adding triethanolamine, wherein the mass of the triethanolamine accounts for 1 percent of the mass of mineral components (namely the cement, the mineral powder and the coal gangue), and carrying out mixing and wet milling for 20 min.
The modified phosphogypsum slurry is obtained by the following steps: undisturbed phosphogypsum; mineral powder: the steel slag is placed in a horizontal ceramic ball milling tank according to the mass ratio of 94:2:4, the water-solid ratio and the ball material ratio are respectively adjusted to 1/2 and 6/1, and the steel slag is mixed, wetly milled for 30min and aged for 12 h.
The embodiment provides phosphogypsum-based cementitious material cement mortar, which is obtained by the following steps: the modified phosphogypsum slurry, the composite mineral powder, the modifier prepared in example 2, water and sand are mixed according to the mixing ratio shown in Table 3, the water-cement ratio and the mortar-glue ratio are respectively 0.5 and 1/3, wherein the composite mineral powder has the specific surface area of 400m 2 Kg and 800m 2 The mixture of the mineral powder and the additive is mixed according to the proportion of 4: 1.
Measuring the standard consistency of the cementing material cement mortar according to GB/T1346-2011' method for testing water consumption, setting time and stability of standard consistency of cementTesting the setting time of the cementing material cement mortar under the condition; forming according to GB 17671-1999 method for detecting cement mortar strength, and testing the mortar strength after curing under standard conditions; baking the 28 d-cured mortar sample at 60 ℃ for 48h according to T0581-2020 Cement concrete carbonation test method, and placing the baked mortar sample at 20 ℃ and CO 2 The strength was measured after carbonization for 7d in a carbonization chamber with a concentration of 20% and a relative humidity of 70%. The test results were as follows:
TABLE 3 influence of cement mixing amount on setting hardening and anti-carbonization properties of cementitious materials cement mortar
TABLE 4 EXAMPLE 2 Effect of modifier loading on setting hardening and carbonation resistance of cementitious materials Cement mortars
From the test results in tables 1-4, it can be seen that the cement is adopted as the alkali activator to have a negative effect on the setting and hardening of the phosphogypsum-based cementing material, and with the increase of the doping amount, although the early setting and hardening performance is better, the later strength development is slow, and the carbonization resistance is poorer. Compared with a cement mortar sample which only uses cement as an alkali activator, the cement mortar sample prepared under the condition of doping 7-13% of the modifier instead of cement in the embodiment 1 and the same doping amount shortens the initial setting time and the final setting time of the sample doped with 7% of the modifier by 18.1% and 15.2%, increases the strength of each age by 4.3%, 7.2%, 16.0%, 19.1% and 11.9%, and increases the compressive strength after 7d carbonization by 35.1%; the initial setting time and the final setting time of a sample doped with 9% of the modifier are respectively shortened by 17.9% and 14.1%, the strength of each age period is respectively increased by 16.4%, 27.8%, 28.3%, 36.8% and 37.9%, and the compressive strength after 7d carbonization is increased by 46.4%; the initial setting time and the final setting time of a sample doped with 11% of the modifier are respectively shortened by 14.5% and 13.9%, the strength of each age period is respectively increased by 36.1%, 47.8%, 69.6%, 53.0% and 48.2%, and the compressive strength after 7d carbonization is increased by 86.6%; the initial setting time and the final setting time of a sample doped with 13 percent of the modifier are respectively shortened by 8.1 percent and 16.4 percent, the strength of each age period is respectively increased by 39.7 percent, 68.9 percent, 73.4 percent, 58.7 percent and 55.0 percent, and the compressive strength after 7 days of carbonization is increased by 93.3 percent. Therefore, the longer the curing age is, the more obvious the enhancement effect of the modifier on the strength of the sample is; and when the mixing amount of the modifier is larger, the enhancing effect on the strength and the anti-carbonization performance is better.
Compared with a cement mortar sample which only uses cement as an alkali activator, the cement mortar sample prepared under the condition of doping 7-13% of the modifier in the embodiment 2 to replace the cement has the advantages that the initial setting time and the final setting time of the sample doped with 7% of the modifier are respectively shortened by 4.8% and 5.1%, the 28d strength and the 180d strength are respectively increased by 6.7% and 17.9%, and the compressive strength after 7d carbonization is increased by 25.8%; the initial setting time and the final setting time of a sample doped with 9% of the modifier are respectively shortened by 4.2% and 3.2%, the strength of 7d, 28d and 180d is respectively increased by 2.1%, 18.1% and 13.1%, and the compressive strength after 7d carbonization is increased by 43.9%; the initial setting time and the final setting time of a sample doped with 11% of the modifier are respectively shortened by 3.9% and 7.4%, the strength of 7d, 28d and 180d is respectively increased by 22.9%, 33.7% and 27.1%, and the compressive strength after 7d carbonization is increased by 56.4%; the initial setting time and the final setting time of the sample doped with 13 percent of modifier are respectively shortened by 7.0 percent and 6.1 percent; the strength of 7d, 28d and 180d is respectively increased by 32.5%, 46.4% and 41.4%, and the compressive strength after 7d carbonization is increased by 67.9%. In example 2, the modifier has a negative effect on the 3d strength because the modifier has a poor early modification effect on the sample, because the gradually hydrated magnesium oxide will continuously affect the precipitation efficiency of impurities in phosphogypsum compared with soluble magnesium ions, and the inhibition effect on the alkalinity increase of the pore solution is more obvious, so that the hydration of the mineral admixture is delayed, the crystallization-precipitation rate of the hydration product is reduced, the setting time is prolonged, and the early strength is slowly developed; the longer the curing age is, the more obvious the strength is enhanced by the modifier; and when the mixing amount of the modifier is larger, the enhancing effect on the strength and the anti-carbonization performance is better.
The above-mentioned embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to implement the same, and the present invention shall not be limited to the embodiments, i.e. the equivalent changes or modifications made within the spirit of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. A modifier for improving the setting and hardening performance and the anti-carbonization performance of a phosphogypsum-based gelling material is characterized by consisting of a mineral component and a hydration accelerator; the mineral components comprise, by mass, 50-80% of a calcium-based alkali excitant, 10-30% of an active calcium siliceous mineral admixture and 10-20% of an active aluminum siliceous mineral admixture; the hydration accelerator comprises a magnesium raw material and an early strength agent, wherein the consumption of the magnesium raw material and the consumption of the early strength agent are respectively 12-30% and 1-3% of the total mass of mineral components; wherein, the magnesium raw material is one or more of magnesium hydroxide, dead burned magnesium oxide and light burned magnesium oxide.
2. A modifier for improving the setting and hardening performance and the anti-carbonization performance of a phosphogypsum-based gelling material is characterized by consisting of mineral components and a hydration accelerator; the mineral components comprise, by mass, 50-80% of a calcium-based alkali excitant, 10-30% of an active calcium siliceous mineral admixture and 10-20% of an active aluminum siliceous mineral admixture; the hydration promoter comprises a magnesium raw material and an early strength agent; the magnesium raw material is one or more of magnesium salt solution, seawater and brine, and the concentration of magnesium ions is not more than 0.2 mol/L.
3. The modifier for improving the setting and hardening performance and the carbonization resistance of the phosphogypsum-based cementing material according to claim 1 or 2, characterized in that the early strength agent is one or two of triethanolamine and triisopropanolamine.
4. The modifier for improving the setting and hardening performance and the carbonization resistance of the phosphogypsum-based cementing material according to claim 1 or 2, characterized in that the calcium-based alkali activator comprises one or more of silicate or ordinary portland cement, clinker and calcined dehydrated phase; the active calcium-aluminum admixture comprises one or more of S95-grade and above mineral powder and I-grade fly ash, and the specific surface area is 400-500 m 2 Per kg; the active silica-alumina admixture comprises one or more of metakaolin, calcined coal gangue and red mud, wherein the oxide component (SiO) is 2 +Al 2 O 3 +Fe 2 O 3 ) Greater than 70%.
5. The preparation method of the phosphogypsum-based gelling material modifier according to claim 1, which is characterized in that the mineral component and the hydration accelerator are mixed according to the proportion of claim 1 and then wet-milled for 10-20 min to obtain the phosphogypsum-based gelling material modifier; wherein the water-solid ratio in the wet grinding process is between 0.3 and 0.5.
6. The phosphogypsum-based cementitious material cement mortar is characterized by comprising a cementitious material, water and quartz sand, wherein the weight ratio of the quartz sand to the cementitious material is within the range of 2-4, and the weight ratio of the water to the cementitious material is within the range of 0.3-0.5; the cementing material comprises 30 to 50 percent of modified phosphogypsum slurry, 35 to 60 percent of mineral admixture and 5 to 15 percent of modifier of claim 1 or 2 by weight percent, and the sum of the weight percent of the modified phosphogypsum slurry and the modifier is 100 percent; the mineral admixture comprises 85-95% of calcium-silicon mineral admixture and 5-15% of aluminum-silicon mineral admixture in percentage by mass.
Wherein, when the modifier is the modifier of claim 1, water is introduced through the magnesium raw material in a liquid form without additionally introducing water.
7. The phosphogypsum-based cementitious material cement mortar according to claim 6, characterized in that the preparation method of the modified phosphogypsum is as follows: according to the mass percentage, uniformly mixing or wet grinding 94-96% of phosphogypsum and 4-6% of precipitator for 20-40 min, and aging for 8-24 h to obtain the modified phosphogypsum powder/modified phosphogypsum slurry.
8. The phosphogypsum-based cementitious material cement mortar as claimed in claim 7, wherein the precipitant is selected from one or more of silicate or ordinary silicate cement, clinker, calcined dehydrated phase, quicklime, steel slag, mineral powder and carbide slag.
9. The preparation method of the phosphogypsum-based cementing material cement mortar of claim 6, which is characterized in that according to the formula amount of the phosphogypsum-based cementing material cement mortar, modified phosphogypsum, mineral admixture, modifier, quartz sand and water are respectively weighed and poured into a planetary mortar mixer to be mixed for 2-5 minutes to be mixed uniformly; wherein, if the modified phosphogypsum and the modifier are both slurry-like substances obtained after wet grinding, the water consumption in the wet grinding process needs to be deducted according to the designed water-cement ratio in the stirring process.
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