CN115093150B - Modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing material - Google Patents
Modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing material Download PDFInfo
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- CN115093150B CN115093150B CN202210803781.2A CN202210803781A CN115093150B CN 115093150 B CN115093150 B CN 115093150B CN 202210803781 A CN202210803781 A CN 202210803781A CN 115093150 B CN115093150 B CN 115093150B
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- phosphogypsum
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- cementing material
- magnesium
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 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 82
- 239000003607 modifier Substances 0.000 title claims abstract description 60
- 238000003763 carbonization Methods 0.000 title claims abstract description 41
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 54
- 239000011707 mineral Substances 0.000 claims abstract description 54
- 238000006703 hydration reaction Methods 0.000 claims abstract description 35
- 230000036571 hydration Effects 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001238 wet grinding Methods 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 235000010755 mineral Nutrition 0.000 claims description 52
- 239000004568 cement Substances 0.000 claims description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 21
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000011398 Portland cement Substances 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 229910001653 ettringite Inorganic materials 0.000 abstract description 8
- 229910052599 brucite Inorganic materials 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910003023 Mg-Al Inorganic materials 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 150000001669 calcium Chemical class 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000011083 cement mortar Substances 0.000 description 23
- 238000002156 mixing Methods 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 230000018109 developmental process Effects 0.000 description 11
- 230000001976 improved effect Effects 0.000 description 11
- 238000012360 testing method Methods 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
- 239000002893 slag Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 239000004576 sand Substances 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 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
- 238000004090 dissolution Methods 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
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000003469 silicate cement Substances 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 modified phosphogypsum powder/modified phosphogypsum Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 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
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 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
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000009413 insulation Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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 an phosphogypsum-based cementing material modifier, which comprises a Mg-Al double hydroxide hydration phase (brucite) formed in situ by promoting the self hydration of the cementing material. The modifier is prepared from a calcium-based alkali-activated agent, an activated calcium siliceous mineral admixture, an activated aluminum siliceous mineral admixture, a magnesium raw material and an early strength agent by a mixed wet grinding method, and can be used for replacing the alkali-activated agent part of a common phosphogypsum-based cementing material. The modifier achieves the effect of improving the carbonization resistance of the matrix by promoting the matrix to generate brucite in situ; meanwhile, the combined action of the magnesise:Sub>A raw material and the active aluminosilicate raw material can promote the generation of the non-expansive ettringite and the improvement of the polymerization degree of the C-A-S-H gel, thereby being beneficial to improving the setting and 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 setting and hardening properties and carbonization resistance of phosphogypsum-based cementing materials by promoting the self hydration of the cementing materials to form brucite.
Background
The phosphogypsum is used as solid waste generated in the wet process phosphoric acid production, and the application performance of the phosphogypsum is far lower than that of other byproduct gypsum due to the higher impurity content, so that the utilization rate is lower, and the total stacking amount in the world is over 40 hundred million tons. In order to reduce the land resources occupied by the large-scale accumulation of phosphogypsum and the maintenance cost of a storage yard, and reduce the risk of releasing impurities to pollute soil and underground water, the low-cost, large-doping and high-performance application of phosphogypsum is becoming a research hot spot at home and abroad.
In various application fields, a technology that the over-sulfur phosphogypsum cementing material replaces silicate cement and is applied to partial infrastructure and cement products is highly valued, and the technology greatly reduces carbon emission and energy consumption caused by the traditional silicate cement production while utilizing a large amount of phosphogypsum. The phosphogypsum-based cementing material is based on the design thought of the 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. Taking the cementing material with the design number of 42.5 as an example, the mass ratio of phosphogypsum can be improved to 40% or more by adjusting the proportion of each phase. However, because the fluorine and phosphorus impurities in phosphogypsum are higher, serious retarding effect is caused by dissolution in the hydration stage, and the coagulation time and strength development of the matrix are greatly different according to the difference of the impurity content in phosphogypsum of each batch and the difference of the mixing amount of phosphogypsum designed by the cementing material; in addition, because the phosphogypsum-based cementing material is an ettringite-based cementing material, the system alkalinity is lower, the system is easy to carbonize, the surface is easy to ash in the natural environment, and the application range of the phosphogypsum-based cementing material is severely limited.
CN102745924a discloses a phosphogypsum modification method for shortening setting time of phosphogypsum-based cement concrete, namely, a small amount of steel slag, mineral powder and phosphogypsum are added to be mixed and wet-ground to achieve the purpose of precipitating impurities, however, the polysulfide phosphogypsum cementing material prepared by the method still shows longer setting time. CN114230301a discloses an phosphogypsum hardener, a preparation method and application thereof, and the hardener is only suitable for engineering environments with low requirements on the strength grade of the cementing material, such as road base and the like, and has limited application space. CN107056115a discloses a accelerating early strength agent for phosphogypsum-based cementing materials 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 admixture, the early strength development is easily influenced by the regulation and control of the early performance by inorganic admixture, namely the later strength growth rate is slowed down and even is inverted, and the doping amount needs to be accurately controlled. According to the method for improving the carbonization resistance of phosphogypsum-based cement disclosed in CN102249580A, the carbonization resistance of a matrix is improved by directly introducing magnesium hydroxide, and the carbonization resistance is better, however, the simple doping of magnesium raw materials can affect the coagulation hardening of the matrix in early stage of hydration, and the early strength development is poor; in addition, if the magnesium hydroxide is excessively high in the low-alkalinity cementing material such as the over-sulfur phosphogypsum cementing material, the magnesium hydroxide is directly reacted with silicate to generate magnesium gel under the condition of lacking calcium hydroxide in the pore solution, so that the cementing structure of the matrix is damaged. Therefore, further research is needed on how to improve the carbonization resistance and strength development by a simple and effective means.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the modifier for the phosphogypsum-based cementing material, which accelerates the setting and hardening of the phosphogypsum-based cementing material and improves the carbonization resistance by promoting the hydration of the cementing material to form brucite. The modifier can effectively shorten the setting time of phosphogypsum-based cementing materials and improve the strength development and self carbonization resistance of each age.
The invention adopts the technical proposal for solving the problems that:
a modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing materials comprises mineral components and hydration accelerators; the mineral components comprise, by mass, 50% -80% of a calcium-based alkali-activated agent, 10% -30% of an activated calcium siliceous mineral admixture and 10% -20% of an activated aluminum siliceous mineral admixture; the hydration accelerator comprises a magnesia raw material and an early strength agent; wherein, the magnesia raw materials are classified into I class and II class.
In the scheme, the class I magnesia raw material mainly exists in the form of solid powder and comprises one or more of magnesium hydroxide, dead-burned magnesia, light-burned magnesia and the like; the magnesium type II raw material mainly exists in the form of magnesium ions in the solution, is introduced by mixing the solution with the cement-based material, and comprises magnesium salt solution (such as magnesium nitrate solution), seawater, brine and the like.
In the scheme, when the class I magnesium raw material is used, the dosages of the class I 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 class II magnesium raw material is used, magnesium salt solutions such as magnesium nitrate solutions 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 0.2mol/L. The class II magnesia raw material can be directly used for the preparation process of phosphogypsum-based cementing material cement mortar instead of tap water, and class I magnesia raw material is not required 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 or cement clinker, and has the strength grade of 42.5 or 52.5, such as calcination dehydration.
In the scheme, the active calcium aluminum admixture comprises S95 grade or more mineral powder, I grade fly ash and the like, and has a specific surface area of 400-500 m 2 /kg。
In the above scheme, the active aluminosilicate admixture comprises metakaolin, calcined coal gangue, red mud and the like, wherein the oxide component (SiO 2 +Al 2 O 3 +Fe 2 O 3 ) Greater than 70%.
According to the preparation method of the phosphogypsum-based cementing material modifier, the mineral components and the hydration accelerator are mixed according to the proportion, and then wet-milled for 10-20 min for direct use, or dried for use and storage. 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 cementing materials, water and quartz sand, wherein the weight ratio of the quartz sand to the cementing materials is in the range of 2-4, and the weight ratio of the water to the cementing materials is in the range of 0.3-0.5; the cementing material comprises, by mass, 30% -50% of modified phosphogypsum, 35% -60% of mineral admixture and 5% -15% of phosphogypsum-based cementing material modifier, wherein the sum of the weight percentages of the modified phosphogypsum, the mineral admixture and the phosphogypsum-based cementing material modifier is 100%. The 28d compressive strength of the phosphogypsum-based cementing material cement mortar is 20-60 MPa.
According to the formula amount of the phosphogypsum-based cementing material cement mortar, the modified phosphogypsum, the mineral admixture (preferably mineral powder and the like), the modifier, the quartz sand and the water are respectively weighed, and poured into a planetary mortar stirrer to be stirred for 2-5 minutes to be uniformly mixed. If the modified phosphogypsum and the modifier are slurry materials obtained after wet grinding treatment, the water consumption in the wet grinding process is required to be deducted according to the designed water-cement ratio in the stirring process. In the region with proper conditions, the magnesium material in the modifier can be introduced through sea water or bittern and other class II magnesium materials, and sea water (or bittern) is adopted for mixing in the preparation process of the modifier and the preparation process of cement and mortar, so that class I magnesium materials are not required to be added.
In the scheme, the preparation method of the modified phosphogypsum comprises the following steps: uniformly mixing 94-96% of phosphogypsum and 4-6% of precipitant according to mass percent or wet grinding for 20-40 min, and aging for 8-24 h to obtain modified phosphogypsum powder/modified phosphogypsum slurry. Wherein the precipitant can be selected from common silicate or silicate cement, clinker, calcined dehydration phase, quicklime, steel slag, carbide slag, etc.
The main technical concept of the invention is as follows:
1) Compared with the modifier obtained by compounding one or more of cement, clinker, quicklime, steel slag, sodium hydroxide, sodium silicate and the like, the modifier designed by the invention has the advantages that by adding the active aluminosilicate mineral admixture, namely metakaolin, coal gangue or red mud, under the dual effects of wet grinding and early strength agents, aluminate and silicate are quickly dissolved in early hydration stage, cement hydration is promoted, early ettringite and gel are accelerated, and the setting time is effectively shortened; this hydration promoting effect will continue to advance and the aluminate will migrate into the gel, increasing the degree of polymerization of the gel, enhancing the matrix barrier and producing more ettringite. The formation of ettringite and gel further optimizes the matrix pore size distribution, increasing the solidity, which is also beneficial to delay the invasion of carbon dioxide. The phosphogypsum-based cementing material prepared by the modifier can effectively promote early setting and hardening of a matrix.
2) The magnesia raw material existing in the modifier consumes a part of hydroxyl at the early stage of the hydration of the phosphogypsum cementing material, improves the content of calcium ions in the pore solution, and inhibits the further dissolution of phosphogypsum in the hydration induction period, so that the re-dissolution of impurities in the phosphogypsum is delayed, and the hydration acceleration period is accelerated. By inducing hydration reaction of cement, mineral admixture and magnesia raw materials, the generation of a hydration phase (brucite) of a Mg-Al double hydroxide radical structure in the phosphogypsum-based cementing material is promoted, and the layered structure has a 'caging effect' on carbonate ions in thermodynamics, so that free phosphorus, fluorine and other impurities which obstruct setting and hardening can be stored between layers, and carbonate which causes carbonization can be filled into 'cages' between layers, so that the concentration of carbonate in a pore solution is effectively reduced, the purpose of improving the carbonization resistance of the phosphogypsum-based cementing material is achieved, the setting and hardening of the phosphogypsum-based cementing material are accelerated, and the carbonization risk of the hardened cementing material is reduced. In addition, magnesium ions participate in the hydration of the cementing material, so that the hydration degree of mineral powder can be improved, and the formation of ettringite can be promoted.
3) The cementing material prepared by using the modified phosphogypsum, the mineral admixture and the modifier takes ettringite as a main hydration product, and has the characteristics of micro-expansion performance and small contraction; the matrix with high phosphogypsum doping amount has good sulfate erosion resistance, and does not generate expanded ettringite to cause matrix cracking. The phosphogypsum-based cementing material not only maintains the advantages of the gypsum cementing material, but also has high strength, impermeability and water resistance, and the mortar prepared by using the cementing material has the advantages of small 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 phosphogypsum, shorten the initial setting time and the final setting time, and regulate and control the setting time and the development of the strength of each age by adjusting 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 magnesia 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, and the carbonization resistance of the phosphogypsum cementing material with low alkalinity is improved by guiding the self-hydration form of the cementing material to generate brucite, so that the cost is lower.
3) The modifier can improve the water resistance and chemical stability of phosphogypsum-based cementing materials.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, which are provided to further illustrate the features and advantages of the invention, and not to limit the claims of the invention.
In the following embodiment, the activated calcium aluminum admixture is S95 grade ore powder or more, and the specific surface area is 400-500 m 2 /kg; the active aluminosilicate admixture is one of metakaolin and calcined gangue, and the oxide component (SiO 2 +Al 2 O 3 +Fe 2 O 3 ) Greater than 70%.
Example 1
A phosphogypsum-based cementing material modifier consists of a mineral component and a hydration promoter; the hydration accelerator comprises magnesium nitrate and triethanolamine; wherein the dosages of the magnesium raw material and the triethanolamine are 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 by mass percent.
The preparation method of the phosphogypsum-based cementing material modifier comprises the following steps: placing cement, mineral powder, coal gangue and magnesium nitrate in 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% of the total mass of mineral components (namely cement, mineral powder and coal gangue), and mixing and wet milling for 20min to obtain the phosphogypsum-based cementing material modifier.
The modified phosphogypsum slurry is prepared by the following steps: the original phosphogypsum is prepared; 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 be 1/2 and 6/1, and the steel slag is mixed, wet-milled for 30min and aged for 12h.
The common phosphogypsum-based cementing material consists of modified phosphogypsum slurry, mineral powder and alkali-exciting agent, and the modifier prepared in the embodiment 1 is adopted to mainly replace the alkali-exciting agent in the embodiment. Therefore, the embodiment provides phosphogypsum-based cementing material cement mortar, which is prepared by the following steps: the modified phosphogypsum slurry, mineral powder, alkali activator (modifier prepared in example 1), water and standard sand are mixed according to the mixing ratio of Table 2, and the water-gel ratio and the gel-sand ratio are respectively 0.5 and 1/3. And the alkali-activator in the phosphogypsum-based cementing material cement mortar is subjected to a control test by adopting cement, and the alkali-activator is mixed according to the mixing ratio shown in the table 1.
Testing the setting time of the cementing material cement mortar under standard curing conditions after measuring the standard consistency of the cementing material cement mortar according to GB/T1346-2011 method for testing the water consumption, setting time and stability of the cement standard consistency; molding according to GB 17671-1999 'cement mortar strength detection method', and testing mortar strength after curing under standard conditions; drying the 28d cured mortar sample at 60deg.C for 48 hr, and placing at 20deg.C and CO according to T0581-2020 2 The strength was measured after 7d carbonization in a carbonization tank having a concentration of 20% and a relative humidity of 70%.
TABLE 1 influence of Cement Admixture on setting hardening and carbonization resistance of cement mortar as a cementing material
TABLE 2 Effect of modifier addition on setting hardening and carbonization resistance of cement mortar of Cement mortar of cement
Example 2
A phosphogypsum-based cementing material modifier consists of a mineral component and a hydration promoter; the hydration accelerator comprises light burned magnesia and triethanolamine; wherein the dosages of the magnesium raw material and the triethanolamine are 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 by mass percent.
The preparation method of the phosphogypsum-based cementing material modifier comprises the following steps: cement, mineral powder, metakaolin and light burned magnesia are placed in a horizontal ceramic ball milling tank according to the mass ratio of 60:18:10:12, the water-solid ratio and the ball-material ratio are respectively adjusted to be 1/2 and 6/1, and triethanolamine is added, wherein the mass of the triethanolamine accounts for 1% of the mass of mineral components (namely cement, mineral powder and coal gangue), and the mixture is subjected to mixing wet milling for 20min.
The modified phosphogypsum slurry is prepared by the following steps: the original phosphogypsum is prepared; 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 be 1/2 and 6/1, and the steel slag is mixed, wet-milled for 30min and aged for 12h.
The embodiment provides phosphogypsum-based cementing material cement mortar, which is prepared 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 of Table 3, the water cement ratio and the cement sand ratio are respectively 0.5 and 1/3, wherein the specific surface area of the composite mineral powder is 400m 2 Kg and 800m 2 The mineral powder of/Kg is mixed according to the proportion of 4:1.
Testing the setting time of the cementing material cement mortar under standard curing conditions after measuring the standard consistency of the cementing material cement mortar according to GB/T1346-2011 method for testing the water consumption, setting time and stability of the cement standard consistency; molding according to GB 17671-1999 'cement mortar strength detection method', and testing mortar strength after curing under standard conditions; drying the 28d cured mortar sample at 60deg.C for 48 hr, and placing at 20deg.C and CO according to T0581-2020 2 The strength was measured after 7d carbonization in a carbonization tank having a concentration of 20% and a relative humidity of 70%. The test results were as follows:
TABLE 3 influence of Cement Admixture on setting and hardening and carbonization resistance of cement mortar as a cementing material
TABLE 4 Effect of modifier addition on setting hardening and carbonization resistance of cement mortar of Cement mortar of cement
As can be seen from the test results in tables 1 to 4, the simple use of cement as an alkali-activator has a negative effect on setting and hardening of phosphogypsum-based cementing materials, and with the increase of the doping amount, the early setting and hardening performance is better, but the later strength development is slow, the carbonization resistance is poorer, and the later strength development of a matrix can be effectively improved and the better carbonization resistance is shown by using the modifier as the alkali-activator. Compared with a cement mortar sample which only uses cement as an alkali-activated agent, in the cement mortar sample prepared under the condition of the same mixing amount by adding 7% -13% of modifier instead of cement in the embodiment 1, the initial setting time and the final setting time of the sample which are added with 7% of modifier are shortened by 18.1% and 15.2%, the strengths of the respective ages are respectively increased by 4.3%, 7.2%, 16.0%, 19.1% and 11.9%, and the compressive strength after 7d carbonization is increased by 35.1%; the initial setting time and the final setting time of a sample doped with 9% of modifier are respectively shortened by 17.9% and 14.1%, the strength of each age is respectively increased by 16.4%, 27.8%, 28.3%, 36.8% and 37.9%, and the compressive strength after 7d carbonization is improved by 46.4%; the initial setting time and the final setting time of a sample doped with 11% of modifier are respectively shortened by 14.5% and 13.9%, the strength of each age is respectively increased by 36.1%, 47.8%, 69.6%, 53.0% and 48.2%, and the compressive strength after 7d carbonization is improved by 86.6%; the initial setting time and the final setting time of the sample doped with 13% of modifier are respectively shortened by 8.1% and 16.4%, the strength of each age is respectively increased by 39.7%, 68.9%, 73.4%, 58.7% and 55.0%, and the compressive strength after 7d carbonization is improved by 93.3%. The longer the curing age, the more obvious the reinforcing effect of the modifier on the strength of the sample is; and when the blending amount of the modifier is larger, the reinforcing effect on the strength and the carbonization resistance is better.
Compared with a cement mortar sample which uses cement as an alkali-activated agent, in the cement mortar sample prepared under the condition of the same mixing amount by adding 7-13% of modifier instead of cement in the embodiment 2, the initial setting time and the final setting time of the sample which are added with 7% of modifier are respectively shortened by 4.8%, 5.1%, the 28d and 180d strengths are respectively increased by 6.7% and 17.9%, and the compressive strength after 7d carbonization is improved by 25.8%; the initial setting time and the final setting time of the sample doped with the modifier of 9 percent are respectively shortened by 4.2 percent, 3.2 percent, the strengths of 7d, 28d and 180d are respectively increased by 2.1 percent, 18.1 percent and 13.1 percent, and the compressive strength after 7d carbonization is improved by 43.9 percent; the initial setting time and the final setting time of a sample doped with 11% of modifier are respectively shortened by 3.9% and 7.4%, the strength of 7d, 28d and 180d are respectively increased by 22.9% and 33.7% and 27.1%, and the compressive strength after 7d carbonization is improved by 56.4%; the initial setting time and the final setting time of the sample doped with 13% of modifier are respectively shortened by 7.0% and 6.1%; the strength of 7d, 28d and 180d are 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, since the modifier has a poor early modification effect on the sample, the modifier has a negative effect on the 3d strength, since the gradually hydrated magnesium oxide will continuously affect the precipitation efficiency of impurities in phosphogypsum, and the inhibition effect on the increase of the alkalinity of the pore solution is more obvious compared with the soluble magnesium ions, thereby delaying the hydration of the mineral admixture, reducing the crystallization-precipitation rate of hydration products, prolonging the coagulation time and slowing the development of the early strength; the longer the curing age, the more obvious the strength enhancement is by the modifier; and when the blending amount of the modifier is larger, the reinforcing effect on the strength and the carbonization resistance is better.
The above-described embodiments are only for illustrating the technical spirit and features of the present invention, and it is intended that those skilled in the art can understand the content of the present invention and implement it accordingly, and the scope of the present invention is not limited to the embodiments, i.e. equivalent changes or modifications to the spirit of the present invention are still within the scope of the present invention.
Claims (4)
1. A modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing materials is characterized by comprising a mineral component and a hydration accelerator; the mineral component comprises calcium base in mass percent50-80% of alkali-activated agent, 10-30% of active calcium aluminum mineral admixture and 10-20% of active silicon aluminum mineral admixture; the hydration accelerator comprises a magnesium raw material and an early strength agent, wherein the dosages of the magnesium raw material and the early strength agent are respectively 12% -30% and 1% -3% of the total mass of mineral components; wherein the magnesia raw material is one or more of magnesium hydroxide, dead-burned magnesium oxide and light-burned magnesium oxide; oxide component SiO in the active aluminosilicate mineral admixture 2 +Al 2 O 3 +Fe 2 O 3 Greater than 70%;
according to the preparation method of the modifier for improving the setting and hardening properties and the carbonization resistance of the phosphogypsum-based cementing material, mineral components and a hydration accelerator are mixed in proportion and then wet-milled for 10-20 min, so that the modifier for improving the setting and hardening properties and the carbonization resistance of the phosphogypsum-based cementing material is obtained; wherein the water-solid ratio in the wet grinding process is 0.3-0.5;
the active calcium aluminum mineral 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 /kg; the active aluminosilicate mineral admixture comprises one or more of metakaolin, calcined coal gangue and red mud.
2. A modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing materials is characterized by comprising a mineral component and a hydration accelerator; the mineral components comprise, by mass, 50% -80% of a calcium-based alkali-activated agent, 10% -30% of an active calcium aluminum mineral admixture and 10% -20% of an active aluminum mineral admixture; the hydration accelerator comprises a magnesia 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 0.2mol/L; oxide component SiO in the active aluminosilicate mineral admixture 2 +Al 2 O 3 +Fe 2 O 3 Greater than 70%;
the active calcium aluminum mineral 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 /kg; the active aluminosilicate mineral admixture comprisesOne or more of metakaolin, calcined coal gangue and red mud.
3. The modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cementing materials according to claim 1 or 2, wherein the early strength agent is one or two of triethanolamine and triisopropanolamine.
4. A modifier for improving setting and hardening properties and carbonization resistance of phosphogypsum-based cement according to claim 1 or 2, characterized in that the calcium-based alkali activator comprises one or both of portland cement and cement clinker.
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