CN113264751A - Porous material using magnesium solid carbon product as raw material and preparation method thereof - Google Patents
Porous material using magnesium solid carbon product as raw material and preparation method thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 53
- 239000011777 magnesium Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 40
- 239000007787 solid Substances 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 45
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000001723 curing Methods 0.000 claims abstract description 18
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009966 trimming Methods 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract 2
- 238000006297 dehydration reaction Methods 0.000 claims abstract 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 235000010755 mineral Nutrition 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000013007 heat curing Methods 0.000 claims description 6
- 239000011490 mineral wool Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 239000010451 perlite Substances 0.000 claims description 4
- 235000019362 perlite Nutrition 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011494 foam glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012784 inorganic fiber Substances 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 239000003469 silicate cement Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 238000009827 uniform distribution Methods 0.000 claims description 2
- 239000012615 aggregate Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 38
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- 235000012245 magnesium oxide Nutrition 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- -1 bischofite Chemical compound 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- NEKPCAYWQWRBHN-UHFFFAOYSA-L magnesium;carbonate;trihydrate Chemical compound O.O.O.[Mg+2].[O-]C([O-])=O NEKPCAYWQWRBHN-UHFFFAOYSA-L 0.000 description 3
- 230000009919 sequestration Effects 0.000 description 3
- 229910000175 cerite Inorganic materials 0.000 description 2
- 239000011381 foam concrete Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C04B28/30—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 magnesium cements or similar cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
-
- 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
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a porous material taking a magnesium carbon fixation product as a raw material and a preparation method thereof, belonging to the field of building materials and filtering materials. The preparation method of the porous material comprises the steps of taking hydromagnesite, trihydromagnesite, dihydramagnesite or products of partial dehydration of the hydromagnesite as raw materials, mixing the raw materials with water, an auxiliary agent, aggregate, reinforcing fibers and the like, and carrying out molding, curing, demoulding, drying, trimming and board finishing to obtain the porous material with the basic magnesium carbonate as a binding phase and a fine pore structure. According to the invention, in the process of converting the magnesium solid carbon product containing crystal water into basic magnesium carbonate under the action of an auxiliary agent or under a damp-heat condition, the large volume effect caused by phase change does not cause the strong shrinkage of the macroscopic volume of the material, but obtains the light material with high specific strength. The porous material does not contain components such as halide, sulfate and the like, not only has the characteristics of light weight, high strength, non-combustibility, carbon fixation and the like, but also has the advantages of simple and convenient production and the like.
Description
Technical Field
The invention relates to the field of building materials and filter materials, in particular to a porous material taking a magnesium solid carbon product as a raw material and a preparation method thereof.
Background
China CO2The emission amount is the first to jump the world in 2006, and due to the huge carbon emission, the international pressure is borne, and meanwhile, the resource and environment cost is heavy. Reduction of CO2Emission of, to CO2The recycling is a necessary way for the future development of China. From a technical point of view, on CO2The trapping and the sealing are also an effective emission reduction means.
High emission industrial CO2In addition to physical sequestration, which is performed for deep geological structures, capture or chemical sequestration using the mineral carbonation method (MC method) has proven to have great potential. It is estimated that the total carbon sequestration capacity of the MC process can exceed 10 trillion tons for global CO over the next 100 years2The newly increased discharge amount is about 2.3 trillion tons. However, the MC method requires the mineral to be heat treated or ground in advance, and the carbon fixation cost is high. Therefore, the method for preparing the building material by utilizing the carbon fixation product is a good method for solving the cost problem.
In the MC method, the research on magnesium-containing minerals is many, and theoretically 1kg of MgO can cure CO of 1.092kg at most2Above the corresponding value of CaO of 0.785 kg. The magnesium-containing mineral has rich sources, and the carbon fixation product is easy to be applied industrially. The magnesium-containing minerals which can be used for carbon fixation include silicate minerals such as serpentine and forsterite, halides such as bischofite, brucite, and cryptocrystalline or amorphous minerals in basalt (5-12 wt% of MgO). The minerals are widely present in basic-ultrabasic rock pulp and metamorphic rock, tailings, metallurgical slag and salt mine, and are rich in sources. In addition, brineAnd seawater all contain rich Mg2+Also to solidify CO2The important medium of (1).
The main carbon-fixing product of the method is MgCO according to different carbonization conditions3And hydrated magnesium carbonate. The latter of which is commonly known as magnesite trihydrate (MgCO)3·3H2O), periclase [4MgCO ]3·Mg(OH)2·5H2O]And hydromagnesite [4MgCO ]3·Mg(OH)2·4H2O]And the like. The trihydromagnesite is the reaction product of normal temperature and pressure water solution and is also the most easily obtained product. Hydrous magnesium carbonate similar to trihydromagnesite and pentahydromagnesite (MgCO)3·5H2O) and magnesite dihydrate (MgCO)3·2H2O), and their products after removal of part of the water of crystallization [ MgCO ]3·(0.1～1.8)H2O]。
The invention relates to a MgCO solid carbon product containing crystal water magnesium such as magnesite trihydrate3·xH2And O (x is 0.1-1.8, 2, 3 and 5) is used as a raw material, is converted into basic magnesium carbonate which is flaky, mutually staggered and has a hollow or honeycomb structure under specific auxiliary agents and curing conditions, generates a cementing effect and is prepared into the porous material. The porous material has the characteristics of high specific strength and fine pore structure, does not contain components such as halide, sulfate and the like, has the characteristics of light weight, high strength, non-combustibility, carbon fixation and the like, has the advantages of simple and convenient production and the like, can be used as building fireproof materials, heat-insulating wall materials and furniture materials, and can also be used as filtering materials.
Disclosure of Invention
The invention provides a porous material taking a magnesium carbon-fixing product as a raw material and a preparation method thereof, wherein the porous material which can be used as a building material and a filtering material is prepared by utilizing a crystal water-containing magnesium carbon-fixing product such as magnesite trihydrate and the like which are simple and easy to obtain at normal temperature and normal pressure, and an operable method is provided for reducing the carbon-fixing cost.
A porous material taking a magnesium solid carbon product as a raw material is characterized in that: basic magnesium carbonate is used as a cementing phase to combine the aggregate and the reinforced fiber, and the basic magnesium carbonate cementing phase is a magnesium solid carbon product Mg containing crystal waterCO3·xH2And O (x is 0.1-1.8, 2, 3 and 5) is used as a raw material, is converted into basic magnesium carbonate which is flaky, mutually staggered and has a hollow or honeycomb structure under specific auxiliary agents and curing conditions, generates a cementing effect and is prepared into the porous material.
Further, the basic magnesium carbonate is one or a compound of more of cerite, sphenopnesite, hydromagnesite and isohydromagnesite; the aggregate is a light porous material, comprises ceramsite, foam glass particles, expanded vermiculite particles, expanded perlite particles and the like, and has the granularity of 1-10 mm; the reinforcing fiber is organic fiber or inorganic fiber, and comprises paper pulp fiber, cellulose fiber, polyester fiber, glass fiber, mineral wool, rock wool, ceramic fiber, carbon fiber and the like, and the length of the reinforcing fiber is 3-20 mm.
Furthermore, the mass fraction of the alkali type magnesium carbonate cementing phase in the porous material is 40-90%, the mass fraction of the aggregate is 0-50%, and the mass fraction of the reinforcing fiber is 0-10%.
Further, the crystal water-containing magnesium solid carbon product is MgCO3·xH2The formula of O, wherein x is 0.1-1.8, 2, 3 and 5, and comprises minerals such as pentahydromagnesite (x is 5), trihydromagnesite (x is 3), dihydramagnesite (x is 2) and the like or partially dehydrated products thereof (x is 0.1-1.8); the auxiliary agent is a substance capable of promoting the conversion of the magnesium carbon fixation product to basic magnesium carbonate, and comprises light-burned MgO (magnesite), Mg (OH)2Caustic dolomite, lime, silicate cement, and the like; the addition amount of the auxiliary agent is 0-15% of the mass of the magnesium solid carbon product.
The preparation method of the porous material taking the magnesium solid carbon product as the raw material comprises the following specific preparation steps:
s1: the magnesium solid carbon product containing crystal water, the auxiliary agent and water are weighed, mixed and stirred uniformly according to a proportion to form viscous mixed slurry;
s2: adding reinforcing fibers into the mixed slurry for uniform dispersion, and then adding aggregate which is sprayed with water with saturated surface dry water content in advance for mixing to form a mixture with uniform distribution of the fibers, the aggregate and the slurry, wherein the saturated surface dry water content is the water content of the aggregate in a saturated surface dry state;
s3: pouring, or carrying out suction filtration or extrusion molding on the mixture, and carrying out normal-temperature curing or wet-heat curing on the obtained green body after mold locking to obtain a cooked blank;
s4: demoulding the cooked blank, drying at the temperature lower than 170 ℃, and trimming and finishing the board surface to obtain the magnesium porous material.
Further, the addition amount of water in the S1 is 0.1 to 2.0 times of the total mass of the crystallization water-containing magnesium solid carbon product and the auxiliary agent.
Further, the curing in S3 is performed for 0.5h to 28d under the sealed condition of normal temperature to 100 ℃.
The porous material comprises basic magnesium carbonate as a cementing phase to bond the aggregate and the reinforcing fiber together, wherein the basic magnesium carbonate cementing phase is a solid carbon product MgCO containing crystal water and magnesium3·xH2And O (x is 0.1-1.8, 2, 3 and 5) is used as a raw material, is converted into basic magnesium carbonate which is flaky, mutually staggered and has a hollow or honeycomb structure under specific auxiliary agents and curing conditions, generates a cementing effect and is prepared into the porous material. Interestingly, in the process of converting the crystalline water-containing magnesian solid carbon product into basic magnesium carbonate, the large-volume effect caused by the phase change does not cause the strong shrinkage of the macroscopic volume of the material, but obtains the light material with high specific strength.
The technical scheme of the invention has the following beneficial effects:
in the scheme, in the process of converting the crystalline water-containing magnesian solid carbon product into basic magnesium carbonate, the large-volume effect caused by phase change does not cause the strong shrinkage of the macroscopic volume of the material, but obtains the light material with high specific strength and fine pore structure characteristics. The porous material does not contain components such as halide, sulfate and the like, not only has the characteristics of light weight, high strength, non-combustibility, carbon fixation and the like, but also has the advantages of simple and convenient production and the like, can be used as building fireproof materials and heat-insulating wall materials, and can also be used as filtering materials. When the volume density is close, the strength of the porous material is superior to that of aerated concrete and foam concrete, the higher strength of the aerated concrete is obtained by an autoclaved process and high-temperature curing, and the porous material is prepared by normal-temperature curing or normal-pressure wet-heat curing, so that the production process is more energy-saving.
Drawings
FIG. 1 is a schematic flow chart of the production process of the present invention;
FIG. 2 is a graph of the structural features of the bonded phase pore of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a porous material taking a magnesium solid carbon product as a raw material and a preparation method thereof.
The porous material comprises basic magnesium carbonate as a cementing phase to bond the aggregate and the reinforcing fiber together, wherein the basic magnesium carbonate cementing phase is a solid carbon product MgCO containing crystal water and magnesium3·xH2And O (x is 0.1-1.8, 2, 3 and 5) is used as a raw material, is converted into basic magnesium carbonate which is flaky, mutually staggered and has a hollow or honeycomb structure under specific auxiliary agents and curing conditions, generates a cementing effect and is prepared into the porous material. In the process of converting the crystal water-containing magnesium solid carbon product into basic magnesium carbonate, the large volume effect caused by phase change does not cause the strong shrinkage of the macroscopic volume of the material, but obtains the light material with high specific strength and fine pore structure characteristics.
The basic magnesium carbonate as the cementing phase is one or a compound of more of cerite, sphenoprite, hydromagnesite and isohydromagnesite; the aggregate is a light porous material and comprises ceramsite, foam glass particles, expanded vermiculite particles and expanded perlite particles, and the granularity of the aggregate is 1-10 mm; the reinforcing fiber is organic fiber or inorganic fiber, and comprises paper pulp fiber, cellulose fiber, polyester fiber, glass fiber, mineral wool, rock wool, ceramic fiber and carbon fiber, and the length of the reinforcing fiber is 3-20 mm.
In the porous material, the mass fraction of the basic magnesium carbonate cementing phase is 40-90%, the mass fraction of the aggregate is 0-50%, and the mass fraction of the reinforcing fiber is 0-10%.
The magnesium solid carbon product containing crystal water is MgCO3·xH2O moleculeThe formula is shown in the specification, wherein x is 0.1-1.8, 2, 3 and 5, and the formula comprises minerals such as pentahydromagnesite (x is 5), trihydromagnesite (x is 3) and dihydramagnesite (x is 2) or partially dehydrated products thereof (x is 0.1-1.8); the auxiliary agent is a substance capable of promoting the conversion of the magnesium carbon fixation product to basic magnesium carbonate, and comprises light-burned MgO (magnesite), Mg (OH)2Caustic dolomite, lime, silicate cement;
the preparation process flow of the porous material taking the magnesium solid carbon product as the raw material is shown in figure 1. The magnesium solid carbon product containing crystal water, the auxiliary agent and water are weighed, mixed and stirred uniformly according to a proportion to form viscous mixed slurry, wherein the addition amount of the auxiliary agent is 0-15% of the mass of the magnesium solid carbon product. The addition amount of water is 0.1 to 2.0 times of the total mass of the magnesium carbon fixation product and the auxiliary agent, and is related to the forming process. The reinforcing fibers are added into the mixed slurry to be uniformly dispersed, if longer fibers are used, the adding amount of the fibers is reduced, and if chopped fiber bundles or tabletting fibers are used, the consistency of the mixed slurry is controlled, so that the fiber dispersion is not facilitated due to the too thin thickness of the mixed slurry. In order to prevent the slurry from being difficult to stir after the water-absorbing aggregate is added, the aggregate needs to be pretreated, namely, the aggregate is sprayed by water with the saturated surface dry moisture content of the aggregate, so that the interior of the aggregate is saturated with water.
And (3) uniformly mixing the mixed slurry with the fibers and the aggregates, and then molding the mixture. The volume density of the porous material is designed to be 800kg/m3In the following, casting molding or vacuum filtration molding may be employed. After casting molding, the mold needs to be vibrated to discharge large bubbles in the mold. And (4) recycling the filtrate after suction filtration molding. When fine aggregate with the particle size of less than 2mm is adopted and the water consumption is controlled to enable the mixture to be in a plastic mud shape, an extrusion forming process can be adopted. When the volume density is designed to be 800kg/m3In the above process, the water consumption of the lower limit value of the adding amount is adopted, the material is in a semi-dry state, and the press forming process is considered.
And (3) stacking the molded green body and the mold or the mold in a multi-layer mode with limited four sides, locking the mold and sealing. Curing for 0.5 h-28 d at normal temperature-100 ℃ to obtain a cooked blank. Demoulding the cooked blank, drying at the temperature lower than 170 ℃, and trimming and finishing the board surface to obtain the magnesium porous material.
Fig. 2 compares the difference in pore structure characteristics between the cast and press-molded cementitious phases, both samples being wet heat cured samples at 100 ℃ x 4 h. According to the invention, a casting molding sample is subjected to wet and hot curing, and the relative pore volume distribution curves in a cementing phase respectively show two peak values at 0.1 μm and 0.3 μm, wherein the peak value at 0.3 μm is relatively higher and thinner, and most of pores are below 0.5 μm. The pore curve of the cementitious phase of the press-formed samples shows only a single narrow peak with a smaller peak value of about 0.05 μm and a substantial majority of the pores lying below 0.1. mu.m. A small number of larger pores were also found in both samples at a pore size of 400 μm.
The following description is given with reference to specific examples.
Example 1
Magnesium-based solid carbon product (MgCO) with crystal water quantity x ═ 33·3H2O), and the light calcined magnesia and water which are used as auxiliary agents are weighed, mixed and stirred uniformly according to the proportion in the table 1 to form viscous mixed slurry. Wherein the adding amount of the light-burned magnesium oxide is 6.79 wt% of the mass of the magnesium carbonate trihydrate, and the mass ratio of water to solid (the magnesium carbonate trihydrate and the light-burned magnesium oxide) is 0.8. Pouring the mixed slurry into a mold, curing for 28 days at 20 ℃, demolding, drying at 70 ℃ for 12 hours, and measuring the average dry density of five sample blocks to be 656kg/m3The average value of the compressive strength was 11.49 MPa. XRD shows that the basic magnesium carbonate in the cementing phase is mainly sphenophytite and hydromagnesite (Table 1).
Example 2
Magnesium-based solid carbon product (MgCO) with crystal water quantity x ═ 33·3H2O), mixing with 0.8 times of water, and uniformly stirring to form viscous mixed slurry. Pouring the mixed slurry into a mold, performing damp-heat curing under the closed condition of 60 ℃ multiplied by 24h, demolding, drying at 70 ℃ multiplied by 12h, and measuring that the average dry density of five sample blocks is 673kg/m3The average value of the compressive strength is 10.56 MPa. XRD shows that the basic magnesium carbonate in the cementing phase is mainly sphenophytite and hydromagnesite (Table 1).
Example 3
Magnesium-based solid carbon product (MgCO) with crystal water quantity x ═ 33·3H2O)，Mixing with 0.2 times of water, and stirring to obtain semi-dry powder. Placing the mixed powder into a mold, molding under 90MPa, clamping the molded body, performing wet-heat curing under a closed condition of 100 ℃ for 4h, demolding, drying at 100 ℃ for 4h, and measuring the average dry density of five sample blocks to be 1088kg/m3The average value of the compressive strength is 34.95 MPa. XRD shows that the main basic magnesium carbonate in the cementing phase is hydromagnesite (Table 1).
Example 4
Magnesium-based solid carbon product (MgCO) with crystal water quantity x ═ 33·3H2O), mixing with 2.0 times of water, and uniformly stirring to form mixed slurry. Polyester fibers with the length of 10mm and the mass of 1% of magnesium carbonate trihydrate are added into the mixed slurry to serve as reinforcing fibers, and the fibers are uniformly dispersed. Selecting expanded perlite particles with the particle size of less than 2mm, spraying 1.1 times of water in advance, and then adding the particles into the slurry for mixing to form a mixture with uniformly distributed fibers, aggregates and slurry. And putting the mixture into a porous mold, and performing vacuum filtration until no water drips below the mold. Stacking the sample green blocks after demoulding, fixing the periphery, locking the mould on the plate surface, performing damp-heat curing at 70 ℃ for 12h under a closed condition, drying the demoulded mature blank at 70 ℃ for 12h, and measuring the volume density average value of five dry blank sample blocks to be 580kg/m3The average value of the compressive strength is 8.18 MPa. XRD shows that the main basic magnesium carbonate in the cementing phase is hydromagnesite and spheronesite (Table 1).
Example 5
Magnesium solid carbon product (MgCO) with crystal water quantity x being 1.223·1.22H2O), mixing with 1.1 times of water, and uniformly stirring to form semi-dry powder. Wherein MgCO is present3·1.22H2O is MgCO3·3H2Heating the O crystal in an electric furnace at 200 ℃ for 2h to obtain the product. Pouring the mixed slurry into a mold, curing at 20 deg.C for 28d, curing at 70 deg.C for 24h, demolding, drying at 70 deg.C for 12h to obtain five sample blocks with average dry density of 595kg/m3The average value of the compressive strength is 11.02 MPa. XRD shows that the main basic magnesium carbonate in the cementing phase is hydromagnesite (Table 1).
Comparative example 1 and comparative example 2
Data were taken from aerated concrete (GB11968-2006) and from foam concrete (JG/T266-2011), respectively.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
TABLE 1 comparison of inventive examples with comparative examples
Claims (7)
1. A porous material taking a magnesium solid carbon product as a raw material is characterized in that: the basic magnesium carbonate is used as a cementing phase to combine the aggregate and the reinforced fiber together, and the basic magnesium carbonate cementing phase is a magnesium solid carbon product MgCO containing crystal water3·xH2And O (x is 0.1-1.8, 2, 3 and 5) is used as a raw material, is converted into basic magnesium carbonate which is flaky, mutually staggered and has a hollow or honeycomb structure under specific auxiliary agents and curing conditions, generates a cementing effect and is prepared into the porous material.
2. The porous material using the solid carbon magnesium product as the raw material according to claim 1, wherein: the basic magnesium carbonate is one or a compound of more of fibrobrucite, sphenopesite, hydromagnesite and isohydromagnesite; the aggregate is a light porous material and comprises ceramsite, foam glass particles, expanded vermiculite particles and expanded perlite particles, and the granularity of the aggregate is 1-10 mm; the reinforcing fiber is organic fiber or inorganic fiber, and comprises paper pulp fiber, cellulose fiber, polyester fiber, glass fiber, mineral wool, rock wool, ceramic fiber and carbon fiber, and the length of the reinforcing fiber is 3-20 mm.
3. The porous material using the solid carbon magnesium product as the raw material according to claim 1, wherein: in the porous material, the mass fraction of the basic magnesium carbonate cementing phase is 40-90%, the mass fraction of the aggregate is 0-50%, and the mass fraction of the reinforcing fiber is 0-10%.
4. The porous material using the solid carbon magnesium product as the raw material according to claim 1, wherein: the solid carbon product containing crystal water and magnesium is MgCO3·xH2The formula of O, wherein x is 0.1-1.8, 2, 3 and 5, and the formula comprises hydromagnesite (x is 5), hydromagnesite (x is 3), hydromagnesite (x is 2) minerals or partial dehydration products thereof (x is 0.1-1.8); the auxiliary agent is a substance capable of promoting the conversion of the magnesium carbon fixation product to basic magnesium carbonate, and comprises light-burned MgO (magnesite), Mg (OH)2Caustic dolomite, lime, silicate cement; the addition amount of the auxiliary agent is 0-15% of the mass of the magnesium solid carbon product.
5. The method for preparing a porous material by using a magnesium solid carbon product as a raw material according to claim 1, wherein the method comprises the following steps: the preparation steps are as follows:
s1: the magnesium solid carbon product containing crystal water, the auxiliary agent and water are weighed, mixed and stirred uniformly according to a proportion to form viscous mixed slurry;
s2: adding reinforcing fibers into the mixed slurry for uniform dispersion, and then adding aggregate which is sprayed with water with saturated surface dry water content in advance for mixing to form a mixture with uniform distribution of the fibers, the aggregate and the slurry, wherein the saturated surface dry water content is the water content of the aggregate in a saturated surface dry state;
s3: pouring, or carrying out suction filtration or extrusion molding on the mixture, and carrying out normal-temperature curing or wet-heat curing on the obtained green body after mold locking to obtain a cooked blank;
s4: demoulding the cooked blank, drying at the temperature lower than 170 ℃, and trimming and finishing the board surface to obtain the magnesium porous material.
6. The method for preparing a porous material from a magnesium solid carbon product as a raw material according to claim 5, wherein the method comprises the following steps: the addition amount of the water in the S1 is 0.1 to 2.0 times of the total mass of the crystallization water-containing magnesium solid carbon product and the auxiliary agent.
7. The method for preparing a porous material from a magnesium solid carbon product as a raw material according to claim 5, wherein the method comprises the following steps: the curing system in the S3 is curing for 0.5h to 28d under the sealed condition at the normal temperature to 100 ℃.
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