CN114956774A - Co-mineralization by utilizing bulk solid wastes 2 Method for producing building materials - Google Patents
Co-mineralization by utilizing bulk solid wastes 2 Method for producing building materials Download PDFInfo
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- CN114956774A CN114956774A CN202210531365.1A CN202210531365A CN114956774A CN 114956774 A CN114956774 A CN 114956774A CN 202210531365 A CN202210531365 A CN 202210531365A CN 114956774 A CN114956774 A CN 114956774A
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- 239000002910 solid waste Substances 0.000 title claims abstract description 122
- 239000004566 building material Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000000903 blocking effect Effects 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 96
- 239000002893 slag Substances 0.000 claims description 25
- 239000010440 gypsum Substances 0.000 claims description 19
- 229910052602 gypsum Inorganic materials 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 239000010881 fly ash Substances 0.000 claims description 13
- 239000002956 ash Substances 0.000 claims description 9
- 239000010882 bottom ash Substances 0.000 claims description 9
- 239000004568 cement Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 101100002917 Caenorhabditis elegans ash-2 gene Proteins 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- -1 silicon-aluminum-iron Chemical compound 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
-
- 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
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
-
- 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
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of IPC classified C04B28/00, in particular to CO-mineralization of CO by utilizing bulk solid wastes 2 A method for preparing building materials and application thereof. Co-mineralization by using bulk solid wastes 2 The method for preparing the building material at least comprises the steps of mixing solid waste raw materials, mineralization reaction, hydrothermal reaction and blocking forming. According to the invention, through the raw material proportion and material design, the activity of each element in the solid waste is fully exerted from the thermodynamic perspective, the problem of treatment and disposal of the bulk silicon-aluminum solid waste is solved by means of low carbon emission, and meanwhile, the CO can be treated 2 To carry outHigh-efficiency utilization and obtaining a resource product with high cost performance.
Description
Technical Field
The invention relates to the field of IPC classification C04B28/00, in particular to CO-mineralization of CO by utilizing bulk solid wastes 2 A method of making a building material.
Background
With the development of economy, the urbanization of the living environment of people is accelerated, industries such as coal, electric power and building are rapidly developed, and meanwhile, the quality of a large amount of solid wastes discharged in related fields is also increased year by year. The occurrence of the bulk solid wastes not only occupies a large amount of land resources for storage, but also causes serious pollution to the environment, water bodies and the like due to the complex components in the bulk solid wastes.
At present, the solid waste recycling means mainly focuses on building material utilization, and most of the existing solid waste building material utilization means are high in energy consumption. For example, in the prior art (CN104072193B), a foamed ceramic material based on silicon-aluminum-containing solid waste and a method for preparing a fireproof heat-insulating board are disclosed, wherein silicon-aluminum-containing solid waste is used as a raw material, and a small amount of calcium-containing ore, cosolvent and foaming agent are added to prepare the foamed ceramic material and the fireproof heat-insulating board 2 . The prior art (CN106915938B) discloses a system and a method for preparing a sulphoaluminate ultra-high water filling material by using industrial solid wastes, wherein silicon-aluminum-iron-based solid wastes such as coal gangue and the like and calcium sulfate-based solid wastes such as desulfurized gypsum and the like are mainly used as raw materials, and a matrix material is prepared by processes such as raw material grinding, homogenization, sintering, clinker grinding and the like, wherein the processes such as grinding, sintering and the like used in the method are high in energy consumption. In addition, in the prior art, researches on resource recycling are less in the aspects of synergic mineralization of a large amount of solid wastes and carbon dioxide, the strength of a building material product prepared through mineralization reaction is generally low, auxiliary cementing materials such as cement and the like are additionally added to ensure the service performance, and the production process of the cementing materials is high in carbon emission.
Therefore, the CO-mineralization of the bulk solid waste and the CO mineralization of the CO with the bulk solid waste, which have the advantages of low energy consumption and low carbon emission, can effectively utilize the synergistic effect of the bulk solid waste and the carbon dioxide, and the prepared building material has excellent mechanical strength, is urgently needed 2 A method of making a building material.
Disclosure of Invention
To solve the above problems, the first aspect of the present inventionProvides a method for CO-mineralizing CO by utilizing bulk solid wastes 2 The method for preparing the building material comprises the steps of preparing a solid-waste mixture, carrying out mineralization reaction, carrying out hydrothermal reaction and blocking molding; the mineralization reaction sequence is before or after the block forming step; the solid waste mixture comprises solid waste and water.
As a preferred scheme, the sequence of the mineralization reaction is before the step of forming into blocks, and the method for preparing the building material sequentially comprises the following steps: (1) preparing a solid waste mixture; (2) carrying out mineralization reaction; (3) forming into blocks; (4) and (4) carrying out hydrothermal reaction.
As a preferable scheme, the solid content of the solid waste mixture is adjusted between the mineralization reaction step and the blocking forming step; the solid content of the solid waste mixture is regulated specifically as follows: supplementing solid waste or supplementing solid waste and gypsum into the solid waste mixture;
as a preferable scheme, the mass ratio of water to solid waste in the solid waste mixture prepared in the step (1) is 1: 1-10: 1.
As a preferred scheme, the sequence of the mineralization reaction is positioned after the block molding step, and the method for preparing the building material sequentially comprises the following steps: (1) preparing a solid waste mixture; (2) forming into blocks; (3) carrying out mineralization reaction; (4) and (4) carrying out hydrothermal reaction.
As a preferable scheme, the blocking molding is casting vibration molding in a mold, and the solid content of a solid-waste mixture used for the blocking molding is 50-85%; the blocking forming is compression forming, and the solid content of the solid waste mixture used for the blocking forming is 65-95%.
In the application, the solid-waste mixture for blocking molding can be the solid-waste mixture prepared in the step (1) or the solid-waste mixture after solid content is adjusted according to different mineralization reaction sequences.
As a preferable scheme, the blocking molding is casting vibration molding in a mold, and the solid waste mixture used for the blocking molding also comprises gypsum.
As a preferred scheme, the element composition in the solid waste mixture satisfies the following conditions:
n(CaO)≥4n(Al 2 O 3 )+1.5n(SiO 2 )-n(CaSO 4 )；
wherein n (CaO) is the molar weight of Ca element in oxide composition which can generate carbonization reaction in the solid waste; n (Al) 2 O 3 ) Is the molar weight of Al element in the solid waste calculated by oxide composition; n (SiO) 2 ) Is the mole amount of Si element in the solid waste by oxide composition; n (CaSO) 4 ) Is CaSO in gypsum 4 The molar amount of (c).
As a preferable scheme, the content of the gypsum is 0.1-5% of the total mass of the solid waste in the solid waste mixture.
In the application, by limiting the addition of the gypsum, not only is the cooperative utilization of bulk solid wastes and waste gas effectively realized, but also the mechanical property of the prepared building material is effectively improved, so that the building material has excellent antioxidant strength and CO 2 And (4) absorption effect. The applicant speculates that: the addition of the gypsum with proper content can accelerate the forming and demoulding efficiency of the mixture in the process of the blocking forming of the solid-waste mixture, enhance the connecting strength of the content cement and the solid waste after the mixing forming, and promote the formed micro-pores to effectively generate the conversion action of silver grains and cracks, thereby improving the upper limit of the pressure bearing of the building material under the action of the extreme external force. However, the addition amount of gypsum needs to be kept within a proper range, and if the addition amount of gypsum is too large, so that the optimization of the types of final products is not facilitated, and the product performance is influenced.
As a preferable scheme, the blocking molding is press molding, and the element composition in the solid waste mixture meets the following requirements:
n(CaO)≥4n(Al 2 O 3 )+1.5n(SiO 2 )；
wherein, n (CaO) is the molar weight of Ca element in oxide composition which can generate carbonization reaction in the solid waste; n (Al) 2 O 3 ) Is the molar weight of Al element in the solid waste by the composition of oxides; n (SiO) 2 ) Is the mole amount of Si element in the solid waste based on the oxide composition.
As a preferable scheme, the solid waste is at least one of carbide slag, magnesium slag, phosphorus slag, steel slag, furnace ash, iron slag, gasified slag, fly ash, slag ash, bottom ash, fly ash, red mud, construction waste, waste cement, tailings and ore raw materials.
As a preferred scheme, the mineralization reaction adopts a material containing CO 2 Said gas containing CO 2 CO in the gas of (2) 2 The volume fraction of the mineral is 8-100%, the mineralization reaction time is 30-240 min, and the mineralization reaction temperature is 20-120 ℃.
Preferably, the catalyst contains CO 2 The gas is at least one of coal-fired power plant flue gas, lime kiln flue gas, steel plant flue gas, chemical plant flue gas, cement plant flue gas and gas after carbon capture and analysis.
As a preferred scheme, the hydrothermal reaction is specifically operated as follows: and placing the blank body to be subjected to the hydrothermal reaction into a reaction kettle, vacuumizing, introducing high-temperature water vapor to perform the hydrothermal reaction, wherein the reaction temperature is 120-240 ℃, and the reaction time is 4-12 hours.
As a preferable scheme, the mineralization pressure in the mineralization reaction process is 0.3-2 MPa.
Preferably, the pressure in the hydrothermal reaction process is 1-3 MPa.
The second aspect of the invention provides the CO-mineralization method by utilizing the bulk solid waste 2 Application of method for preparing building material, including CO-mineralizing CO by utilizing bulk solid waste 2 Method for producing building materials, production of building materials and CO 2 And the recycling process of (2).
Has the advantages that:
1. according to the preparation method of the building material, through multi-source bulk solid waste compounding and material design, active calcium elements in solid waste can be fully utilized to capture CO in waste gas 2 And the activity of each element in a large amount of solid wastes can be fully utilized from the thermodynamic angle, so that the building material with extremely high cost performance is obtained.
2. The preparation method of the building material provided in the application can simultaneously solve the treatment and disposal problems of bulk solid wastes and CO by means of extremely low carbon emission 2 The method has the advantages of solving the problem of trapping and utilizing, reducing energy consumption, being suitable for the existing building material preparation production line, having simple flow, having general equipment and rich appearance of strong products, and the like.
3. The present application is not particularly limited to CO 2 Gas source and concentration, CO saving 2 Energy consumption and cost in the trapping process are reduced, high carbon emission raw materials commonly used by building materials such as cement and gravel are hardly added in the formula design, and the carbon emission of the whole process is reduced from the raw material end.
4. According to the preparation method of the building material, the addition amount of gypsum is limited and the cement proportion is controlled, so that the synergistic utilization of a large amount of solid wastes and waste gas is effectively realized, the mechanical property of the prepared building material is effectively improved, and the building material has excellent antioxidant strength and CO (carbon monoxide) 2 The absorption effect can be further applied to various industrial scenes, such as steel, electric power, coal chemical industry, cement, glass, ceramics and the like, and has wide applicability.
Detailed Description
The performance tests of the test block in the following embodiments and comparative examples comprise carbon dioxide absorptivity and compressive strength, wherein the carbon dioxide absorptivity is the percentage of the mass of carbon dioxide absorbed by solid wastes in the mass of the test block, the content of carbon dioxide absorbed by solid wastes is obtained by testing a TG/DTG curve of a mineralized product, the content of carbon dioxide absorbed by solid wastes is 550-850 ℃, and the mass of the test block is the mass of the mineralized product at 105 ℃; the compressive strength was measured according to GBT4111-2013 "test methods for concrete blocks and bricks".
Solid waste information in examples and comparative examples: the solid waste 1 is from a fertilizer-mixing and certain salt coal chemical plant and is a mixture of gasified slag, carbide slag and large slag ash; the solid waste 2 comes from a certain domestic garbage incineration plant in Suzhou and is a mixture of garbage incineration bottom ash and fly ash.
CO-CONTAINING COMPARATIVE EXAMPLES AND COMPARATIVE EXAMPLES 2 Composition information (volume fraction) of the gas of (2): the gas a comes from tail gas of a fertilizer-mixing and salt-coal chemical plant; the gas b is CO generated by flue gas of a certain domestic garbage incineration plant in Suzhou after dust removal, desulfurization and denitrification and an organic amine method carbon laying device 2 A gas.
| Gas composition | CO 2 | N 2 | SO x | NO x | VOCs |
| Gas a | 76.5％ | 18.9％ | 2.3％ | 2％ | 0.3％ |
| Gas b | 98.6％ | 1.4％ | 0％ | 0％ | 0％ |
Example 1
Example 1 in a first aspect, there is provided a method for CO-mineralizing CO using bulk solid waste 2 The method for preparing the building material comprises the following specific steps: (1) preparing a solid waste mixture; (2) carrying out mineralization reaction; (3) adjusting the solid content of the solid waste mixture; (4) forming into blocks; (5) and (4) carrying out hydrothermal reaction.
Embodiment mode S1-1:
(1) the solid waste 1 is prepared from the following fly ash in percentage by mass: carbide slag: mixing the large slag ash in a ratio of 4:5:1, recording as SW1, weighing 10 parts of SW1 and 10 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixture 1; (2) introducing gas a into the mixture 1 at 60 ℃, wherein the mineralization reaction time is 120 min; (3) after the mineralization reaction is finished, supplementing 40 parts of SW1 into the reactor, and quickly stirring to obtain a mixture 2, wherein the solid content of the mixture 2 is 81.9%; (4) conveying the mixture 2 into a mould, performing compression molding under the pressure of 15MPa, and demolding to obtain a green body; (5) and (3) placing the demolded green body into a hydrothermal reaction kettle for reaction at the temperature of 180 ℃ for 8 hours.
Embodiment C1-1:
(1) the solid waste 1 is prepared from the following fly ash in percentage by mass: carbide slag: mixing the large slag ash in a ratio of 6:3:1, recording as SW2, weighing 10 parts of SW2 and 10 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixture 3; (2) introducing gas a into the mixture 3 at 60 ℃, wherein the mineralization reaction time is 120 min; (3) after the mineralization reaction is finished, supplementing 40 parts of SW2 into the reactor, and quickly stirring to obtain a mixture 4, wherein the solid content of the mixture 4 is 81.9%; (4) conveying the mixture 4 into a mould, performing compression molding under the pressure of 15MPa, and demolding to obtain a green body; (5) and (3) placing the demolded green body into a hydrothermal reaction kettle for reaction at the temperature of 180 ℃ for 8 hours.
Embodiment mode S1-2:
(1) the solid waste 1 is prepared from the following components in percentage by mass: carbide slag: mixing large slag ash at a ratio of 4:5:1, recording as SW1, weighing 10 parts of SW1 and 10 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixture 5; (2) introducing gas a into the mixture 5 at 100 ℃, wherein the mineralization reaction time is 40 min; (3) after the mineralization reaction is finished, supplementing 20 parts of SW1 and 0.4 part of gypsum into the reactor, and quickly stirring to obtain a mixture 6, wherein the solid content of the mixture 6 is 76.9%; (4) conveying the mixture 6 into a mold, pouring and vibrating for molding, and completing demolding when the green body has demolding strength to obtain a green body; (5) and (3) placing the demolded green body into a hydrothermal reaction kettle for reaction at the temperature of 200 ℃ for 6 hours.
Embodiment C1-2:
(1) the solid waste 1 is prepared from the following components in percentage by mass: carbide slag: mixing the large slag ash in a ratio of 6:3:1, recording as SW2, weighing 10 parts of SW2 and 10 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixture 7; (2) introducing gas a into the mixture 1 at 100 ℃, wherein the mineralization reaction time is 40 min; (3) after the mineralization reaction is finished, supplementing 20 parts of SW1 and 0.4 part of gypsum into the reactor, and quickly stirring to obtain a mixture 8, wherein the solid content of the mixture 8 is 76.9%; (4) conveying the mixture 8 into a mold, pouring and vibrating for molding, and completing demolding when the green body has demolding strength to obtain a green body; (5) and (3) placing the demolded green body into a hydrothermal reaction kettle for reaction at the temperature of 200 ℃ for 6 hours.
The results of the performance testing of each embodiment in example 1 are shown in the following table:
| name of test block | Carbon dioxide absorption rate (%) | Average compressive strength (Mpa) |
| S1-1 | 18.33 | 18.2 |
| C1-1 | 16.71 | 9.23 |
| S1-2 | 19.47 | 21.3 |
| C1-2 | 16.24 | 10.32 |
In the above table, it can be found that the ratio of calcium oxide, silicon dioxide and aluminum oxide, which are components of the test block obtained by pressing the mineralized slurry into blocks or pouring the mineralized slurry into blocks for hydrothermal experiments, has a large influence on the carbon dioxide absorption rate and compressive strength of the test block. Comparing S1-1 and C1-1 with S1-2 and C1-2 respectively, when the proportion of the calcium oxide, the silicon dioxide and the aluminum oxide in the mixed raw materials meets the condition that n (CaO) is more than or equal to 4n (Al) 2 O 3 )+1.5n(SiO 2 ) Under the condition, the strength and the absorptivity of the final product are higher, because when the proportion of calcium oxide, silicon dioxide and aluminum oxide does not satisfy the formula, on one hand, the content of calcium oxide in the raw material is reduced, and the contact probability of carbon dioxide and the raw material is reduced in the mineralization reaction stage, so that the absorptivity of a sample to the carbon dioxide is lower; on the other hand, calcium oxide is reacted in the mineralization stage, and the residual calcium oxide cannot fully react with the silicon and aluminum to generate a strength enhanced phase (CSH/Aft/AFm), so that the compressive strength of the sample is greatly reduced.
Example 2
Example 2 in a first aspect, a CO-mineralization method using bulk solid waste is provided 2 The method for preparing the building material comprises the following specific steps: (1) preparing a solid waste mixture; (2)forming into blocks; (3) carrying out mineralization reaction; (4) and (4) carrying out hydrothermal reaction.
Embodiment mode S2-1:
(1) and (3) burning fly ash by using solid waste 2 in a mass ratio: mixing 3:2 of incineration bottom ash, recording as SW3, weighing 100 parts of SW3 and 20 parts of water, conveying the materials into a reactor with a stirrer, and uniformly mixing to obtain a mixed material 9, wherein the solid content of the mixed material 9 is 83.3%; (2) conveying the mixture 9 into a die for blocking forming, pressing and forming under the pressure of 15MPa to obtain a green blank, and completing demoulding when the green blank has demoulding strength; (3) placing the demolded green body into a reaction kettle, vacuumizing, introducing gas b, and carrying out a mineralization reaction at 40 ℃ for 180 min; and (4) after the mineralization reaction is finished, evacuating gas in the reaction kettle, vacuumizing again, and then introducing high-temperature steam to carry out hydrothermal reaction at the reaction temperature of 160 ℃ for 10 hours.
Embodiment C2-1:
(1) burning bottom ash by using solid waste 2 in a mass ratio: mixing the incineration fly ash 2:3, recording as SW4, weighing 100 parts of SW4 and 20 parts of water, conveying the materials into a reactor with a stirrer, and uniformly mixing to obtain a mixture 10, wherein the solid content of the mixture 10 is 83.3%; (2) conveying the mixture 10 to a die for blocking and forming, pressing and forming under the pressure of 15MPa to obtain a green blank, and completing demoulding when the green blank has demoulding strength; (3) placing the demolded green body into a reaction kettle, vacuumizing, introducing gas b, and carrying out a mineralization reaction at 40 ℃ for 180 min; and (4) after the mineralization reaction is finished, evacuating gas in the reaction kettle, vacuumizing again, and then introducing high-temperature steam to carry out hydrothermal reaction at the reaction temperature of 160 ℃ for 10 hours.
Embodiment mode S2-2:
(1) burning bottom ash by using solid waste 2 in a mass ratio: mixing the incineration fly ash with the ratio of 3:2, recording as SW3, weighing 30 parts of SW3, 15 parts of water and 0.2 part of gypsum, conveying the materials into a reactor with stirring, and uniformly mixing to obtain a mixture 11, wherein the solid content of the mixture 11 is 66.67%; (2) conveying the mixture 11 into a mold, pouring and vibrating for molding, and completing demolding when the green body has demolding strength to obtain a green body; (3) placing the demolded green body into a reaction kettle, vacuumizing, introducing gas b, and carrying out a mineralization reaction at the reaction temperature of 80 ℃ for 80 min; (4) after the mineralization reaction is finished, evacuating the gas in the reaction kettle, vacuumizing again, and then introducing high-temperature water vapor to carry out hydrothermal reaction at the reaction temperature of 140 ℃ for 12 hours.
Embodiment C2-2:
(1) burning bottom ash by using solid waste 2 in a mass ratio: mixing the incineration fly ash 2:3, recording as SW4, weighing 30 parts of SW1, 15 parts of water and 0.2 part of gypsum, conveying the materials into a reactor with a stirrer, and uniformly mixing to obtain a mixture 12, wherein the solid content of the mixture 12 is 66.67%; (2) conveying the mixture 12 into a mold, pouring and vibrating for molding, and completing demolding when the green body has demolding strength to obtain a green body; (3) placing the demolded green body into a reaction kettle, vacuumizing, introducing gas b, and carrying out a mineralization reaction at the reaction temperature of 80 ℃ for 80 min; (4) after the mineralization reaction is finished, evacuating the gas in the reaction kettle, vacuumizing again, and then introducing high-temperature water vapor to carry out hydrothermal reaction at the reaction temperature of 140 ℃ for 12 hours.
The results of the performance testing of each embodiment in example 2 are shown in the following table:
| name of test block | Carbon dioxide absorption rate (%) | Average compressive strength (MPa) |
| S2-1 | 15.43 | 18.47 |
| C2-1 | 11.01 | 7.23 |
| S2-2 | 16.01 | 17.94 |
| C2-2 | 12.55 | 9.71 |
From the above table, it can be found that, although the solid waste raw material is changed, the influence of the proportions of calcium oxide, silicon dioxide and aluminum oxide on the compression strength and carbon dioxide absorption rate of the test block is the same. As long as the proportion of calcium oxide, silicon dioxide and aluminum oxide in the mixed raw materials satisfies n (CaO) is more than or equal to 4n (Al) 2 O 3 )+1.5n(SiO 2 )-n(CaSO 4 ) In the case of no gypsum in the solid waste mixture, n (CaSO) 4 ) 0), the strength and absorption of the final product will be high, which also proves that the rule applies to various scenarios.
Comparative example 1
Comparative example 1 in a first aspect, there is provided a CO-mineralisation process using bulk solid waste 2 The method for preparing the building material comprises the following specific steps:
(1) burning fly ash by using solid waste in a mass ratio: mixing the incineration bottom ash in a ratio of 6:4, recording as SW2-1, weighing 100 parts of SW1 and 20 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixture 13; (2) conveying the mixture 13 into a die for blocking forming, pressing and forming under the pressure of 15MPa to obtain a green blank, and completing demoulding when the green blank has demoulding strength; (3) and (3) putting the demolded green body into a reaction kettle, vacuumizing, introducing gas b, and performing mineralization reaction at the reaction temperature of 40 ℃ for 180 min.
Comparative example 2
(1) And (3) burning fly ash by using solid waste 2 in a mass ratio: mixing the incineration bottom ash in a ratio of 6:4, recording as SW2-1, weighing 100 parts of SW1 and 20 parts of water, conveying the mixture into a reactor with a stirrer, and uniformly mixing to obtain a mixed material 14; (2) conveying the mixture 14 to a die for blocking and forming, and pressing and forming under the pressure of 15MPa to obtain a green blank, and completing demoulding when the green blank has demoulding strength; (3) and (3) putting the demolded green body into a reaction kettle, vacuumizing, and introducing high-temperature steam to perform hydrothermal reaction at the temperature of 160 ℃ for 10 hours.
| Name of test block | Carbon dioxide absorption rate (%) | Average compressive strength (MPa) |
| Example 2-S2-1 | 15.43 | 18.47 |
| Comparative example 1 | 14.89 | 5.23 |
| Comparative example 2 | - | 16.31 |
It is understood from the comparative examples and comparative examples that the carbon fixation ratio of the test block subjected to only the mineralization reaction is guaranteed, but the strength of the test block after the reaction is low because the mineralized product is mainly platy calcite, and although some pores are filled, a small amount of pores are formed among crystals by printing and dyeing, so that microcracks are easily generated, and the strength of the mineralized test block is low. The compression strength of the product to carbon dioxide after hydrothermal treatment is higher than that of the product only mineralized, because CSH is generated by hydrothermal treatment and is in a gel shape, and can be used as a binder to be filled between crystal phases, the strength of the product is greatly improved; however, the strength of the test piece is lower than that of the test piece of the example only, because the crystal lattice energy of the hydrothermal reaction is reduced and the hydrothermal reaction is promoted to be more sufficient because the plate-shaped calcium carbonate generated by mineralization is used as an impurity phase in the hydrothermal reaction stage.
Claims (10)
1. Co-mineralization by utilizing bulk solid wastes 2 A method of preparing a building material, characterized by: the method comprises the steps of preparing a solid waste mixture, carrying out mineralization reaction, hydrothermal reaction and blocking molding; the mineralization reaction sequence is before or after the block forming step; the solid waste mixture comprises solid waste and water.
2. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the mineralization reaction sequence is positioned before the blocking and forming step, and the method for preparing the building material sequentially comprises the following steps: (1) preparing a solid waste mixture; (2) carrying out mineralization reaction; (3) forming into blocks; (4) and (4) carrying out hydrothermal reaction.
3. The CO-mineralization of bulk solid waste as claimed in claim 2 2 A method of preparing a building material, characterized by: the solid content of the solid waste mixture is adjusted between the mineralization reaction step and the blocking forming step; the solid content of the solid waste mixture is regulated specifically as follows: supplementing solid waste or supplementing solid waste and gypsum into the solid waste mixture;
the mass ratio of water to solid waste in the solid waste mixture prepared in the step (1) is 1: 1-10: 1.
4. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the sequence of the mineralization reaction is after the step of the block forming, the preparationThe method for preparing the building material sequentially comprises the following steps: (1) preparing a solid waste mixture; (2) forming into blocks; (3) carrying out mineralization reaction; (4) and (4) carrying out hydrothermal reaction.
5. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the blocking forming is pouring vibration forming in a mould, and the solid content of a solid-waste mixture used for the blocking forming is 50-85%; the blocking forming is compression forming, and the solid content of the solid waste mixture used for the blocking forming is 65-95%.
6. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the blocking molding is casting vibration molding in a mold, and the solid waste mixture used for the blocking molding also comprises gypsum.
7. The CO-mineralization of a bulk solid waste product as claimed in claim 6 2 A method of preparing a building material, characterized by: the element composition in the solid waste mixture meets the following requirements:
n(CaO)≥4n(Al 2 O 3 )+1.5n(SiO 2 )-n(CaSO 4 )；
wherein n (CaO) is the molar weight of Ca element in oxide composition which can generate carbonization reaction in the solid waste; n (Al) 2 O 3 ) Is the molar weight of Al element in the solid waste by the composition of oxides; n (SiO) 2 ) Is the mole amount of Si element in the solid waste by oxide composition; n (CaSO) 4 ) Is CaSO in gypsum 4 The molar amount of (c).
8. The CO-mineralization of a bulk solid waste product as claimed in claim 6 2 A method of preparing a building material, characterized by: the content of the gypsum is 0.1-5% of the total mass of the solid waste in the solid waste mixture.
9. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the blocking forming is compression forming, and the element composition in the solid waste mixture meets the following requirements:
n(CaO)≥4n(Al 2 O 3 )+1.5n(SiO 2 )；
wherein n (CaO) is the molar weight of Ca element in oxide composition which can generate carbonization reaction in the solid waste; n (Al) 2 O 3 ) Is the molar weight of Al element in the solid waste by the composition of oxides; n (SiO) 2 ) Is the mole amount of Si element in the solid waste based on the oxide composition.
10. The CO-mineralization of a bulk solid waste product as claimed in claim 1 2 A method of preparing a building material, characterized by: the solid waste is at least one of carbide slag, magnesium slag, phosphorus slag, steel slag, furnace ash, iron slag, gasified slag, fly ash, large slag ash, bottom ash, fly ash, red mud, construction waste, waste cement, tailings and ore raw materials;
the mineralization reaction adopts a material containing CO 2 Said gas containing CO 2 CO in the gas of (2) 2 The volume fraction of the mineral is 8-100%, the mineralization reaction time is 30-240 min, and the mineralization reaction temperature is 20-120 ℃; the reaction temperature of the hydrothermal reaction is 120-240 ℃, and the reaction time is 4-12 h.
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