CN114920523A - Composite particle capable of adsorbing carbon dioxide and preparation method thereof - Google Patents
Composite particle capable of adsorbing carbon dioxide and preparation method thereof Download PDFInfo
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- 239000011246 composite particle Substances 0.000 title claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 57
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003546 flue gas Substances 0.000 claims abstract description 53
- 239000010881 fly ash Substances 0.000 claims abstract description 40
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 40
- 239000010440 gypsum Substances 0.000 claims abstract description 40
- 239000002893 slag Substances 0.000 claims abstract description 28
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000004568 cement Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 238000005563 spheronization Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 239000011398 Portland cement Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 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
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000010883 coal ash Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000004927 clay Substances 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 239000010453 quartz Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002956 ash Substances 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 230000036571 hydration Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002910 solid waste Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 235000007237 Aegopodium podagraria Nutrition 0.000 description 2
- 244000045410 Aegopodium podagraria Species 0.000 description 2
- 235000014429 Angelica sylvestris Nutrition 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 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
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a composite particle capable of adsorbing carbon dioxide and a preparation method thereof, which comprises the steps of putting coal-fired power plant fly ash, bottom slag and desulfurized gypsum into a ball mill for fine grinding; putting the pulverized coal ash, the bottom slag, the desulfurized gypsum, the cement, the alkaline activator and the binder into a stirrer for fully and uniformly mixing; and putting the uniformly mixed materials into a granulator for spheronization or extrusion granulation to obtain composite particles with the particle size range of 5-35 mm. The obtained composite particles are subjected to industrial source flue gas curing and natural curing treatment, so that the strength of the particles is improved, and the industrial source flue gas CO is realized 2 Low cost capture. The invention uses the fly ash, bottom slag and desulfurized gypsum which are stacked in large area in a coal-fired power plant as raw materials, and the prepared composite particles can replace part of mineral raw materials such as quartz, clay, sandstone and the like, and can also capture industrial source CO 2 And realizes the 'treatment of pollution by waste'.
Description
Technical Field
The invention belongs to the technical field of coal-fired solid waste resource utilization, and particularly relates to an adsorbable CO 2 The composite particles of (1) and a process for producing the same.
Background
Fly ash, end sediment and desulfurization gypsum are the burning accessory substance in the coal-fired power generation process, are the solid waste of the biggest chinese output, and the fly ash, end sediment and the desulfurization gypsum that are not utilized are piled up the processing mostly, all have certain harm to environment and human body, therefore, the utilization of coal ash, end sediment and desulfurization gypsum is the problem that the solid waste treatment technical field needs a long time to solve.
The fly ash has volcanic ash reactivity, and the volcanic ash reaction of the fly ash can be accelerated under the action of the alkaline excitant to generate a compound with hydraulic gelation property, so that the fly ash can be used for preparing composite particles with certain strength. The desulfurized gypsum is used as an excitant, which can further enhance the strength of the composite particles. In addition, CaO in the fly ash and the bottom slag can adsorb CO 2 Can be used for industrial source flue gas CO 2 And (4) trapping.
In conclusion, the adsorbable CO which is simple in process flow, low in cost and suitable for industrial large-scale production is developed by taking the solid waste fly ash, bottom slag and desulfurized gypsum stacked in large area in the coal-fired power plant as raw materials 2 The preparation method of the composite particles not only can reduce the demand on mineral particles such as quartz, clay, sandstone and the like, but also can capture industrial CO (carbon monoxide) from coal-fired power plants, steel plants and the like 2 And the aim of 'double carbon' is fulfilled.
Disclosure of Invention
The invention aims to provide composite particles capable of adsorbing carbon dioxide and a preparation method thereof, and aims to solve the problems of high solid waste yield and low utilization rate of a coal-fired power plant and CO in industrial source flue gas 2 The problem of trapping is solved, thereby realizing the solid waste fly ash, bottom slag, desulfurized gypsum and industrial source flue gas CO of the coal-fired power plant 2 And (5) performing synergistic treatment.
According to one aspect of the invention, a composite particle capable of adsorbing carbon dioxide is provided, which comprises the following components in parts by weight:
35-40 parts of Portland cement, 20-35 parts of fly ash, 15-25 parts of bottom slag, 2-3 parts of desulfurized gypsum, 2-3 parts of alkaline activator, 10-12 parts of binder and 20-30 parts of water. Wherein, the fly ash, the bottom slag and the desulfurized gypsum are all solid wastes of a coal-fired power plant.
Further, the alkali activator is one of sodium hydroxide, potassium hydroxide and calcium oxide.
Further, the binder is one of kaolin, refractory soil and water glass.
According to another aspect of the present invention, the above-described method for preparing carbon dioxide adsorbable composite particles comprises:
putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling;
step two, putting the fly ash, the bottom slag, the desulfurized gypsum, the cement, the alkaline activator and the binder which are obtained after ball milling in the step one into a stirrer for stirring to obtain a uniformly mixed powdery mixture;
step three, putting the powdery mixture obtained in the step two into a granulator for spheronization or extrusion granulation;
and step four, carrying out flue gas curing and natural curing on the particles obtained in the step three.
Further, in the step one, the particle size of the particles obtained after ball milling is 50-100 μm.
Further, in the third step, the formed particles are spherical or ellipsoidal.
Further, in the third step, the particle size of the molded particles is 5 mm-35 mm.
Further, in the fourth step, the flue gas is cured in the industrial source of CO 2 The method is carried out in a flue gas atmosphere; the curing flue gas contains 10-50% of CO 2 5% -25% of water vapor; the temperature of the curing flue gas is 60-200 ℃.
Further, in the fourth step, the flue gas curing time is 1-12 hours; the flue gas curing pressure is 0.5 MPa-2.0 MPa.
Further, in the fourth step, the natural curing process is carried out at normal temperature and normal pressure, and the curing time is 7-30 days.
Compared with the prior art, the invention has the following technical effects:
(1) the composite particles prepared by the invention take the fly ash, the bottom slag and the desulfurized gypsum as main raw materials, the utilization rate of the fly ash, the bottom slag and the desulfurized gypsum as the coal-fired solid waste of the power plant is improved to a certain extent, and the prepared composite particles can replace part of mineral raw materials such as quartz, clay, sandstone and the like, reduce the pressure required by China on the mineral raw materials such as quartz, clay, sandstone and the like, and have certain economic benefit.
(2) The invention uses the desulfurized gypsum to stimulate the volcanic ash activity of the fly ash, the desulfurized gypsum is solid waste with larger output of a coal-fired power plant, and the problem of low utilization rate of the desulfurized gypsum is solved.
(3) The invention uses the industrial source flue gas to maintain the composite particles, and the composite particles absorb carbon dioxide in the flue gas in the maintenance process, thereby realizing 'treatment of pollution by waste', and having important significance for realizing the 'double-carbon' goal.
(4) The preparation method of the composite particles is simple, has low cost and can be used for large-scale production.
Drawings
FIG. 1 is a schematic representation of a sample of composite particles of example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) photograph of the composite particles of example 1 and comparative example 2 of the present invention.
Detailed Description
The composite particle capable of adsorbing carbon dioxide provided by the typical embodiment of the invention comprises the following components in parts by weight:
35-40 parts of portland cement, 20-35 parts of fly ash, 15-25 parts of bottom slag, 2-3 parts of desulfurized gypsum, 2-3 parts of alkaline activator, 10-12 parts of binder and 20-30 parts of water.
Among them, 425 portland cement is preferably used as the portland cement.
In the composite particles, the portland cement forms hydration products and Ca (OH) at the initial stage of hydration 2 Enhancing early strength of the composite particles and increasing CO of the composite particles 2 The amount of adsorption.
The describedSiO in fly ash 2 、Al 2 O 3 The content of free CaO accounts for more than 70 percent of the total amount, and the active substance SiO 2 With Al 2 O 3 Ca (OH) provided with portland cement under hydrothermal conditions 2 The reaction is carried out to generate C-S-H (calcium silicate hydrate) gel and C-A-H (calcium aluminate hydrate) gel, namely the fly ash and the portland cement generate hydration synergistic effect, the generation of hydration reactants is increased, the early strength of the composite particles is improved, and the free CaO, the water and the CO are mixed 2 React to form CaCO 3 Increase CO 2 The adsorption quantity is increased and the compressive strength of the composite particles is increased.
The bottom slag (or ash slag) contains SiO 2 、Al 2 O 3 Accounts for more than 60 percent of the total amount. After fine grinding, SiO in the bottom slag 2 、Al 2 O 3 The activity is excited, and the active substance reacts with Ca (OH) under hydrothermal conditions 2 The reaction is carried out to generate C-S-H (calcium silicate hydrate) gel, thereby increasing the generation of hydration reactant and improving the strength of the composite particles.
The desulfurized gypsum can be used as a salt excitant to excite SiO in the fly ash and the bottom slag 2 With Al 2 O 3 The activity of the composite particles promotes the hydration of active substances in the fly ash, increases the generation amount of hydration products, and improves the strength of the composite particles and CO 2 The amount of adsorption.
The alkali activator is one of sodium hydroxide, potassium hydroxide and calcium oxide. Basic activators to provide OH - Destroy the original structure of the fly ash and further excite SiO in the fly ash 2 With Al 2 O 3 The activity of the composite particles can promote the hydration of active substances in the fly ash, increase the generation amount of hydration products, and improve the strength of the composite particles and CO 2 The amount of adsorption.
The binder is one of kaolin, refractory soil and water glass. The binder improves the flow properties of the raw materials, so that the composite particles are easy to form during preparation.
The preparation method of the composite particle capable of adsorbing carbon dioxide comprises the following steps:
step one, putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling.
The ball milling time is usually 3-5 hours, and the particle size of the particles obtained after ball milling is 50-100 μm.
And step two, putting the fly ash, the bottom slag, the desulfurized gypsum, the cement, the alkali activator and the binder which are obtained after the ball milling in the step one into a stirrer for stirring to obtain a uniformly mixed powdery mixture.
Preferably, stirring is carried out in a stirrer for 30min to obtain the powdery mixture.
And step three, putting the powdery mixture obtained in the step two into a granulator for spheronization or extrusion granulation.
The particles after granulation molding are spherical or ellipsoidal, and the particle size of the particles is 5 mm-35 mm.
And step four, carrying out flue gas curing and/or natural curing on the particles obtained in the step three.
Aiming at the flue gas curing, the flue gas curing is carried out on industrial source CO 2 The method is carried out in a flue gas atmosphere; the curing flue gas contains 10-50% of CO 2 5% -25% of water vapor; curing flue gas at the temperature of 60-200 ℃; the flue gas curing time is 1-12 hours; the flue gas curing pressure is 0.5 MPa-2.0 MPa.
And aiming at the natural curing, the natural curing process is carried out at normal temperature and normal pressure, and the curing time is 7-30 days.
The principle involved in the maintenance process is that under the composite excitation action of the desulfurized gypsum and the alkaline exciting agent, the active substance SiO in the fly ash 2 With Al 2 O 3 Is further excited to generate C-S-H (calcium silicate hydrate) and C-A-H (calcium aluminate hydrate) gel, so that the strength of the composite particles is improved to a certain extent; the cement component in the mixed powder and water are subjected to hydration reaction to generate a certain amount of Ca (OH) 2 The free CaO in the remaining components of the mixed powder reacts with water to further form more Ca (OH) 2 During curing with flue gas, Ca (OH) 2 With CO 2 Reaction to form CaCO 3 The C-S-H gel generated in the process of hydrating the fly ash is mineralized with water to generate certain CaCO 3 So that the composite particles can adsorb CO while improving the compressive strength 2 . The main reaction formula is as follows:
the production process of the present invention is illustrated by examples 1 to 4 and comparative examples 1 to 2. The examples and comparative examples are intended to illustrate embodiments of the invention without departing from the scope of the subject matter of the invention, and the scope of protection of the invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
The carbon fixing rate of the composite particles in the examples and comparative examples was calculated by:
wherein m is 2 Means the mass m of the composite particles after flue gas curing 1 Which refers to the quality of the composite particles before flue gas curing.
Example 1
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 4 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 425 parts of portland cement, 30 parts of pulverized coal ash, 13 parts of pulverized ash, 3 parts of pulverized desulfurized gypsum, 3 parts of sodium hydroxide and 11 parts of kaolin, putting the materials into a stirrer, stirring for 30 minutes, putting the materials into a disc granulator, granulating, and uniformly spraying 30 parts of water on the surface of powder in the granulation process to form particles, wherein the particle size of the formed particles is 5-35 mm. The prepared pellets are shown in FIG. 1, and the scanning electron microscope image of the cured pellets for 7 days is shown in FIG. 2 (a).
The molded particles are charged at 60 deg.C under 1MPa of CO 2 And (3) carrying out flue gas curing in simulated flue gas with the concentration of 20% and the concentration of 15% for 6 hours, taking out after curing, and placing in a normal-temperature normal-pressure environment for curing for 28 days.
The compressive strengths of the granules after curing for 3 days, 7 days, 14 days and 28 days are 5.846MPa, 5.778MPa, 6.021MPa and 6.463MPa respectively, and the change of the compressive strength of the granules with time is shown in Table 1.
TABLE 1
| 3d | 7d | 14d | 28d | |
| Compressive strength (MPa) | 5.864 | 5.778 | 6.021 | 6.463 |
The composite particles before and after the flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.47%, as shown in table 2.
Example 2
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 4 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 425 parts of portland cement, 30 parts of pulverized coal ash, 13 parts of pulverized ash, 3 parts of desulfurized gypsum, 3 parts of sodium hydroxide and 11 parts of refractory soil, putting into a stirrer, stirring for 30 minutes, putting into a disc granulator, granulating, uniformly spraying 30 parts of water on the surface of powder in the granulation process, and forming particles, wherein the particle size of the formed particles is 5-35 mm.
The molded particles are put into the reactor at a temperature of 60 ℃ and a pressure of 1MPa, and are CO 2 And (3) carrying out flue gas curing in simulated flue gas with the concentration of 20% and the concentration of 15% for 6 hours, taking out after curing, and placing in a normal-temperature normal-pressure environment for curing for 28 days. The 7-day compressive strength was 6.150MPa, as shown in Table 2.
The composite particles before and after the flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.35%, as shown in table 2.
Example 3
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 4 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 425 parts of portland cement, 30 parts of pulverized coal ash, 13 parts of pulverized ash, 3 parts of desulfurized gypsum, 3 parts of sodium hydroxide and 11 parts of refractory soil, putting into a stirrer, stirring for 30 minutes, putting into a disc granulator, granulating, uniformly spraying 27 parts of water and 3 parts of water glass on the surface of powder in the granulation process, and forming particles, wherein the particle size of the formed particles is 5-35 mm.
The molded particles are charged at 60 deg.C under 1MPa of CO 2 And (3) carrying out flue gas curing in simulated flue gas with the concentration of 20% and the concentration of water vapor of 15% for 6 hours, taking out after curing, and placing in a normal-temperature normal-pressure environment for curing for 28 days. The 7-day compressive strength was 3.452MPa, as shown in Table 2.
The composite particles before and after the flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.63%, as shown in table 2.
Example 4
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 4 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 425 parts of portland cement, 30 parts of finely ground fly ash, 13 parts of finely ground ash, 3 parts of desulfurized gypsum, 3 parts of potassium hydroxide and 11 parts of refractory soil, putting the materials into a stirrer, stirring the materials for 30 minutes, putting the materials into a disc granulator, granulating the materials, uniformly spraying 30 parts of water on the surface of powder in the granulation process, and forming the particles, wherein the particle size of the formed particles is 5-35 mm.
Shaping ofThe granule is charged at 60 deg.C under 1MPa of pressure and CO 2 And (3) carrying out flue gas curing in simulated flue gas with the concentration of 20% and the concentration of 15% for 6 hours, taking out after curing, and placing in a normal-temperature normal-pressure environment for curing for 28 days. The 7-day compressive strength was 4.112MPa, as shown in Table 2.
The composite particles before and after flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.54%, as shown in table 2.
Example 5
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 3 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 35 parts of cement, 20 parts of pulverized coal ash, 15 parts of pulverized ash, 2 parts of desulfurized gypsum, 2 parts of sodium hydroxide and 10 parts of kaolin, putting the materials into a stirrer, stirring for 30 minutes, putting the materials into a granulator, extruding and granulating, and uniformly spraying 20 parts of water on the surface of powder in the granulation process to form particles, wherein the particle size of the formed particles is 5-35 mm.
The molded particles have a charging temperature of 60 deg.C, a pressure of 0.5MPa, and CO 2 And (3) carrying out flue gas curing in simulated flue gas with the concentration of 10% and the concentration of 5% of water vapor for 1 hour, taking out after curing, and placing in a normal-temperature normal-pressure environment for curing for 28 days. The 7-day compressive strength was 4.532MPa, as shown in Table 2.
The composite particles before and after flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.14%, as shown in table 2.
Example 6
And putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling for 5 hours, wherein the particle size of particles obtained after ball milling is 50-100 mu m.
Weighing 425 parts of portland cement, 35 parts of finely ground fly ash, 25 parts of finely ground ash, 3 parts of finely ground desulfurized gypsum, 3 parts of calcium oxide and 12 parts of kaolin, putting the materials into a stirrer, stirring for 30 minutes, putting the materials into a disc granulator, granulating, uniformly spraying 30 parts of water on the surface of powder in the granulation process, and forming particles, wherein the particle size of the formed particles is 5-35 mm.
Feeding the formed granulesTemperature of 200 deg.C, pressure of 2.0MPa, and CO 2 Flue gas curing is carried out in simulated flue gas with the concentration of 50% and the concentration of 25% for 12 hours, and the flue gas is taken out after curing and is placed in a normal-temperature normal-pressure environment for curing for 28 days. The 7-day compressive strength was 3.726MPa, as shown in Table 2
The composite particles before and after flue gas curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 5.39%, as shown in table 2.
Comparative example 1
Weighing 425 parts of portland cement, 30 parts of pulverized coal ash, 13 parts of pulverized ash and 3 parts of desulfurized gypsum, putting into a stirrer to stir for 30 minutes without adding an alkaline activator, then putting into a disc granulator to granulate, and uniformly spraying 30 parts of water on the surface of powder in the granulation process to form granules. The prepared granules were directly cured naturally without flue gas curing, and the compressive strength was 2.472MPa after 7 days, which was reduced by 3.306MPa compared to the composite granules prepared in example 1, as shown in table 2.
The composite particles before and after natural curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 0.29%, as shown in table 2.
Comparative example 2
Weighing 425 parts of portland cement, 30 parts of pulverized coal ash, 13 parts of pulverized ash, 3 parts of desulfurized gypsum, 3 parts of sodium hydroxide and 11 parts of kaolin, putting the materials into a stirrer, stirring for 30 minutes, putting the materials into a disc granulator for granulation, and uniformly spraying 30 parts of water on the surface of powder in the granulation process to form granules. The prepared particles are directly naturally cured without flue gas curing, and an electron microscope scanning picture of curing for 7 days is shown in figure 2 (b), so that the particle structure is looser and the porosity is high. The 7-day compressive strength was 2.824MPa, which is a 2.954MPa reduction in compressive strength compared to the granules prepared in example 1, as shown in Table 2.
The composite particles before and after natural curing were weighed, and the carbon fixation rate of the composite particles was calculated to be 0.34%, as shown in table 2.
TABLE 2
| Compressive strength (MPa) | Carbon fixation Rate (%) | |
| Example 1 | 5.778 | 5.47 |
| Example 2 | 6.150 | 5.35 |
| Example 3 | 3.452 | 5.63 |
| Example 4 | 4.112 | 5.54 |
| Example 5 | 4.532 | 5.14 |
| Example 6 | 3.726 | 5.39 |
| Comparative example 1 | 2.472 | 0.29 |
| Comparative example 2 | 2.824 | 0.34 |
The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and scope of the invention are intended to be included therein.
Claims (10)
1. A composite particle capable of adsorbing carbon dioxide, which is characterized in that: the paint comprises the following components in parts by weight:
35-40 parts of Portland cement, 20-35 parts of fly ash, 15-25 parts of bottom slag, 2-3 parts of desulfurized gypsum, 2-3 parts of alkaline activator, 10-12 parts of binder and 20-30 parts of water.
2. The carbon dioxide adsorbable composite particle according to claim 1, wherein: the alkaline activator is one of sodium hydroxide, potassium hydroxide and calcium oxide.
3. The carbon dioxide adsorbable composite particle according to claim 1 or 2, wherein: the binder is one of kaolin, refractory soil and water glass.
4. The method for producing carbon dioxide adsorbing composite particles according to any one of claims 1 to 3, comprising:
putting the fly ash, the bottom slag and the desulfurized gypsum into a ball mill for ball milling;
step two, putting the fly ash, the bottom slag, the desulfurized gypsum, the cement, the alkali activator and the binder which are obtained after ball milling in the step one into a stirrer for stirring to obtain a uniformly mixed powdery mixture;
step three, putting the powdery mixture obtained in the step two into a granulator for spheronization or extrusion granulation;
and step four, carrying out flue gas curing and natural curing on the particles obtained in the step three.
5. The method of manufacturing according to claim 4, characterized in that: in the first step, the particle size of the particles obtained after ball milling is 50-100 μm.
6. The production method according to claim 4 or 5, characterized in that: in the third step, the formed particles are spherical or ellipsoidal.
7. The method of claim 6, wherein: in the third step, the particle size of the formed particles is 5 mm-35 mm.
8. The production method according to claim 4 or 7, characterized in that: in the fourth step, the flue gas is maintained in an industrial source of CO 2 The method is carried out in a flue gas atmosphere; the curing flue gas contains 10-50% of CO 2 5% -25% of water vapor; the temperature of the curing flue gas is 60-200 ℃.
9. The method for producing according to claim 8, characterized in that: in the fourth step, the flue gas curing time is 1-12 hours; the flue gas curing pressure is 0.5 MPa-2.0 MPa.
10. The production method according to claim 4 or 7, characterized in that: and in the fourth step, the natural curing process is carried out at normal temperature and normal pressure, and the curing time is 7-30 days.
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