CN112250097A - Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof - Google Patents

Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof Download PDF

Info

Publication number
CN112250097A
CN112250097A CN202011141239.2A CN202011141239A CN112250097A CN 112250097 A CN112250097 A CN 112250097A CN 202011141239 A CN202011141239 A CN 202011141239A CN 112250097 A CN112250097 A CN 112250097A
Authority
CN
China
Prior art keywords
adsorbent
calcium
temperature
microstructure
gel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011141239.2A
Other languages
Chinese (zh)
Inventor
罗聪
罗童
张立麒
李小姗
邬凡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN202011141239.2A priority Critical patent/CN112250097A/en
Publication of CN112250097A publication Critical patent/CN112250097A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention discloses a method for regulating and controlling calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and its preparation method, sol of the inventionThe ignition stage in the gel combustion synthesis process adopts different ignition temperatures of 300-900 ℃, and different micro-morphology adsorbents are observed to be formed by a detection means of a transmission electron microscope, which shows that the calcium-based CO can be regulated and controlled by controlling the temperature to be ignited at constant temperature of 300-900 DEG C2The microstructure of the adsorbent; the invention finds that spherical nano calcium oxide particles with different particle sizes appear in samples with different ignition temperatures within the ignition temperature range of 300-500 ℃, the particles play an important role in enhancing the reaction rate of the adsorbent, and the prepared adsorbent has higher CO content2The capture rate.

Description

Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a method for regulating and controlling calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2An adsorbent and a preparation method thereof.
Background
Large emission of CO for human activities2The influence of greenhouse effect on ecological environment is continuously intensified. Coal still dominates the current energy structure of China, wherein CO discharged by coal-fired power plants2The total amount is huge and cannot be ignored. CO after combustion2In the technical field of trapping, the calcium-based adsorbent has a series of advantages of wide sources, low price, renewable utilization, large adsorption capacity and the like, thereby gaining wide attention.
However, at present, for calcium-based sorbents, an unavoidable problem is that with CO2The trapping process is carried out, the product calcium carbonate is accumulated on the outer layer of the adsorbent to block pores, and the reaction rate is reduced when the reaction enters a product layer diffusion stage; and the sintering action causes the CO of the sorbent to increase as the number of carbonation-calcination cycles increases2The trapping capacity rapidly decreases. To improve the performance of natural calcium-based sorbents, current research efforts have focused on increasing the CO of calcium-based sorbents2Capture rate and capture capacity and delay of CO under multiple cycles2The trapping ability is decreased. Among them, the sol-gel combustion synthesis method, as an important technique for synthesizing nanomaterials, has also been used in recent years for research on the preparation of nano-scale calcium-based adsorbents.
Therefore, the temperature of the molten metal is controlled,how to develop a method for regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2The adsorbent and the preparation method thereof become a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2The inventor adopts different ignition temperatures of 300-900 ℃ in the ignition stage of the sol-gel combustion synthesis process, observes that the adsorbents with different microscopic appearances are formed by the detection means of a transmission electron microscope, and shows that the calcium-based CO can be regulated and controlled by controlling the temperature to be ignited at constant temperature of 300-900 ℃ and controlling the temperature to be ignited at different temperatures of 300-900 DEG C2The microstructure of the adsorbent; the invention finds that spherical nano calcium oxide particles with different particle sizes appear in samples with different ignition temperatures within the ignition temperature range of 300-500 ℃, the particles play an important role in enhancing the reaction rate of the adsorbent, and the prepared adsorbent has higher CO content2The capture rate can reach 54 to 68 percent of the maximum conversion rate in the carbonation reaction stage within 1 to 2 min.
In a first aspect of the invention, there is provided a method of modulating calcium-based CO2A method of microstructure of an adsorbent, the method comprising:
dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
carrying out thermostatic water bath on the mixed solution to obtain gel;
aging and drying the gel to obtain dry gel;
the xerogel is ignited at constant temperature, calcined after being burnt out, and calcium-based CO with different microstructures is obtained by controlling the ignition temperature at the constant temperature to be 300-900 DEG C2An adsorbent.
In some embodiments, the molar ratio of the calcium nitrate tetrahydrate, the citric acid monohydrate, and the deionized water in the mixed solution is 1: 1: (33-37).
In some embodiments, the temperature in the thermostatic water bath is 75-85 ℃ and the time is 3-5 h.
In some embodiments, the aging is carried out at a temperature of 23-27 ℃ for 18-22 hours.
In some embodiments, the drying comprises: drying for 3-6 h at 75-85 ℃, and then drying for 10-14 h at 100-120 ℃.
In some embodiments, the calcination temperature is 840 to 860 ℃ and the calcination time is 15 to 25 min.
In a second aspect of the invention, a high performance calcium based CO is provided2A method of making an adsorbent, the method comprising:
dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
carrying out thermostatic water bath on the mixed solution to obtain gel;
aging and drying the gel to obtain dry gel;
igniting the xerogel at the constant temperature of 300-500 ℃, and burning out to obtain a reaction material;
calcining the reaction material to obtain high-performance calcium-based CO2An adsorbent.
In a third aspect of the invention, a high-performance calcium-based CO prepared by the method is provided2An adsorbent.
The adsorbent has high CO content2The capture rate can reach 54 to 68 percent of the maximum conversion rate in the carbonation reaction stage within 1 to 2 min.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a method for regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2The present inventor adopts different ignition temperatures of 300-900 ℃ in the ignition stage of the sol-gel combustion synthesis process, and observes that the adsorbents with different micro-morphologies are formed by the detection means of a transmission electron microscope, which shows that the temperature is controlled to be 300-900 ℃ and different temperaturesIgniting at constant temperature to regulate calcium-based CO2The microstructure of the adsorbent; the invention finds that spherical nano calcium oxide particles with different particle sizes appear in samples with different ignition temperatures within the ignition temperature range of 300-500 ℃, the particles play an important role in enhancing the reaction rate of the adsorbent, and the prepared adsorbent has higher CO content2The capture rate can reach 54 to 68 percent of the maximum conversion rate in the carbonation reaction stage within 1 to 2 min.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of a method for regulating calcium-based CO according to an embodiment of the present invention2A flow diagram of a method of microstructure of an adsorbent;
FIG. 2 shows a high performance calcium-based CO provided by an embodiment of the present invention2A flow diagram of a method of making the adsorbent;
FIG. 3 is TEM images of sorbents prepared at different ignition temperatures, wherein (a) is 300 ℃; (b)400 ℃; (c)500 ℃; (d)600 ℃; (e)700 ℃; (f)800 ℃; (g)900 ℃;
FIG. 4 is a TEM image showing the appearance of spherical nano calcium oxide in the adsorbents prepared at different ignition temperatures; wherein, (a) is 300 ℃; (b)400 ℃; (c) at 500 ℃.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by an existing method.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, a method for modulating calcium-based CO is provided2A method of microstructure of an adsorbent, as shown in fig. 1, the method comprising:
s101, dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
s102, carrying out thermostatic water bath on the mixed solution to obtain gel;
s103, ageing and drying the gel to obtain dry gel;
s104, igniting the xerogel at constant temperature, calcining after the xerogel is burnt out, and obtaining calcium-based CO with different microstructures by controlling the ignition temperature at the constant temperature to be 300-900 DEG C2An adsorbent.
The inventor adopts different ignition temperatures of 300-900 ℃ in the ignition stage of the sol-gel combustion synthesis process, observes that different adsorbents with microscopic appearances are formed by a detection means of a transmission electron microscope, and shows that the calcium-based CO can be regulated and controlled by controlling the temperature to be ignited at constant temperature of 300-900 ℃2The microstructure of the adsorbent;
in the preparation method, nitrate of calcium is used as a precursor, an organic substance is used as a fuel and a reducing agent, the mixture is stirred to form gel, the gel is ignited at a certain temperature to spontaneously combust, so that the organic substance and the nitrate generate oxidation-reduction reaction and generate gas. The modified calcium-based adsorbent can be obtained after calcination.
By changing certain processes in the preparation process, the microstructure of the adsorbent can be significantly changed. The performance of the adsorbent is strongly correlated with the microstructure. The ignition temperature is an important parameter in the preparation process, and the oriented control of the micro-morphology of the adsorbent can be realized by changing the ignition temperature, so that the effect of influencing the performance of the adsorbent is achieved.
When the temperature is lower than 200 ℃, the organic matters are insufficiently combusted due to the excessively low temperature in the combustion stage, the total gas release amount is reduced in the combustion process, the specific surface area and the pore volume of the finally prepared adsorbent are reduced, and the performance is deteriorated. When the temperature is higher than 900 ℃, the sintering effect is obviously intensified due to the overhigh temperature, the average grain diameter is enlarged due to the fusion of crystal grains, the specific surface area and the pore volume are rapidly reduced, and the performance attenuation is serious, so that the temperature higher than 900 ℃ is not suitable for preparing the adsorbent. The temperature in these two cases can control the morphology, but is not suitable for preparing high-performance calcium-based adsorbents.
In some embodiments, the molar ratio of the calcium nitrate tetrahydrate, the citric acid monohydrate, and the deionized water in the mixed solution is 1: 1: (33-37). Preferably, the molar ratio is 1: 1: 35; when the amount of water added is extremely large (e.g., 1: 100), the hydrolysis proceeds sufficiently and rapidly, but the increase of the amount of water is limited to increase the adsorbent, and the gel formation time becomes long and the crystal grains become large by the excessive amount of water. The added water amount is extremely small (such as 1: 10), the hydrolysis cannot be completed, and the capture performance of the adsorbent circulating CO2 finally prepared is reduced by 20-40%. Taken together, the molar ratio is 1: 1: 35 is the optimum amount of water added to balance preparation time with sorbent performance.
In some embodiments, the temperature in the thermostatic water bath is 75-85 ℃ and the time is 3-5 h. The temperature of the constant-temperature water bath is too low, the hydrolysis speed is slow, the hydrolysis is insufficient, the time for forming gel is prolonged, and the performance of the finally prepared adsorbent is poor; the water bath temperature is too high, and the water in the solution is evaporated too fast, which is not favorable for forming stable gel.
In some embodiments, the aging is carried out at a temperature of 23-27 ℃ for 18-22 hours. The influence of the aging temperature on the adsorbent is small, the adsorbent is aged at room temperature basically, and the small-amplitude temperature change cannot cause large influence. The greater effect is the aging time. Such as: the absence of an aging process or an extremely long aging time may result in insufficient formation of stable three-dimensional network structure of particles in the gel, resulting in non-uniform particle size distribution and poor performance of the finally prepared adsorbent. If the aging time is too long, the particle size of the finally prepared adsorbent is obviously increased, and the performance is influenced.
In some embodiments, the drying comprises: drying for 3-6 h at 75-85 ℃, and then drying for 10-14 h at 100-120 ℃. The purpose of the first drying is to remove free water in the gel; the purpose of the second drying is to remove crystal water from the gel.
In some embodiments, the calcination temperature is 840 to 860 ℃ and the calcination time is 15 to 25 min. The calcination temperature is too high, so that the sintering and fusing tendency of crystal grains is increased, and the performance of the adsorbent is further adversely affected; if the calcination temperature is too low, the residual carbon in the adsorbent due to insufficient combustion cannot be completely removed, and the performance is also adversely affected.
According to another exemplary embodiment of the present invention, a high performance calcium-based CO is provided2A method of making an adsorbent, as shown in fig. 2, the method comprising:
s201, dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
s202, carrying out thermostatic water bath on the mixed solution to obtain gel;
s203, ageing and drying the gel to obtain dry gel;
s204, igniting the xerogel at a constant temperature of 300-500 ℃, and burning out to obtain a reaction material;
s205, calcining the reaction material to obtain high-performance calcium-based CO2An adsorbent.
The inventor finds that spherical nano calcium oxide particles with different particle sizes appear in samples with different ignition temperatures in the ignition temperature range of 300-500 ℃, and the existence of the particles is used for reinforcing the adsorbentThe reaction rate plays an important role, and the prepared adsorbent has higher CO2The capture rate can reach 54 to 68 percent of the maximum conversion rate in the carbonation reaction stage within 1 to 2 min.
The specific conditions in the steps S201 to S203 are the same as those in the steps S101 to S103;
the method of the present application will be described in detail below with reference to examples, comparative examples, and experimental data.
Example 1
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at 300 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the muffle furnace rises to 850 ℃ to obtain calcium-based CO2The adsorbent has a micro-morphology as shown in FIG. 3 (a).
Example 2
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at 400 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the furnace is raised to 850 ℃,obtaining calcium-based CO2The adsorbent has a micro-morphology as shown in FIG. 3 (b).
Example 3
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at 500 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the muffle furnace rises to 850 ℃ to obtain calcium-based CO2The adsorbent has a micro-morphology as shown in FIG. 3 (c).
Example 4
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at 600 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the muffle furnace rises to 850 ℃ to obtain calcium-based CO2The adsorbent has a micro-morphology as shown in FIG. 3 (d).
Example 5
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at 700 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the muffle furnace rises to 850 ℃ to obtain calcium-based CO2The adsorbent has a micro-morphology as shown in FIG. 3 (e).
Example 6
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the dry gel into a muffle furnace at 800 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again and calcining the muffle furnace for 20min when the temperature of the muffle furnace rises to 850 ℃ to obtain calcium-based CO2The adsorbent has a microstructure shown in FIG. 3 (f).
Example 7
1. Dissolving a precursor calcium nitrate tetrahydrate and citric acid monohydrate in deionized water to obtain a mixed solution, wherein the molar ratio of the calcium nitrate to the citric acid to the deionized water in the raw materials is 1: 1: 35;
2. stirring the mixed solution in a water bath with constant temperature of 80 ℃ for 4 hours until gel is formed;
3. after the gel is formed, the sample is aged at room temperature for 19h, dried in an oven at 80 ℃ for 5h, and then dried at 110 ℃ for 12 h to obtain xerogel;
4. directly putting the xerogel into a muffle furnace at the temperature of 900 ℃ for ignition;
5. taking out the muffle furnace after the sample is burnt out, putting the muffle furnace again when the furnace temperature reaches 850 ℃ and calcining the muffle furnace for 20min to obtain calcium-based CO2The micro-topography of the adsorbent is shown in FIG. 3 (g).
Comparative example 1
In this comparative example, the ignition temperature was 200 ℃ and the rest was the same as in example 1.
Comparative example 2
In this comparative example, the ignition temperature was 1000 ℃ and the rest was the same as in example 1.
Test example 1
Calcium-based CO prepared in each example and each comparative example2The performance of the adsorbents was measured and counted as shown in table 1. The test conditions are as follows: 1) a carbonation stage: 650 ℃, 20min, 100ml/min total gas flow, atmosphere: 15% CO2+85％N22) And (3) a calcination stage: 850 ℃, 10min, 100ml/min total gas flow, atmosphere: 100% N2The number of cycles: 20;
TABLE 1
Figure RE-GDA0002785676130000081
From the data in table 1, it can be seen that:
in comparative example 1, the ignition temperature was 200 ℃ and the first cycle CO2The trapping capacity is only 0.50;
in comparative example 2, the ignition temperature was 1000 ℃ and the first cycle CO2The trapping capacity was only 0.44;
with the rise of the ignition temperature, the prepared adsorbent has obvious agglomeration tendency, increased boundary fusion tendency, gradually obvious sintering effect, gradually closed interparticle pores, gradually rough particle edges and gradually increased average particle size. Accordingly, the carbonation reaction rate and the initial conversion rate are gradually reduced along with the increase of the ignition temperature in the preparation process, but the cycle performance of the prepared adsorbent is more stable along with the increase of the ignition temperature. The data show that by controlling the temperature to be ignited at constant temperature of 300-900 ℃,can regulate and control calcium-based CO2The microstructure of the adsorbent; further regulate and control calcium-based CO2The relative properties of the adsorbent.
FIG. 4 is a TEM image showing the appearance of spherical nano calcium oxide in the adsorbents prepared at different ignition temperatures; as can be seen from fig. 4, spherical nano calcium oxide particles having different particle sizes appear in samples having different ignition temperatures in the ignition temperature range of 300 to 500 ℃. And the presence of these particles plays a very important role in enhancing the reaction rate of the sorbent, first cycle CO in examples 1-3 in table 12Capacity for Capture, first cycle CO2The capture rate is greatly improved compared with the front and rear groups. Therefore, the high-performance calcium-based CO can be obtained by controlling the ignition temperature to be 300-500 DEG C2An adsorbent. The high-performance calcium-based CO of the invention2Adsorbent means first cycle CO2Capacity for Capture, first cycle CO2The capture rate is high.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. A kind of accentCalcium controlled based CO2A method of microstructure of an adsorbent, characterized in that the method comprises:
dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
carrying out thermostatic water bath on the mixed solution to obtain gel;
aging and drying the gel to obtain dry gel;
the xerogel is ignited at constant temperature, calcined after being burnt out, and calcium-based CO with different microstructures is obtained by controlling the ignition temperature at the constant temperature to be 300-900 DEG C2An adsorbent.
2. The method of claim 1 for modulating calcium-based CO2The method for the microstructure of the adsorbent is characterized in that in the mixed solution, the molar ratio of the calcium nitrate tetrahydrate, the citric acid monohydrate and the deionized water is 1: 1: (33-37).
3. The method of claim 1 for modulating calcium-based CO2The method for the microstructure of the adsorbent is characterized in that the temperature in the constant-temperature water bath is 75-85 ℃ and the time is 3-5 hours.
4. The method of claim 1 for modulating calcium-based CO2The method for the microstructure of the adsorbent is characterized in that in the aging process, the temperature is 23-27 ℃, and the time is 18-22 h.
5. The method of claim 1 for modulating calcium-based CO2A method of microstructure of an adsorbent, wherein the drying comprises: drying for 3-6 h at 75-85 ℃, and then drying for 10-14 h at 100-120 ℃.
6. The method of claim 1 for modulating calcium-based CO2The method for the microstructure of the adsorbent is characterized in that the calcination temperature is 840-860 ℃, and the calcination time is 15-25 min.
7. High-performance calcium-based CO2A method for producing an adsorbent, the method comprising:
dissolving calcium nitrate tetrahydrate and citric acid monohydrate into deionized water to obtain a mixed solution;
carrying out thermostatic water bath on the mixed solution to obtain gel;
aging and drying the gel to obtain dry gel;
igniting the xerogel at the constant temperature of 300-500 ℃, and burning out to obtain a reaction material;
calcining the reaction material to obtain high-performance calcium-based CO2An adsorbent.
8. A high performance calcium based CO according to claim 62The preparation method of the adsorbent is characterized in that in the mixed solution, the molar ratio of the calcium nitrate tetrahydrate to the citric acid monohydrate to the deionized water is 1: 1: (33-37).
9. A high performance calcium based CO according to claim 62The preparation method of the adsorbent is characterized in that the temperature in the constant-temperature water bath is 75-85 ℃, and the time is 3-5 hours; in the aging process, the temperature is 23-27 ℃, and the time is 18-22 h; the drying includes: drying for 3-6 h at 75-85 ℃, and then drying for 10-14 h at 100-120 ℃; the calcination temperature is 840-860 ℃, and the calcination time is 15-25 min.
10. A high performance calcium based CO prepared according to the method of any one of claims 7 to 92An adsorbent.
CN202011141239.2A 2020-10-22 2020-10-22 Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof Pending CN112250097A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011141239.2A CN112250097A (en) 2020-10-22 2020-10-22 Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011141239.2A CN112250097A (en) 2020-10-22 2020-10-22 Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112250097A true CN112250097A (en) 2021-01-22

Family

ID=74263252

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011141239.2A Pending CN112250097A (en) 2020-10-22 2020-10-22 Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112250097A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405495A (en) * 2022-02-16 2022-04-29 华中科技大学 Mesoporous calcium-based catalyst and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CONG LUO ET AL.: ""Manufacture of calcium-based sorbents for high temperature cyclic CO2 capture via a sol–gel process"", 《INTERNATIONAL JOURNAL OF GREENHOUSE GAS CONTROL》 *
WENQIANG LIU ET AL.: ""Performance Enhancement of Calcium Oxide Sorbents for Cyclic CO2 Capture A Review"", 《ENERGY FUELS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405495A (en) * 2022-02-16 2022-04-29 华中科技大学 Mesoporous calcium-based catalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107282030A (en) A kind of three-dimensional lignin porous carbon/zinc oxide composite and its preparation and the application in photocatalysis field
CN105271268B (en) A kind of monodisperse mesoporous silica microballoon powder and preparation method thereof
CN106824163B (en) Composite oxides and preparation method thereof
CN103754921A (en) Preparation method of monodisperse cerium oxide loose nanospheres
CN101486941A (en) Process for preparing iron based oxygen carrier
CN111333127A (en) Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof
CN105883780A (en) Method for preparing high-purity flake graphite
CN112250097A (en) Regulating calcium-based CO2Method for microstructure of adsorbent and high-performance calcium-based CO2Adsorbent and preparation method thereof
CN102180675A (en) Process for preparing gamma-AlON powder by chemical coprecipitation and carbothermal reduction method
CN110548528A (en) SiO 2/SiC material with core-shell structure and preparation method and application thereof
Liu et al. Fabrication of calcium zirconate fibers by the sol–gel method
CN113479934A (en) BiOCl nanosheet and preparation method and application thereof
CN112246213B (en) Calcium-based CO2Method for preparing adsorbent and product thereof
CN112316887A (en) Regulation and control calcium-based CO2Method for microstructure of adsorbent
CN111146435A (en) Spherical-like lithium manganate material and preparation method of raw material manganese dioxide thereof
KR20140114732A (en) Method for fabricating of YAG : Ce phosphor powder by polymer solution route and alumina seed application
CN114349041B (en) Preparation method of zinc sulfide and cobalt sulfide core-shell cube nanomaterial suitable for sodium ion battery electrode
CN110433669A (en) A kind of preparation method of ball-type manganese base lithium ion sieve composite membrane
CN106966423B (en) Foramen magnum-mesoporous-microporous alumina Zinc material of one kind and its preparation method and application
KR20220140466A (en) Composition for water splitting material
CN104326500A (en) Preparation method of fluffy nano yttrium oxide powder
CN111943253B (en) Bowl-shaped zinc oxide and preparation method thereof
CN108273559A (en) A kind of support type Fe2O3Composite photo-catalyst
JP2007070161A (en) Porous composite body, and method for producing the same
CN111450837A (en) Supported magnetically modified molybdenum oxide desulfurization catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210122

RJ01 Rejection of invention patent application after publication