CN116943602A - Porous solid adsorbent for carbon dioxide and preparation method thereof - Google Patents

Porous solid adsorbent for carbon dioxide and preparation method thereof Download PDF

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Publication number
CN116943602A
CN116943602A CN202311101688.8A CN202311101688A CN116943602A CN 116943602 A CN116943602 A CN 116943602A CN 202311101688 A CN202311101688 A CN 202311101688A CN 116943602 A CN116943602 A CN 116943602A
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boehmite
carbon dioxide
adsorbent
porous solid
solid adsorbent
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李博
王伟明
彭帅
刘豪
徐沛歆
邱明明
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Dongguan Keleipeng Atomization Technology Co ltd
Wuhan Textile University
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Dongguan Keleipeng Atomization Technology Co ltd
Wuhan Textile University
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    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • 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
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres

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  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The application discloses a carbon dioxide porous solid adsorbent and a preparation method thereof, and relates to the technical field of carbon dioxide adsorption. The adsorbent comprises boehmite of hollow microspheres, wherein the surface of the boehmite is loaded with alkali metal or alkaline earth metal carbonate, and the corresponding preparation method comprises the steps of taking the boehmite as a carrier and loading the alkali metal or alkaline earth metal carbonate on the boehmite by adopting an impregnation method. The adsorbent of the application perfectly combines the characteristic of graded porosity of the hollow microsphere boehmite with the characteristic of large carbon dioxide adsorption capacity of alkali metal or alkaline earth metal carbonate; the adsorbent has the advantages of large carbon dioxide adsorption capacity, low regeneration energy and stable cycle performance; meanwhile, the preparation method is simple in process and mild in reaction condition, and the prepared adsorbent has strong adsorption performance on carbon dioxide which is a main greenhouse gas.

Description

Porous solid adsorbent for carbon dioxide and preparation method thereof
Technical Field
The application relates to the technical field of carbon dioxide adsorption, in particular to a carbon dioxide porous solid adsorbent and a preparation method thereof.
Background
Due to frequent human activities, such as the burning of fossil fuels (coal, oil and natural gas) in large quantities, greenhouse gas concentrations increase, greenhouse effect exacerbation and global climate anomalies. Carbon dioxide (CO) 2 ) As a greenhouse gas, it is considered as a main cause of exacerbation of greenhouse effect, and thus how to effectively control CO 2 The emission of (c) becomes very important. In a plurality of COs 2 In the emission reduction technical route, CO 2 The capture, utilization and sequestration (CCUS) of (c) are considered as an indispensable technical route for achieving the emission reduction objective at the present stage. Wherein CO 2 Is considered as an integral part of the CCUS technology and is also an important difficulty in impeding the sustainable development of the CCUS technology. In various CO capturing 2 Of the processes of (2), the industrial application of chemisorption is the most mature and is considered the most potential for large scale CO capture 2 Is a technical route of the (a).
Among the various chemisorption methods, the porous solid adsorption method is easier to realize CO 2 The adsorption-desorption cycle process of the catalyst has great comprehensive advantages in the aspects of adsorption efficiency, energy consumption, environment, cost and the like. Porous solid adsorbent for adsorbing CO 2 The properties of (3) are closely related to the texture properties such as specific surface area, pore volume and average pore diameter, and the physicochemical properties such as the number of alkaline sites and alkali strength. Ideal CO 2 The adsorbent should meet the following criteria: low preparation cost, high mechanical strength, hydrothermal stability and chemical stability; high adsorption capacity, high selectivity, fast adsorption/desorption kinetics, high regeneration performance and long service life. Currently, commonly used CO 2 The porous solid adsorption material mainly comprises active carbon (base) material, carbon molecular sieve, carbon nano tube base material, zeolite, metal organic framework compound, metal oxide and hydrotalciteA compound, and the like. The general idea of development is for CO 2 Is characterized by weak acidity, and the surface of the porous solid material is grafted with alkaline components such as organic amine, alkali (earth) metal and the like, or the alkaline porous solid material is directly synthesized.
For alkaline components, alkali metal carbonates (e.g., K 2 CO 3 And Na (Na) 2 CO 3 ) Can be combined with CO in the presence of water 2 The reaction generates alkali metal bicarbonate, which has the advantages of large adsorption capacity, stable adsorption performance, low regeneration energy and the like, and the optimal working temperature (40-80 ℃) is highly consistent with the temperature of the waste gas of a fossil fuel power plant, thus the hydrogen carbonate is used in CO 2 The use of alkali metal carbonates as adsorbents has received considerable attention in adsorption.
But of pure K 2 CO 3 /Na 2 CO 3 In the presence of CO at low temperature and constant pressure 2 The problem of low absorptivity is that the catalyst is generally loaded on a proper carrier to increase the active reaction area, thereby achieving the efficient and energy-saving CO adsorption 2 Of which the most commonly used support is activated alumina. However, CO prepared from conventional activated alumina-supported alkali metal carbonates 2 The adsorption capacity of adsorbents is generally low.
Disclosure of Invention
In view of the above problems, the present application provides a CO 2 The porous solid adsorbent has the advantages of large adsorption capacity, low regeneration energy and stable cycle performance, and the preparation method is simple and the reaction condition is mild.
The application solves the technical problems by adopting the following technical scheme:
a porous solid adsorbent for carbon dioxide comprising hollow microspheres of boehmite, the surface of which is loaded with alkali or alkaline earth carbonate. The adsorbent of the application has rich pore structure and surface alkaline sites, and the rich pore structure increases CO 2 With the adsorbent, more surface alkaline sites are used for adsorbing CO 2 。
In a specific embodiment, the alkali metal or alkaline earth metal carbonate is K 2 CO 3 。
In a specific embodiment, the K 2 CO 3 The mass fraction of the porous solid adsorbent is 10-38wt%.
In a specific embodiment, the K 2 CO 3 The mass fraction of the porous solid adsorbent is 27wt%.
In another aspect, the present application also provides a method for preparing a porous solid adsorbent for carbon dioxide, comprising: the boehmite is used as a carrier, and alkali metal or alkaline earth metal carbonate is loaded on the boehmite by adopting an impregnation method.
In a specific embodiment, the process of loading alkali metal or alkaline earth metal carbonates onto boehmite by impregnation comprises: preparing an aqueous solution of alkali metal or alkaline earth metal carbonate, adding the boehmite into the aqueous solution, stirring and mixing, and heating and drying to obtain the product.
In a specific embodiment, the alkali metal or alkaline earth metal carbonate is K 2 CO 3 。
In a specific embodiment, the K 2 CO 3 Occupy the K 2 CO 3 And boehmite in an amount of 10 to 40% by weight.
In a specific embodiment, the K 2 CO 3 Occupy the K 2 CO 3 And boehmite in an amount of 30% by weight.
Compared with the prior art, the carbon dioxide porous solid adsorbent and the preparation method thereof have the following main advantages:
(1) The boehmite is used as a carrier, has rich pore structure and increases CO 2 Contact with the adsorbent; the alkali (earth) metal carbonate supported on its surface provides surface alkaline sites for CO in the presence of water 2 The reaction generates bicarbonate, and has the advantages of large adsorption capacity, stable adsorption performance, low regeneration energy and the like; the carbon dioxide porous solid adsorbent obtained by combining the two has the advantages of large adsorption capacity, high adsorption efficiency, low regeneration energy and stable cycle performance;
(2) The preparation method has simple process and warm reaction conditionAnd, preparing the porous solid adsorbent for main greenhouse gas CO 2 Has stronger adsorption performance.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of boehmite prepared according to one embodiment of the application (showing images at different magnifications);
FIG. 2 is an XRD spectrum of boehmite of FIG. 1;
FIG. 3 is an SEM image of a porous solid adsorbent of carbon dioxide prepared in example 1 (images showing different magnifications);
FIG. 4 is an SEM image of a porous solid adsorbent of carbon dioxide prepared in example 2 (images showing different magnifications);
FIG. 5 is an SEM image of a porous solid adsorbent of carbon dioxide prepared in example 3 (images showing different magnifications);
FIG. 6 is an SEM image of a porous solid adsorbent of carbon dioxide prepared in example 4 (images showing different magnifications);
FIG. 7 is an SEM image of the adsorbent prepared according to the comparative example (images at different magnifications are shown);
FIG. 8 is an adsorption-desorption cycle chart of the carbon dioxide porous solid adsorbent prepared in example 3.
Description of the embodiments
The present application will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present application to those skilled in the art. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the application. All other embodiments, based on the embodiments of the application, which are obtained by a person of ordinary skill in the art without making any inventive effort, are within the scope of the application.
As mentioned in the background, porous solid adsorption to adsorb CO 2 Is a promising technical route. On this technical route, in order to obtain CO adsorption 2 The porous material with excellent performance requires that the carrier has better thermal stability, and can still maintain the unique pore structure (specific surface area, pore volume and average pore diameter) at higher temperature; it is also desirable that its surface has a sufficiently high number of basic sites and is highly dispersed to enhance its CO 2 Adsorption capacity.
Searching for more efficient CO 2 During the adsorbent process, the use of boehmite (AlOOH) has been rarely studied. The literature describes that AlOOH, also known as kyropoulos, is one of the very important aluminium ore minerals, the crystal structure of which belongs to the monoclinic system; it is often present in fibrous or platelet form, and is usually white, off-white or yellowish-white in color; alOOH is a hydrated aluminum oxide that contains crystalline water molecules in its crystal structure. In the laboratory, boehmite can be synthesized by hydrolyzing an aluminum salt solution or calcining aluminum hydroxide by heating. Boehmite has certain chemical stability, but can also change with the change of environmental conditions; under the acidic condition, the boehmite can be dissolved and generate corresponding aluminum salt; under alkaline conditions, boehmite can be converted to aluminum hydroxide.
At the same time alkali metal carbonates (e.g. K 2 CO 3 And Na (Na) 2 CO 3 ) Can be combined with CO in the presence of water 2 The reaction generates alkali metal bicarbonate, which has the advantages of large adsorption capacity, stable adsorption performance, low regeneration energy and the like, and the optimal working temperature (40-80 ℃) is highly consistent with the temperature of the waste gas of a fossil fuel power plant, thus the hydrogen carbonate is used in CO 2 The concentrated use of alkali metal carbonates as adsorbents has received considerable attention.
The application creatively combines the two, takes the hollow microsphere boehmite as a carrier and loads alkali (earth) metal carbonate to prepare the carbon dioxideThe porous solid adsorbent has very excellent CO 2 The adsorption quantity achieves unexpected technical effects.
The raw materials mentioned in the application are all commercially available and obtained unless otherwise specified.
The application provides a carbon dioxide porous solid adsorbent, which comprises boehmite of hollow microspheres, wherein the surface of the boehmite is loaded with alkali metal or alkaline earth metal carbonate. The adsorbent has rich pore structure and surface alkaline sites; rich pore structure increases CO 2 With the adsorbent, more surface alkaline sites are used for adsorbing CO 2 . The corresponding preparation method of the adsorbent is that boehmite is used as a carrier, and alkali metal or alkaline earth metal carbonate is loaded on the boehmite by adopting an impregnation method; the preparation method has simple process and mild reaction conditions.
Wherein, the hollow microsphere boehmite raw material can be commercial raw material purchased, wherein, the hollow microsphere is mainly spherical raw material particles, the inside of the spherical particles is hollow and provided with a shell, and the average diameter of the spherical particles is in the micron order. The surface of the boehmite of the hollow microsphere has a layered pore structure.
The hollow microsphere boehmite can also be prepared by the following hydrothermal method: dissolving aluminum sulfate in water, adding urea and malonic acid, and stirring until the mixture is clear; and then heating for reaction, cooling to room temperature, washing and drying the precipitate to obtain the hollow microsphere boehmite. Specific examples of the preparation of hollow microsphere boehmite are:
first, 15.0g of aluminum sulfate was dissolved in 140ml of deionized water, 6.8g of urea and 0.8g of malonic acid were added sequentially, and stirred until clear. Then transferring the solution to a 200ml hydrothermal reactor, carrying out hydrothermal reaction for 12 hours in an oven at 160 ℃, naturally cooling the precipitate to room temperature, washing for multiple times, filtering, drying at 60 ℃ for 1 day and night, and drying at 150 ℃ for 3 hours. The obtained white powder is hollow microsphere boehmite.
The preparation method takes malonic acid as a structure guiding agent, and prepares the graded porous hollow microsphere boehmite by an economic and simple hydrothermal method. The appearance and the structure of the hollow microsphere are shown in figure 1, and the hollow microsphere is uniform in appearance, the particle size is about 7-9 mu m, the thickness of a shell layer is about 2-3 mu m, and the surface of the hollow microsphere has a rich pore structure as shown in figure 1; using N 2 The specific surface area measured by the adsorption-desorption method is 168.7m 2 Per gram, pore volume of 0.73cm 3 And/g, the average pore diameter is 18.4nm. Because the catalyst has shell layer and multi-stage pore structure, CO is reduced 2 And further obtain stronger CO 2 Adsorption capacity. In addition, as shown in the XRD spectrum of FIG. 2, only diffraction peaks belonging to AlOOH (ICDD PDF file 01-088-2112) are detected, which indicates that the purity of the prepared hierarchical porous hollow microsphere boehmite is higher.
In one embodiment, the carbonate of an alkali metal or alkaline earth metal supported on the surface of the hollow microsphere boehmite may be K 2 CO 3 、Na 2 CO 3 、MgCO 3 、CaCO 3 In (2), where K is only 2 CO 3 An example is described. It will be appreciated that K 2 CO 3 、Na 2 CO 3 、MgCO 3 、CaCO 3 Or other alkali (earth) metals, all of which are similar in nature to CO 2 Reaction (H) 2 O is present) to form bicarbonate salts, which can be loaded onto the surface of the hollow microsphere boehmite in a hydrothermal process.
The preparation process includes soaking hollow microsphere boehmite as carrier in K 2 CO 3 The hollow microsphere is loaded on boehmite, and specifically comprises the following steps: configuration K 2 CO 3 Adding hollow microsphere boehmite into the aqueous solution, stirring and mixing, and heating and drying to obtain the aqueous solution. In a specific embodiment, K 2 CO 3 The addition amount of (2) is K 2 CO 3 And the mass fraction of the hollow microsphere boehmite is 10 to 40wt%, more preferably 30wt%. K in the prepared carbon dioxide porous solid adsorbent 2 CO 3 The content of (2) is obtained by conversion according to the mass percentage of K element in EDS energy spectrum analysis, preferably K in the carbon dioxide porous solid adsorbent 2 CO 3 The mass fraction of (C) is 10-38wt%, more preferably27wt% is selected.
The application will be further described with reference to examples and figures.
Example 1: preparation of carbon dioxide porous solid adsorbent by taking hollow microsphere boehmite as carrier
Uses hollow microsphere boehmite as carrier and K as carrier 2 CO 3 Preparation of K by impregnation 2 CO 3 &AlOOH adsorbent. The preparation process comprises preparing K 2 CO 3 Adding 2.0g of hollow microsphere boehmite into the aqueous solution, wherein K 2 CO 3 The addition amount of (2) is K 2 CO 3 And 10wt% of the total mass of the hollow microsphere boehmite; soaking for 12 hr, filtering, drying at 60deg.C for 1 day and night, and drying at 150deg.C for 3 hr to obtain K 2 CO 3 &AlOOH adsorbent, SEM image of which is shown in FIG. 3.
Example 2: is different from example 1 in that K 2 CO 3 The addition amount of (2) is K 2 CO 3 20wt% of the total mass of the hollow microsphere boehmite, and the other steps are the same, thus obtaining K 2 CO 3 &An SEM image of the AlOOH adsorbent is shown in fig. 4.
Example 3: is different from example 1 in that K 2 CO 3 The addition amount of (2) is K 2 CO 3 30wt% of the total mass of the hollow microsphere boehmite, and the other steps are the same, thus obtaining K 2 CO 3 &An SEM image of the AlOOH adsorbent is shown in fig. 5.
Example 4: is different from example 1 in that K 2 CO 3 The addition amount of (2) is K 2 CO 3 40wt% of the total mass of the hollow microsphere boehmite, and the other steps are the same, thus obtaining K 2 CO 3 &An SEM image of the AlOOH adsorbent is shown in fig. 6.
Comparative example: a commercial alumina was selected as a control, and an adsorbent was prepared in the same manner as in example 1, wherein K 2 CO 3 The addition amount of (2) is K 2 CO 3 And Al 2 O 3 30wt% of the total mass, the other steps being the same; the adsorbent is K 2 CO 3 &Al 2 O 3 An SEM image thereof is shown in fig. 7.
Referring to fig. 3-7, it can be seen that the load K 2 CO 3 The shape and structure of the rear hollow microsphere boehmite are not changed. With K 2 CO 3 The increase of the number of the hollow microsphere boehmite surface can obviously observe K 2 CO 3 This results in some pores of the surface of the hollow microsphere boehmite being blocked, particularly on the adsorbent prepared in example 4 (as shown in fig. 6). In addition, EDS spectroscopy analysis of the adsorbents prepared in examples 1 to 4 and comparative example indicated that the energy scattering spectrum of K element was uniformly dispersed, namely K 2 CO 3 Uniformly dispersing on the surface of the hollow microsphere boehmite; meanwhile, calculating the K in the adsorbent according to the mass percent of the K element in the EDS result 2 CO 3 The mass percentages of the components are as follows: k in example 1 2 CO 3 The mass percentage of the adsorbent was 10wt%, K in example 2 2 CO 3 17wt% of the adsorbent, K in example 3 2 CO 3 The mass percent of the adsorbent is 27 percent, K in example 4 2 CO 3 The mass percentage of the adsorbent is 38 percent, and K in the comparative example 2 CO 3 The mass percentage of the adsorbent is 27wt%.
Using N 2 Adsorption-desorption methods specific surface areas, pore volumes, and pore size distributions of the respective adsorbents prepared in examples 1 to 4 and comparative examples were studied; the results are shown in Table 1 below.
TABLE 1 pore structure characteristics of adsorbents
Specific surface area (m) 2 /g） Pore volume (cm) 3 /g） Average pore diameter (nm)
Example 1 129.8 0.65 17.7
Example 2 75.8 0.46 17.1
Example 3 44.8 0.23 15.3
Example 4 33.9 0.17 14.5
Comparative example 189.8 0.37 2.1
The specific surface area of the adsorbents produced in examples 1 to 4 was dependent on K 2 CO 3 The load increases and decreases rapidly. For example, the adsorbents produced in example 1 and example 4 had specific surface areas of 129.8m, respectively 2 /g and 33.9m 2 And/g. This may be mainly due to two reasons, on the one hand, with K 2 CO 3 Increased loading, increased density of adsorbent, reduced surface area per unit massThe method comprises the steps of carrying out a first treatment on the surface of the On the other hand, due to K 2 CO 3 The load capacity is increased, and partial pores on the surface of the hollow microsphere boehmite are coated with K 2 CO 3 Occupancy, resulting in a decrease in the average pore diameter and pore volume, results in a rapid decrease in specific surface area. For example, the adsorbents obtained in example 1 had pore average diameters and pore volumes of 17.7nm and 0.65cm, respectively 3 Per g, while the average pore diameter and pore volume of the adsorbents obtained in example 4 were 14.5nm and 0.17cm, respectively 3 And/g. The average pore diameter of the adsorbents prepared in the comparative examples was mainly distributed between 1 and 4nm, and the average pore diameter of the adsorbents prepared in the examples was mainly distributed between 5 and 15 nm. All adsorbents except AlOOH diffraction peaks were used for CO 2 After adsorption, only KHCO is detected 3 Diffraction peaks (ICDD PDF file 01-070-1168) for K 2 CO 3 Has been completely converted into KHCO 3 。
CO 2 Evaluation of adsorption Performance
CO was performed on an analysis system 2 Adsorption and regeneration experiments. Wherein the inner diameter of a quartz tube in which a sample was placed was 8mm, 1.0g of the adsorbents prepared in examples 1 to 4 and comparative example were charged in batches at 100℃and N 2 Pretreating for 0.5h under the atmosphere, and then cooling to 60 ℃; at this temperature, water vapor is combined with N 2 Mixing into quartz tube, and maintaining for 5min.
And then N is added 2 Switch to 10% CO 2 /N 2 Mixture, CO 2 Adsorption experiments. The experimental conditions were that the liquid flow rate of water was 1.2ml/h, 10% CO 2 /N 2 The volume flow rate is 250ml/min, the adsorption temperature is 60 ℃, and the pressure is 1atm. And (5) detecting the adsorption tail gas in an online real-time manner by a gas analyzer.
After the adsorption experiment is completed, the inlet atmosphere is switched to N 2 Atmosphere, turn off the steam flow. The temperature was then increased to 120 ℃ for regeneration experiments. The regeneration experimental conditions are that N 2 The volume flow is 30ml/min, the regeneration temperature is 120 ℃, the regeneration time is 1h, and the pressure is 1atm.
CO 2 Curing process on adsorbents, i.e. CO 2 +H 2 O+K 2 CO 3 →2KHCO 3 . CO corresponding to the adsorbents prepared in examples 1 to 4 and comparative example 2 The adsorption amounts were 103.6mg/g, 138.3mg/g, 153.8. 153.8 mg/g, 149.2. 149.2 mg/g and 71.5. 71.5 mg/g, respectively.
The adsorbents of the present examples have very excellent CO compared to the comparative examples 2 The adsorption quantity achieves unexpected technical effects. The adsorbent of the embodiment of the application has rich pore structure and surface alkaline sites: on the one hand, the rich pore structure increases CO 2 Contact with the adsorbent; hollow microsphere adsorbents, on the other hand, have more surface alkaline sites than traditional adsorbents, i.e., they can expose more alkaline sites to adsorb CO 2 . Notably, the hollow microsphere adsorbent of example 4 was CO 2 The adsorption capacity was lower than that of the hollow microsphere adsorbent of example 3 (4.6 mg/g lower), probably due to excessive K aggregation on the hollow microsphere surface 2 CO 3 Blocking part of the pores. The graded porous hollow microsphere adsorbent has a nano-structured shell and a layered honeycomb pore structure, so that CO is reduced 2 And the hollow microsphere adsorbent has sufficient surface basicity sites.
In practical applications, the adsorbent need not only have a high CO content 2 The amount of adsorption, and after multiple adsorption-desorption cycles, still needs to maintain stable adsorption performance. To be used as CO 2 Stability of adsorbent, CO prepared in example 3 was selected 2 The adsorbent with the maximum adsorption amount is subjected to CO multiple times on the analysis system 2 Curing-regeneration experiments, CO 2 The curing and regeneration temperatures of (C) are 60℃and 120℃respectively, and the experimental results are shown in FIG. 8, which shows that even after 10 cycles, the catalyst is resistant to CO 2 The adsorption capacity of (2) is kept at the level of 150mg/g, and good reversibility and stability are shown.
The experimental or testing process involved in the application is as follows:
(1) After the sample was pretreated at a standard degassing station for 6 hours, N was performed under 77k liquid nitrogen conditions using an APSP2460 automatic specific surface area analyzer from Micromeritics, inc. of America 2 Adsorption-desorption test. Through instrument analysis, isothermal suction is obtainedThe specific surface area of the sample was obtained by the BET method on the attached-desorption curve.
(2) The morphology and elemental energy scattering spectra of the samples were measured using a thermal field emission scanning electron microscope (FESEM-EDS, JSM-7200F, JEOL, japan). The samples were tested after 60 seconds of spraying on an automatic metal spraying machine (JEC-3000 FC). The acceleration voltage of the SEM electron gun was 5KV, the emission current was 10 μA, and the working distance was 8mm.
(3) The phase composition of the samples was determined by an X-ray diffractometer (Smartlab SE, rigaku, japan) equipped with a Cu ka excitation source. Grinding the coarse particle sample to 100-200 meshes before the test, wherein the working voltage is 40KV, the working current is 30mA, and the scanning range is 10-80 degrees.
The above examples are only for the purpose of clearly illustrating the application and are not to be construed as a complete limitation of the embodiments. Other variations in form will be apparent to those of ordinary skill in the art in light of the foregoing description, and it is not necessary to present examples of all embodiments herein, but obvious variations are contemplated as falling within the scope of the application.

Claims (9)

1. A porous solid adsorbent for carbon dioxide, comprising:
a boehmite of hollow microspheres, the surface of which is loaded with carbonates of alkali metals or alkaline earth metals.
2. The porous solid carbon dioxide adsorbent of claim 1, wherein the carbonate of an alkali or alkaline earth metal is K 2 CO 3 。
3. The carbon dioxide porous solid adsorbent of claim 2, wherein the K 2 CO 3 The mass fraction of the porous solid adsorbent is 10-38wt%.
4. A carbon dioxide porous solid adsorbent according to claim 2 or 3, wherein said K 2 CO 3 Occupy the describedThe mass fraction of the porous solid adsorbent was 27wt%.
5. A preparation method of a carbon dioxide porous solid adsorbent is characterized in that boehmite is used as a carrier, and alkali metal or alkaline earth metal carbonate is loaded on the boehmite by adopting an impregnation method.
6. The method for preparing a porous solid adsorbent for carbon dioxide according to claim 5, wherein the process of supporting the carbonate of an alkali metal or an alkaline earth metal on boehmite by an impregnation method comprises: preparing an aqueous solution of alkali metal or alkaline earth metal carbonate, adding the boehmite into the aqueous solution, stirring and mixing, and heating and drying to obtain the product.
7. The method for preparing a porous solid adsorbent for carbon dioxide according to claim 5 or 6, wherein the carbonate of an alkali metal or an alkaline earth metal is K 2 CO 3 。
8. The method for preparing a porous solid adsorbent for carbon dioxide as claimed in claim 7, wherein said K is 2 CO 3 Occupy the K 2 CO 3 And boehmite in an amount of 10 to 40% by weight.
9. The method for preparing a porous solid adsorbent for carbon dioxide as claimed in claim 7, wherein said K is 2 CO 3 Occupy the K 2 CO 3 And boehmite in an amount of 30% by weight.
CN202311101688.8A 2023-08-30 2023-08-30 Porous solid adsorbent for carbon dioxide and preparation method thereof Pending CN116943602A (en)

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