Carbon dioxide solid adsorbent, method for preparing the same, and use thereof

Abstract

The application relates to the field of carbon capture adsorbents, and discloses a carbon dioxide solid adsorbent as well as a preparation method and application thereof. The carbon dioxide solid adsorbent comprises a carrier and a CO2 active component loaded on the carrier; the CO2 active component is one or two or more of a metal carbonate, an organic amine and a metal nitrate; the particle size of the carbon dioxide solid adsorbent is 200-300 mu m, the span of the particle size distribution width of the carbon dioxide solid adsorbent is 2.35-2.55, the pore size of the carbon dioxide solid adsorbent is 2-50 nm, and the dispersity of the CO2 active component in the carbon dioxide solid adsorbent is 0.8-0.9. The carbon dioxide solid adsorbent is uniform in particle size, the loaded CO2 active component is uniformly dispersed on the carrier, and the preparation process is simple.

Description

Technical Field

[0001] This invention relates to the field of carbon capture adsorbents, specifically to a solid carbon dioxide adsorbent, its preparation method, and its application. Background Technology

[0002] CO2 capture technologies for fossil fuels mainly include pre-combustion (e.g., IGCC), in-combustion (e.g., oxygen-enriched combustion and chemical looping combustion), and post-combustion capture (e.g., absorption, adsorption, and membrane separation). Due to its good adaptability, the most mature technology currently developed is wet post-combustion capture based on chemical absorption. However, this technology still suffers from problems such as high energy consumption for absorbent regeneration, strong corrosivity, and easy degradation. Supported solid CO2 adsorption technology overcomes these shortcomings of wet decarbonization, possessing advantages such as excellent CO2 adsorption performance, low overall regeneration energy consumption, simple carbon capture system, low cost of adsorbent materials, and good stability in complex flue gas environments, thus showing potential application value. To accelerate the large-scale application of this technology, conducting fundamental theoretical research on supported solid adsorbent CO2 capture is crucial.

[0003] However, in industrial applications, supported CO2 solid adsorbents need to be circulated between fluidized bed reactors to adsorb CO2. Powdered supported CO2 solid adsorbents are easily washed out of the fluidized bed reactor. To maintain a stable CO2 capture efficiency, additional fresh adsorbent needs to be continuously replenished, which significantly increases CO2 capture costs. These disadvantages affect the practicality of carbon dioxide adsorbents in large-scale industrial applications. Granulation is an effective method to solve the problem of washing out powdered supported CO2 solid adsorbents.

[0004] Currently, domestic and international research on granulation methods mainly includes (1) extrusion method for preparing CaO-based adsorbents for CO2 capture; (2) extrusion spheroidization method for preparing K2CO3-based adsorbents for CO2 capture (Chemical Engineering Journal, 2019, 374: 20-8.); (3) graphite disc method for preparing K2CO3-based adsorbents for CO2 capture (Separation and Purification Technology, 2022, 292: 120929.). Although previous researchers have conducted relevant studies and explorations, existing granulation methods still have problems such as high mechanical stress, high energy consumption, and complex preparation processes. These problems seriously restrict the development and large-scale application of supported CO2 solid adsorbents. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of high mechanical stress, high energy consumption, and complex preparation processes in existing granulation methods, and to provide a solid carbon dioxide adsorbent, its preparation method, and its applications. The solid carbon dioxide adsorbent of this invention has uniform particle size, and the CO2 active component loaded therein is uniformly dispersed on the carrier. Furthermore, the preparation process is simple, which is beneficial for large-scale industrial production.

[0006] To achieve the above objectives, the present invention provides a solid carbon dioxide adsorbent, which includes a support and a CO2 active component loaded on the support;

[0007] The CO2 active component is one or more of metal carbonates, metal nitrates and organic amines;

[0008] The solid carbon dioxide adsorbent has a particle size of 200-300 μm, a particle size distribution width of 2.35-2.55, and a pore size of 2-50 nm.

[0009] The dispersion of the CO2 active component in the carbon dioxide solid adsorbent is 0.8-0.9.

[0010] Preferably, the particle size of the carrier is 50-100 μm.

[0011] Preferably, the carrier is selected from one or more of zeolite, alumina, activated carbon, silicon dioxide, metal-organic framework materials and zirconium dioxide.

[0012] Preferably, in the carbon dioxide solid adsorbent, the content of the CO2 active component is 10-50 wt%, and the content of the carrier is 50-90 wt%.

[0013] A second aspect of the present invention provides a method for preparing the carbon dioxide adsorbent, the method comprising the following steps:

[0014] (1) The porous material is crushed to obtain the carrier material;

[0015] (2) The carrier material is agitated by airflow, atomized and sprayed with a solution containing CO2 active components onto the carrier material, and the resulting material is dried at 50-250°C.

[0016] In the solution containing CO2 active components, the CO2 active components are one or more of metal carbonates, metal nitrates and organic amines;

[0017] The carrier material is selected from one or more of zeolite, alumina, activated carbon, silicon dioxide, metal-organic framework materials and zirconium dioxide;

[0018] The airflow velocity is 0.75-2m. 3 / min.

[0019] Preferably, in step (2), an airflow with a temperature of 50-250°C is used to agitate the carrier material;

[0020] Preferably, the obtained material is dried using an airflow with a temperature of 50-250°C.

[0021] Preferably, the particle size of the carrier material is 50-100 μm.

[0022] Preferably, the solution containing the CO2 active component is obtained by mixing the CO2 active component and a solvent;

[0023] Preferably, the weight ratio of the CO2 active component to the solvent is 1:1-10;

[0024] Preferably, the solvent is selected from one or more of water, ethanol, and methanol.

[0025] Preferably, the metal carbonate is selected from sodium carbonate and / or potassium carbonate;

[0026] Preferably, the organic amine is selected from one or more of polyethyleneimine, tetraethylenepentamine, and ethylenediamine.

[0027] Preferably, the atomization conditions include: an atomization pressure of 1-2 bar and an atomization time of 30-60 min.

[0028] Preferably, the solution containing the CO2 active component is added dropwise to an atomizing device for atomization;

[0029] Preferably, the dropping rate of the solution containing the CO2 active component is 2.6-3.9 mL / min.

[0030] Preferably, when the CO2 active component is a metal carbonate, the drying temperature is 100-200°C;

[0031] Preferably, when the CO2 active component is an organic amine, the drying temperature is 50-100°C;

[0032] Preferably, when the CO2 active component is a metal nitrate, the drying temperature is 100-200°C.

[0033] Preferably, the specific process of step (2) includes: using airflow to agitate the carrier material, atomizing the solution containing CO2 active components, and then spraying it onto the carrier material, while drying the obtained material at 50-250°C, and then calcining it;

[0034] Preferably, the calcination temperature is 50-500℃, and the calcination time is 1-3 hours;

[0035] Preferably, the heating rate during calcination is 5-10℃ / min.

[0036] Preferably, when the CO2 active component is a metal carbonate, the calcination temperature is 200-300°C;

[0037] Preferably, when the CO2 active component is an organic amine, the calcination temperature is 50-70°C;

[0038] Preferably, when the CO2 active component is a metal nitrate, the calcination temperature is 450-550°C.

[0039] Preferably, when the CO2 active component is an organic amine, the atmosphere during calcination is an inert atmosphere.

[0040] A third aspect of the present invention provides a carbon dioxide solid adsorbent prepared by the method described.

[0041] A fourth aspect of the present invention provides an application of the aforementioned solid carbon dioxide adsorbent in carbon dioxide capture.

[0042] The carbon dioxide solid adsorbent of this invention has a uniform particle size distribution of 200-300 μm, which is moderate and enables good fluidization in a fluidized bed, ensuring sufficient contact between the gas and solid phases, thereby improving the adsorption efficiency and reaction rate of carbon dioxide. In addition, the carbon dioxide active component loaded in the carbon dioxide solid adsorbent of this invention is uniformly dispersed, with a dispersion of 0.8-0.9, indicating that the contained carbon dioxide active component is highly dispersed on the carrier, further improving the adsorption performance of the carbon dioxide solid adsorbent.

[0043] Meanwhile, the preparation process of the carbon dioxide solid adsorbent described in this invention is simple. First, the carrier is crushed to obtain a carrier material with a small particle size. Then, hot air is used to blow the carrier material from bottom to top, disturbing the carrier material and causing it to be suspended by the airflow and move irregularly to achieve a fluidized state. Then, the atomized carbon dioxide active component solution is sprayed onto the fluidized carrier. Next, the carrier loaded with the active component is dried in hot air. During the drying process, the liquid in the atomized active component solution evaporates, and at the same time, the carrier material loaded with the carbon dioxide active component self-aggregates and forms particles with uniform size and increased size. In the method described in this invention, by combining the carrier material with the atomized carbon dioxide active component under non-static conditions, it is not only beneficial for the carbon dioxide active component to be loaded better and more uniformly on the carrier material, but also to increase the loading amount of the active component. Furthermore, by immediately drying the loaded carrier, the aggregation between the carrier materials can be promoted, resulting in a more uniform particle size of the prepared carbon dioxide adsorbent with a particle size distribution width of 2.35-2.55. At the same time, the particle size obtained after aggregation is more suitable for industrial applications.

[0044] In addition, the method described in this invention is simple, the process is straightforward, and the preparation cycle is short, making it more suitable for large-scale industrial production. Attached Figure Description

[0045] Figure 1 These are schematic diagrams illustrating the preparation process of the carbon dioxide solid adsorbent as described in some specific embodiments;

[0046] Figure 2 This is a particle size distribution diagram of the solid carbon dioxide adsorbent and powdered alumina prepared in Example 1;

[0047] Figure 3 These are nitrogen adsorption-desorption curves and pore size distribution diagrams of the carbon dioxide solid adsorbents prepared in Examples 1 and 2. Detailed Implementation

[0048] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0049] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0050] In this invention, the carbon dioxide solid adsorbent comprises a support and a CO2 active component loaded on the support. Specifically, the CO2 active component is one or more of metal carbonates, metal nitrates, and organic amines. The CO2 active component in the carbon dioxide solid adsorbent of this invention can contain two or more components, and the carbon adsorption performance of the carbon dioxide solid adsorbent can be further increased by superimposing multiple active components.

[0051] In this invention, the particle size of the carbon dioxide solid adsorbent is more suitable for industrial applications. The moderate particle size allows for good fluidization in a fluidized bed, ensuring sufficient contact between the gas and solid phases, thereby improving adsorption efficiency and reaction rate. Specifically, the particle size of the carbon dioxide solid adsorbent is 200-300 μm.

[0052] In this invention, the carbon dioxide solid adsorbent particles have a uniform size distribution and a relatively concentrated particle size, thus reducing the problem of particle size stripping during practical applications. The particle size distribution width of the carbon dioxide solid adsorbent is 2.35-2.55. Specifically, the particle size distribution width of the carbon dioxide solid adsorbent can be 2.35, 2.4, 2.45, 2.48, 2.5, 2.52, or 2.55.

[0053] In this invention, the formula for calculating the particle size distribution width (span) is as follows:

[0054] Particle size distribution width span = (D v0.9 -D v0.1 ) / D v0.5 ;

[0055] Wherein, the D v0.9 D v0.1 and D v0.5 These represent the particle size values ​​at which the cumulative particle size distribution reaches 10%, 50%, and 90%, respectively. The larger the value of the particle size distribution width (span), the wider the particle size distribution and the more uneven the particle size.

[0056] In this invention, the carbon dioxide solid adsorbent is rich in mesopores, with the pore sizes concentrated in the range of 2-50 nm. The mesopores in the carbon dioxide solid adsorbent provide a large specific surface area and a suitable pore structure, which allows gas molecules, especially carbon dioxide, to effectively enter and interact with the adsorbent surface, thus facilitating the adsorption of carbon dioxide. Therefore, the carbon dioxide solid adsorbent of this invention has excellent carbon capture performance.

[0057] In this invention, the CO2 active component in the solid carbon dioxide adsorbent has a high degree of dispersion, thereby further improving the adsorption performance of each active site and avoiding the reduction in activity of the active component caused by aggregation, thus making the adsorption performance of the solid carbon dioxide adsorbent for carbon dioxide even better. The dispersion of the CO2 active component in the solid carbon dioxide adsorbent is 0.8-0.9. Specifically, the dispersion of the CO2 active component in the solid carbon dioxide adsorbent can be 0.8, 0.83, 0.85, 0.87, or 0.9.

[0058] In this invention, the method for testing the dispersion of CO2 active components in the carbon dioxide solid adsorbent is as follows: the carbon dioxide solid adsorbent is placed in an atmosphere containing carbon dioxide and water vapor for adsorption, and then the adsorbed material is heated to 900-1000℃ in an inert atmosphere for desorption to obtain desorbed gas. Then, the molar amount of CO2 in the desorbed gas is detected, and the molar amount of active sites is calculated from the molar amount of CO2 obtained by the test. The dispersion of active components in the carbon dioxide solid adsorbent is calculated according to the following formula.

[0059]

[0060] Wherein, the measured molar amount of active sites is the molar amount of CO2 in the desorbed gas, and the theoretical molar amount of adsorption active sites is the molar amount of the CO2 active component actually loaded on the support. Specifically, the molar amount of the CO2 active component actually loaded on the support can be obtained by testing methods commonly used in the art, such as ICP or XRF, and the molar amount of CO2 in the desorbed gas can be detected by an infrared gas analyzer.

[0061] In some specific implementations, the solid carbon dioxide adsorbent is placed in an atmosphere containing carbon dioxide and water vapor for adsorption for 20-40 minutes, followed by desorption detection.

[0062] In the specific testing process, in the atmosphere containing carbon dioxide and water vapor, the volume fraction of carbon dioxide is 8-12 vol%, and the volume fraction of water vapor is 8-12 vol%. If the active carbon dioxide component in the solid carbon dioxide adsorbent has a high degree of dispersion, the active carbon dioxide component on its surface will be more uniformly distributed on the material surface, providing more effective adsorption sites, thereby making the desorption characteristics of CO2 exhibit a smoother curve.

[0063] In a preferred embodiment, the carrier is selected from one or more of zeolite, alumina, activated carbon, silica, metal-organic framework materials and zirconium dioxide, more preferably metal-organic framework materials.

[0064] In a preferred embodiment, the particle size of the carrier is ≥50μm, preferably 50-100μm, and more preferably 70-80μm. Specifically, the particle size of the carrier material is 50μm, 60μm, 70μm, 80μm, 90μm, or 100μm.

[0065] In a preferred embodiment, to further improve the performance of the carbon dioxide solid adsorbent, the content of the CO2 active component is 10-50 wt%, and the content of the carrier is 50-90 wt%.

[0066] In a preferred embodiment, in the CO2 active component, the metal carbonate is potassium carbonate and / or sodium carbonate, the organic amine is selected from one or more of polyethyleneimine, tetraethylenepentamine and ethylenediamine, more preferably polyethyleneimine and / or tetraethylenepentamine; and the metal nitrate is potassium nitrate and / or sodium nitrate.

[0067] In a preferred embodiment, when the active CO2 component is a metal carbonate and an organic amine, the weight ratio of the metal carbonate to the organic amine in the active CO2 component is 5.5-7:1.

[0068] The present invention further provides a method for preparing the aforementioned carbon dioxide adsorbent, the preparation process of which can be referred to in conjunction with [the relevant document / reference]. Figure 1 The method includes the following steps:

[0069] (1) The porous material is crushed to obtain the carrier material;

[0070] (2) The carrier material is disturbed by airflow, the solution containing CO2 active components is atomized and sprayed onto the carrier material, and the resulting material is dried at 50-250°C.

[0071] In a specific embodiment, the porous material is pulverized to obtain a carrier material with a particle size of 50-100 μm, preferably 70-80 μm. By pulverizing the porous material before loading it, the active carbon dioxide component can be better fixed within the pores. Furthermore, during subsequent preparation, the pulverized carrier material will self-aggregate, resulting in a significantly larger and more uniform particle size. This reduces the problem of efflorescence when using the solid carbon dioxide adsorbent in a fluidized bed, thereby improving carbon capture efficiency.

[0072] In a preferred embodiment, the carrier material is selected from one or more of zeolite, alumina, activated carbon, silica, metal-organic framework materials and zirconium dioxide, and is more preferably a metal-organic framework material.

[0073] In a specific embodiment, the CO2 active component in the solution is one or more of metal carbonates, metal nitrates, and organic amines. Specifically, the solution containing the CO2 active component is obtained by mixing the CO2 active component and a solvent.

[0074] In some specific embodiments, the weight ratio of the CO2 active component to the solvent is 1:1-10. Specifically, the weight ratio of the CO2 active component to the solvent can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10.

[0075] In a specific embodiment, the solvent is selected from one or more of water, ethanol, and methanol.

[0076] In a preferred embodiment, the metal carbonate is selected from sodium carbonate and / or potassium carbonate; the organic amine is selected from one or more of polyethyleneimine, tetraethylenepentamine and ethylenediamine, more preferably polyethyleneimine and / or tetraethylenepentamine; and the metal nitrate is selected from sodium nitrate and / or potassium nitrate.

[0077] In the method described in this invention, the carrier material is agitated by airflow, causing it to move irregularly. The airflow velocity is gradually increased to fluidize the carrier material. Then, an atomized solution containing CO2 active components is sprayed onto the fluidized carrier material. Unlike existing technologies where loading occurs in a static state, in this method, the carrier material is fluidized, allowing the atomized droplets to be sprayed evenly and arbitrarily to any location on the carrier material. This results in a more uniform and greater loading of the CO2 active components on the carrier material, further improving the performance of the CO2 active sites and thus enhancing the carbon capture performance of the prepared adsorbent.

[0078] Furthermore, during the contact between the atomized droplets and the carrier particles, the water-forming liquid bridges between the droplets and particle surfaces bind the droplets and carrier particles together, promoting the loading of the CO2 active component onto the carrier material. Simultaneously, the loaded carrier material is dried in a high-temperature airflow, and as the solvent in the droplets evaporates, the CO2 active component gradually solidifies on the carrier. With the continuous atomization and drying process, the formation of liquid bridges on the droplet and particle surfaces, along with the adhesion during drying, causes the particles to gradually increase in size and aggregate into larger particle clusters. These aggregated particles, during further drying, eventually form stable and uniform particles due to the formation of solidified bridges. Therefore, in the method described in this invention, by continuously disturbing the carrier material and fluidizing it, and then loading the atomized active component onto the fluidized carrier material, the loading amount and dispersion uniformity of the CO2 active component on the carrier can be increased. Furthermore, the loading amount of the active component can be increased, and the particle size of the prepared solid adsorbent is significantly increased and the particle size distribution is more uniform. This further reduces the possibility of precipitation in practical applications, improves the practicality of industrial applications, and has great industrial application prospects.

[0079] In some specific embodiments, the carrier material is laid flat on a fixed bed, and then a fan blows from below the bed of carrier material from bottom to top, agitating the carrier material and putting it into an irregular motion state. The carrier material is fluidized by gradually increasing the airflow velocity. The airflow velocity is further controlled by controlling the frequency of the fan.

[0080] In a specific implementation, the gas flow rate is related to the fluidization state of the carrier material. Therefore, the gas flow rate is crucial. When the gas flow rate is too low, the fluidization degree of the carrier material will be too low, thereby affecting the mass and heat transfer between the carrier material and the atomized droplets, and further affecting the dispersion and loading of the CO2 active component on the carrier. When the gas flow rate is too high, the atomized droplets will not be able to make sufficient contact with the carrier. Preferably, the gas flow rate is 0.75-2 m / s. 3 / min, further preferably 1.2-1.8m 3 / min. Specifically, the airflow velocity can be 0.75m. 3 / min, 1m 3 / min, 1.2m 3 / min, 1.5m 3 / min, 1.8m 3 / min or 2m 3 / min.

[0081] In some preferred embodiments, in step (2), the carrier material is agitated with air at a temperature of 50-250°C, and the material obtained after atomization loading is dried with the airflow at the same temperature. Understandably, the provided airflow at 50-250°C is used to simultaneously agitate the carrier material and then dry it; that is, when the atomized solution is sprayed onto the carrier material agitated by hot air, the material obtained after spraying undergoes a drying process with the airflow at 50-250°C.

[0082] In this invention, an airflow is used to agitate the carrier material and further raise the temperature of the airflow to a set value. When the temperature of the airflow reaches the set value, the carrier material becomes fluidized in the airflow. At this time, a solution containing carbon dioxide active components is atomized, and the atomized droplets are sprayed onto the fluidized carrier material simultaneously. The resulting material undergoes random movement and drying in the airflow. In other words, the random movement of the carrier material in the airflow, the atomization of the solution containing carbon dioxide active components, the spraying of the atomized droplets onto the fluidized carrier material, and the drying of the resulting material in the airflow all occur simultaneously.

[0083] In the method described in this invention, an atomization method is used to load the active component onto a carrier. A solution containing the CO2 active component is atomized, and the atomized material is immediately and uniformly sprayed onto a fluidized carrier material. The resulting material is simultaneously dried in an airflow. During the atomization and drying process, as the atomized droplets solidify, the carrier material particles loaded with the CO2 active component continuously stack and agglomerate, eventually forming uniform and stable particles. Furthermore, the particle size of the resulting solid carbon dioxide adsorbent is significantly increased compared to the previous particle size, exhibiting good agglomeration properties. This allows for excellent fluidization in a fluidized bed, ensuring sufficient contact between the gas and solid phases, thereby improving adsorption efficiency and reaction rate. The solid carbon dioxide adsorbent described in this invention has promising industrial application prospects, providing strong support for large-scale industrial applications.

[0084] In a specific implementation, when the CO2 active component contains two or more active substances, during the preparation process, solutions containing the corresponding CO2 active components can be prepared separately. Then, the solutions containing the active components are sequentially atomized, sprayed, and dried. The drying temperature during the preparation process can be adjusted according to the CO2 active components contained in the sprayed droplets to avoid the temperature being too high or too low, which would affect the loading and dispersion of the CO2 active components.

[0085] In a preferred embodiment, the atomization conditions include: a pressure of 1-2 bar. Specifically, the atomization pressure can be 1 bar, 1.5 bar, or 2 bar. The atomization time is 30-60 minutes. Specifically, the atomization time can be 30 minutes, 40 minutes, 50 minutes, or 60 minutes.

[0086] In a specific embodiment, the solution containing the CO2 active component is added dropwise to an atomizing device for atomization. Specifically, a peristaltic pump can be used to add the solution containing the CO2 active component dropwise to the atomizing device for atomization. Furthermore, in a specific embodiment, it is necessary to control the dropping rate of the solution containing the CO2 active component. A dropping rate that is too fast or too slow will affect the particle size and carbon adsorption performance of the final solid adsorbent. Preferably, the dropping rate of the solution containing the CO2 active component is 2.6-3.9 mL / min, more preferably 2.6-3.2 mL / min. Specifically, the dropping rate of the solution containing the CO2 active component can be 2.6 mL / min, 2.8 mL / min, 3 mL / min, 3.2 mL / min, 3.4 mL / min, 3.5 mL / min, 3.7 mL / min, or 3.9 mL / min.

[0087] In the method described in this invention, since the atomization spraying of the CO2-containing active component solution and the drying of the material obtained after spraying are carried out simultaneously, the atomization time described in this invention is the duration of the entire preparation process, and is also the drying time. That is, the drying time and the atomization time are equal, and the starting point of the atomization time is the time point when the CO2-containing active component solution begins to be atomized.

[0088] In the method described in this invention, the drying temperature varies depending on the type of CO2 active component. Specifically, when the CO2 active component is a metal carbonate, the drying temperature is 100-200°C; when the CO2 active component is an organic amine, the drying temperature is 50-100°C; and when the CO2 active component is a metal nitrate, the drying temperature is 100-200°C.

[0089] In this invention, the material obtained after atomization and spraying is immediately dried in a high-temperature airflow. The atomized droplets encapsulate the carrier powder, and the liquid evaporates during the drying process, leaving a porous microstructure. This prevents the particles from shrinking or agglomerating excessively during the drying process, maintains high porosity, and thus improves the performance of the prepared carbon dioxide solid adsorbent.

[0090] In some specific embodiments, the specific process of step (2) includes: using airflow to agitate the carrier material, atomizing the solution containing CO2 active components, spraying the atomized droplets onto the carrier material, and drying the material obtained after spraying at 50-250°C.

[0091] In a preferred embodiment, in order to further improve the adsorption performance of the prepared carbon dioxide solid adsorbent and enhance the sphericity and mechanical strength of the particles, the dried material can be calcined.

[0092] In some preferred embodiments, the specific process of step (2) includes: agitating the carrier material with airflow, atomizing a solution containing CO2 active components and spraying it onto the carrier material, while drying the obtained material at 50-250°C, and then calcining it.

[0093] In a preferred embodiment, the calcination temperature is 50-500℃, and the calcination time is 1-3 hours. Specifically, the calcination temperature can be 50℃, 100℃, 150℃, 200℃, 300℃, 400℃, or 500℃; and the calcination time can be 1 hour, 1.5 hours, 2 hours, or 3 hours.

[0094] In a preferred embodiment, the calcination temperature is adjusted according to the composition of the loaded CO2 active component, thereby improving the carbon capture performance of the prepared carbon dioxide solid adsorbent. Specifically, when the CO2 active component is a metal carbonate, the calcination temperature is 200-300°C; when the CO2 active component is an organic amine, the calcination temperature is 50-70°C; and when the CO2 active component is a metal nitrate, the calcination temperature is 450-550°C.

[0095] In some preferred embodiments, when the CO2 active component is an organic amine, the atmosphere during calcination is an inert atmosphere. Specifically, the inert atmosphere can be a nitrogen atmosphere and / or an argon atmosphere.

[0096] In a further preferred embodiment, the dried material is calcined in an inert gas. The inert gas refers to a gas that does not participate in the reaction. In a specific embodiment, the inert gas is selected from at least one of nitrogen and an inert gas (such as argon).

[0097] In a preferred embodiment, the heating rate during calcination is 5-10°C / min. Specifically, the heating rate during calcination can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, or 10°C / min.

[0098] This invention also provides a solid carbon dioxide adsorbent prepared by the method described above. The solid carbon dioxide adsorbent has a uniform particle size distribution and high dispersion of the loaded carbon dioxide active component, exhibiting excellent carbon dioxide adsorption performance. Furthermore, the particle size of the solid carbon dioxide adsorbent is moderate, and the adsorbent is rich in mesopores, allowing it to be well-filled into a fluidized bed fixed reactor for carbon capture, demonstrating promising prospects for industrial applications. Moreover, the method described in this invention enables large-scale production of the carbon dioxide adsorbent, significantly improving its production efficiency and providing strong support for industrial applications.

[0099] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0100] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0101] Example 1

[0102] (1) Grind 200g of alumina particles to 50-100 micrometers to obtain powdered alumina, and then spread it evenly on a bed with dense pores;

[0103] (2) Mix potassium carbonate granules and deionized water evenly for 30 minutes to obtain a solution containing carbon dioxide active components, wherein the weight ratio of potassium carbonate granules to deionized water is 1:2.5.

[0104] (3) Use a fan to blow hot air (temperature 130℃, airflow speed 1.5m) 3 The carrier material is purged and disturbed from below the bed. The solution containing carbon dioxide active components obtained in step (2) is loaded into a peristaltic pump and added to the atomizing device for atomization (the adding rate is 2.6 mL / min). At the same time as atomization, the atomized solution is sprayed onto the powdered alumina. The material obtained after spraying is dried in hot air at 130°C to obtain a granular mixture. The atomization pressure is 1.5 bar and the atomization time is 40 min.

[0105] (4) The obtained particulate mixture was then calcined at 200°C for 2 hours. The heating rate during calcination was 10°C / min. After calcination, a solid carbon dioxide adsorbent was obtained, which was denoted as K30Al.

[0106] The particle size of the carbon dioxide solid adsorbent K30Al was found to be 200-300 micrometers and the particle size distribution width was 2.43, as determined by laser particle size analyzer.

[0107] The pore size of the carbon dioxide solid adsorbent K30Al was found to be 2-50 nm using BET testing.

[0108] ICP testing revealed that the alumina carrier content in the carbon dioxide solid adsorbent K30Al was 69.99 wt%, the active component content was 29.28 wt%, and the dispersion of the active component was 0.86.

[0109] Example 2

[0110] (1) Grind 200g of alumina particles to 50-100 micrometers to obtain powdered alumina, and then spread it evenly on a bed with dense pores;

[0111] (2) Mix polyethyleneimine and ethanol solution evenly and stir for 30 min to obtain a solution containing carbon dioxide active component, wherein the weight ratio of polyethyleneimine to ethanol solution is 1:10.

[0112] (3) A fan is used to blow hot air (temperature 70℃, airflow speed 1.8m). 3 The carrier material is blown and disturbed from below the bed. The solution containing carbon dioxide active components obtained in step (2) is loaded into the peristaltic pump and added to the atomizing device for atomization (the adding rate is 2.8 mL / min). At the same time as atomization, the atomized solution is sprayed onto the powdered alumina. The material obtained after spraying is dried in hot air at 70°C to obtain a granular mixture. The atomization pressure is 1.5 bar and the atomization time is 40 min.

[0113] (4) Under nitrogen protection, the obtained particulate mixture was calcined at 70°C for 2 hours. The heating rate during calcination was 5°C / min. After calcination, the carbon dioxide solid adsorbent was obtained and denoted as Al2O3-PEI(10).

[0114] The particle size of the carbon dioxide solid adsorbent Al2O3-PEI(10) was measured to be 200-300 μm and the particle size distribution width was 2.51 using a laser particle size analyzer.

[0115] The pore size of the carbon dioxide solid adsorbent Al2O3-PEI(10) was found to be 2-50 nm by BET testing;

[0116] The alumina carrier content in the carbon dioxide solid adsorbent Al2O3-PEI(10) was found to be 90.66 wt% by ICP test; the content of active component was 9.31 wt%; and the dispersion of active component was 0.83.

[0117] Example 3

[0118] (1) Grind 200g of alumina particles to 50-100 micrometers to obtain powdered alumina, and then spread it evenly on a bed with dense pores;

[0119] (2) Potassium carbonate granules and deionized water are uniformly mixed and stirred for 30 min to obtain a solution containing the active component potassium carbonate. Polyethyleneimine and ethanol solution are uniformly mixed and stirred for 30 min to obtain a solution containing the active component polyethyleneimine. In the solution containing the active component potassium carbonate, the weight ratio of potassium carbonate to deionized water is 1:10. In the solution containing the active component polyethyleneimine, the weight ratio of polyethyleneimine to ethanol solution is 1:10.

[0120] (3) A fan is used to blow hot air (temperature 130℃, airflow speed 1.6m). 3 / min) The carrier material is blown and disturbed from below the bed. The solution containing the active component polyethyleneimine obtained in step (2) is loaded into the peristaltic pump and added to the atomizing device for atomization (the adding rate is 2.7 mL / min). At the same time as atomization, the atomized solution is sprayed onto the powdered alumina. At the same time, the material obtained after spraying is dried in hot air at 130°C to obtain material A. The atomization pressure is 1.5 bar and the atomization time is 40 min.

[0121] (4) Adjust the temperature of the hot air to 70°C, and put the solution containing the active component potassium carbonate obtained in step (2) into the peristaltic pump and add it to the atomizing device for atomization (the dripping rate is 2.8 mL / min). While atomizing, spray the atomized solution onto the material A, and dry the sprayed material in hot air at 70°C to obtain a granular mixture. The atomization pressure is 1.5 bar and the atomization time is 40 min.

[0122] (5) Under nitrogen protection, the obtained particulate mixture was calcined at 200℃ for 2h. The heating rate during calcination was 10℃ / min. After calcination, the carbon dioxide solid adsorbent was obtained and denoted as K30Al-PEI(5).

[0123] The particle size of the carbon dioxide solid adsorbent K30Al-PEI(5) was measured to be 200-300 micrometers and the particle size distribution width was 2.39 using a laser particle size analyzer.

[0124] The pore size of the carbon dioxide solid adsorbent K30Al-PEI(5) was found to be 2-50 nm by BET testing;

[0125] The active component content in the carbon dioxide solid adsorbent K30Al-PEI(5) is 35.61wt%, the carrier content is 64.91wt%, and the dispersion of the active component is 0.80.

[0126] Example 4

[0127] (1) Grind 200g of magnesium oxide particles to 50-100 micrometers to obtain powdered magnesium oxide, and then spread it evenly on a bed with dense pores;

[0128] (2) Dissolve sodium nitrate and potassium nitrate in deionized water and mix and stir for 30 minutes to obtain a mixed solution of sodium nitrate and potassium nitrate. The ratio of the total weight of sodium nitrate and potassium nitrate to the weight of deionized water is 1:4.

[0129] (3) A fan is used to blow hot air (temperature 130℃, airflow speed 1.7m). 3 The carrier material is purged and disturbed from below the bed by a purging pump ( / min). The solution containing carbon dioxide active components obtained in step (2) is loaded into a peristaltic pump and added to the atomizing device for atomization (the adding rate is 2.9 mL / min). At the same time as atomization, the atomized solution is sprayed onto the powdered alumina. The material obtained after spraying is dried in hot air at 130°C to obtain a granular mixture. The atomization pressure is 1.5 bar and the atomization time is 60 min.

[0130] (4) The obtained particulate mixture was calcined at 500℃ for 3 hours at a heating rate of 10℃ / min. After calcination, a solid carbon dioxide adsorbent was obtained, denoted as MgO-NaK. 0.15 .

[0131] The carbon dioxide solid adsorbent MgO-NaK was obtained by laser particle size analysis. 0.15 The particle size is 200-300 micrometers, and the particle size distribution width is 2.44.

[0132] The carbon dioxide solid adsorbent MgO-NaK was obtained by BET test. 0.15 The pore size is 2-50 nm;

[0133] Carbon dioxide solid adsorbent MgO-NaK 0.15 The content of the active component is 75.12 wt%, the content of the carrier is 24.52 wt%, and the dispersity of the active component is 0.88.

[0134] Comparative Example 1

[0135] The method of Example 1 was implemented, except that hot air was not used to blow and disturb the carrier material from below the bed. Instead, the carrier material was laid flat on the bed, and then the atomized solution was sprayed onto the carrier material in a static state. After the process was completed, the resulting material was placed in an oven and dried at 130°C for 4 hours.

[0136] The test revealed that there was no CO2 active component loaded on the carrier, the preparation failed, and a solid carbon dioxide adsorbent could not be prepared.

[0137] Comparative Example 2

[0138] (1) Grind 20g of alumina particles to 50-100 micrometers to obtain powdered alumina;

[0139] (2) Mix potassium carbonate granules and deionized water evenly for 30 minutes to obtain a solution containing carbon dioxide active components, wherein the weight ratio of potassium carbonate granules to deionized water is 1:2.

[0140] (3) Powdered alumina is directly immersed in the solution containing carbon dioxide active components, and then stirred in a constant temperature water bath at 80°C for 12 hours. After the stirring is completed, it is taken out and dried in an oven at 105°C for 12 hours to obtain a solid carbon dioxide adsorbent, denoted as K40Al.

[0141] The particle size of the carbon dioxide solid adsorbent K40Al was found to be 50-100 micrometers and the particle size distribution width was 2.74, as determined by laser particle size analyzer.

[0142] The pore size of the carbon dioxide solid adsorbent K40Al was found to be 2-50 nm using BET testing.

[0143] The dispersion of the active component in the carbon dioxide solid adsorbent K40Al is 0.78.

[0144] Comparative Example 3

[0145] The method was implemented according to Example 1, except that the airflow velocity of the hot air was 0.5 m / s. 3 / min;

[0146] The particle size of the carbon dioxide solid adsorbent was measured to be 50-120 micrometers using a laser particle size analyzer, and the particle size distribution width was 2.78.

[0147] The dispersion of the active component in the carbon dioxide solid adsorbent was found to be 0.71.

[0148] Comparative Example 4

[0149] The method was implemented according to Example 1, except that the airflow velocity of the hot air was 2.3 m / s. 3 / min;

[0150] The particle size of the carbon dioxide solid adsorbent was determined to be 50-100 micrometers and the particle size distribution width was 2.89, as measured by a laser particle size analyzer.

[0151] The dispersion of the active component in the carbon dioxide solid adsorbent is 0.73.

[0152] Test case

[0153] Test Example 1

[0154] The particle size distribution of the solid carbon dioxide adsorbent prepared in Example 1 and the powdered alumina obtained in step (1) of Example 1 was measured using a laser particle size analyzer. The particle size distribution is shown in the figure below. Figure 2 As shown, the red line represents the particle size distribution of the solid carbon dioxide adsorbent prepared in Example 1, and the blue line represents the particle size distribution of powdered alumina.

[0155] Depend on Figure 2 As shown in the figure, the d(0.5) value of the powdered alumina is approximately 95.573 micrometers, while the d(0.5) value of the carbon dioxide solid adsorbent obtained after preparation is 236.923 micrometers. The carbon dioxide solid adsorbent powder prepared by the method of this invention has a significantly increased particle size, ranging from 200 to 300 micrometers, indicating good particle agglomeration. Particles of suitable size can achieve good fluidization in a fluidized bed, ensuring sufficient contact between the gas and solid phases, thereby improving adsorption efficiency and reaction rate. Therefore, the carbon dioxide solid adsorbent described in this invention has good prospects for industrial application and provides a strong guarantee for large-scale industrial application.

[0156] Test Example 2

[0157] The carbon dioxide solid adsorbents prepared in Examples 1 and 2 were tested using BET, and the results are as follows: Figure 3 As shown. Among them Figure 3 a represents the nitrogen adsorption-desorption curve. Figure 3 b is the pore size distribution diagram of the material.

[0158] Depend on Figure 3 As can be seen from this, the carbon dioxide solid adsorbents described in this invention are all of type IV, and they have H3 type hysteresis loops in the medium and high pressure regions, indicating that all the molded solid adsorbent materials exhibit slit-type pore structures.

[0159] Depend on Figure 3 As can be seen from b, the pores of the carbon dioxide solid adsorbent described in this invention are all concentrated in the mesopore size range of 2-50 nm, and the mesopore size distribution has been proven to be beneficial for CO2 adsorption. Meanwhile, tests showed that the specific surface area of ​​the solid adsorbent K30Al prepared in Example 1 was 45.389 m² / g, and the specific surface area of ​​the solid adsorbent Al2O3-PEI(10) prepared in Example 2 was 36.572 m² / g, both possessing high specific surface areas, which is beneficial for carbon dioxide capture.

[0160] Test Example 3

[0161] The CO2 adsorption and cycling performance of the materials prepared in the examples and comparative examples were tested using a fixed-bed experimental system. The test results are shown in Table 1.

[0162] Table 1

[0163]

[0164] As can be seen from the results in Table 1, the solid carbon dioxide adsorbent prepared by the method described in this invention has excellent CO2 adsorption performance and cycle stability, and the production process is simple, making it suitable for large-scale mass production and promising for large-scale industrial application.

[0165] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A solid carbon dioxide adsorbent, characterized in that, The carbon dioxide solid adsorbent includes a support and a CO2 active component loaded on the support; The CO2 active component is selected from one or more of metal carbonates, metal nitrates and organic amines; The solid carbon dioxide adsorbent has a particle size of 200-300 μm, a particle size distribution width of 2.35-2.55, and a pore size of 2-50 nm. The dispersion of the CO2 active component in the carbon dioxide solid adsorbent is 0.8-0.

9.

2. The solid carbon dioxide adsorbent according to claim 1, characterized in that, The particle size of the carrier is 50-100 μm; and / or The carrier is selected from one or more of zeolite, alumina, activated carbon, silicon dioxide, metal-organic framework materials and zirconium dioxide.

3. The solid carbon dioxide adsorbent according to claim 1, characterized in that, In the solid carbon dioxide adsorbent, the content of the CO2 active component is 10-50 wt%, and the content of the carrier is 50-90 wt%.

4. A method for preparing a solid carbon dioxide adsorbent, characterized in that, The method includes the following steps: (1) The porous material is crushed to obtain the carrier material; (2) The carrier material is agitated by airflow, atomized and sprayed with a solution containing CO2 active components onto the carrier material, and the resulting material is dried at 50-250°C. In the solution containing CO2 active components, the CO2 active components are one or more of metal carbonates, metal nitrates and organic amines; The carrier material is selected from one or more of zeolite, alumina, activated carbon, silicon dioxide, metal-organic framework materials and zirconium dioxide; The airflow velocity is 0.75-2m. 3 / min.

5. The method according to claim 4, characterized in that, In step (2), the carrier material is disturbed by an airflow with a temperature of 50-250°C; and / or The material is dried using an airflow with a temperature of 50-250℃.

6. The method according to claim 4, characterized in that, The particle size of the carrier material is 50-100 μm.

7. The method according to claim 4, characterized in that, The solution containing the CO2 active component is obtained by mixing the CO2 active component and a solvent; Preferably, the weight ratio of the CO2 active component to the solvent is 1:1-10; Preferably, the solvent is selected from one or more of water, ethanol, and methanol.

8. The method according to claim 4, characterized in that, The metal carbonate is selected from sodium carbonate and / or potassium carbonate; Preferably, the organic amine is selected from one or more of polyethyleneimine, tetraethylenepentamine, and ethylenediamine; Preferably, the metal nitrate is selected from potassium nitrate and / or sodium nitrate.

9. The method according to claim 4, characterized in that, The atomization conditions include: an atomization pressure of 1-2 bar and an atomization time of 30-60 min.

10. The method according to claim 4 or 9, characterized in that, The solution containing the CO2 active component is added dropwise to the atomizing device for atomization; Preferably, the dropping rate of the solution containing the CO2 active component is 2.6-3.9 mL / min.

11. The method according to claim 4 or 8, characterized in that, When the CO2 active component is a metal carbonate, the drying temperature is 100-200℃; and / or When the CO2 active component is an organic amine, the drying temperature is 50-100°C; and / or When the active component of CO2 is a metal nitrate, the drying temperature is 100-200℃.

12. The method according to claim 4, characterized in that, The specific process of step (2) includes: using airflow to agitate the carrier material, atomizing a solution containing CO2 active components and spraying it onto the carrier material, while drying the obtained material at 50-250°C, and then calcining it; Preferably, the calcination temperature is 50-500℃, and the calcination time is 1-3 hours; Preferably, the heating rate during calcination is 5-10℃ / min.

13. The method according to claim 12, characterized in that, When the CO2 active component is a metal carbonate, the calcination temperature is 200-300℃; and / or When the CO2 active component is an organic amine, the calcination temperature is 50-70°C; and / or When the active CO2 component is a metal nitrate, the calcination temperature is 450-550℃.

14. The method according to claim 12 or 13, characterized in that, When the active CO2 component is an organic amine, the atmosphere during calcination is an inert atmosphere.

15. A solid carbon dioxide adsorbent prepared by any one of claims 4-14.

16. The application of the solid carbon dioxide adsorbent according to any one of claims 1-3 or 15 in carbon dioxide capture.

Images