A shell solid amine adsorbent and preparation method thereof

Abstract

The invention relates to the technical field of carbon dioxide capture and storage, and discloses a shell-layer solid amine adsorbent and a preparation method thereof. The shell-layer solid amine adsorbent comprises a porous carrier, a pore shell coated on the outer surface of the porous carrier, and an organic amine loaded on the porous carrier, wherein at least part of the organic amine is loaded in the pores of the porous carrier; wherein the size of the organic amine is greater than the pore size of the pore shell and greater than the size of the carbon dioxide molecule, and the ratio of the pore size of the porous carrier to the size of the organic amine is (2:1) to (10:1). The use of the shell-layer solid amine adsorbent can effectively avoid the volatilization of the organic amine and improve the stability of the shell-layer solid amine adsorbent.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon dioxide capture and storage, and in particular to a shell solid amine adsorbent and a preparation method thereof. Background Art

[0002] As the use of fossil fuels causes the release of carbon dioxide to increase year by year, accelerating global warming, the effective control of carbon dioxide emissions has become a hot topic of concern. Solid amine adsorbents have become carbon dioxide capture materials with broad application prospects due to their high theoretical carbon dioxide adsorption capacity, low energy consumption, and strong interaction with carbon dioxide.

[0003] However, after multiple cycles of high-temperature adsorption and desorption, some organic amines evaporate, resulting in a decrease in the amount of carbon dioxide captured and a decrease in the recycling efficiency of solid amine materials. There is an urgent need to enhance the stability of solid amines. Summary of the invention

[0004] The embodiment of the present invention discloses a shell solid amine adsorbent and a preparation method thereof. The shell solid amine adsorbent can effectively increase the adsorption amount of carbon dioxide by the shell solid amine adsorbent, effectively avoid the volatilization of organic amines, and improve the stability of the shell solid amine adsorbent.

[0005] In a first aspect, an embodiment of the present application discloses a shell-layer solid amine adsorbent, the shell-layer solid amine adsorbent comprising a porous carrier, a pore shell coated on the outer surface of the porous carrier, and an organic amine supported on the porous carrier, at least part of the organic amine being supported in the pores of the porous carrier;

[0006] The size of the organic amine is greater than the pore size of the pore shell and greater than the size of the carbon dioxide molecule. The ratio of the pore size of the porous carrier to the size of the organic amine is (2:1) to (10:1).

[0007] Furthermore, the pore volume of the porous carrier is greater than 1.2 cm 3 / g.

[0008] Furthermore, the average thickness of the pore shell is 1 μm-10 μm.

[0009] Furthermore, the pore size of the pore shell is 0.3nm to 0.6nm, and the size of the organic amine is 1nm to 3nm.

[0010] Further, the organic amine includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine and polyethyleneimine; and / or,

[0011] The porous carrier comprises at least one of silicon oxide, aluminum oxide, resin and MOFs; and / or,

[0012] The pore shell comprises a zeolite molecular sieve whose primary structural unit is a TO4 tetrahedron, wherein T comprises at least one of silicon, aluminum, boron, phosphorus, gallium, beryllium and tin.

[0013] In a second aspect, the present application discloses a method for preparing the shell solid amine adsorbent as described in the first aspect, the preparation method comprising the following steps:

[0014] The organic amine, the porous carrier and a surfactant are mixed so that the organic amine is loaded in the pores of the porous carrier to obtain a solid amine powder;

[0015] The solid amine powder and the binder are mixed and then extruded and granulated to prepare solid amine particles, wherein the size of the solid amine particles is larger than the size of the solid amine powder;

[0016] The pore shell is coated on the outside of the solid amine particles to obtain the shell-layer solid amine adsorbent.

[0017] Furthermore, the organic amine is loaded into the pores of the porous carrier by an impregnation method, wherein the impregnation temperature is 25° C. to 80° C., the wind speed is 1 m / s to 3 m / s, and the time is 2 h to 12 h.

[0018] Furthermore, the mass ratio of the organic amine to the porous carrier is (5:8) to (15:8).

[0019] Furthermore, the mass ratio of the binder to the solid amine powder is (1:10) to (1:1).

[0020] Furthermore, the step of coating the pore shell on the outside of the solid amine particles includes: heating the solid amine particles, and placing the heated solid amine particles into a solution containing zeolite seeds to coat the zeolite seeds on the outer surface of the solid amine particles.

[0021] Furthermore, the mass ratio of the zeolite seed crystals to the solid amine particles is (1:100) to (1:1).

[0022] Furthermore, the step of heating the solid amine particles comprises: heating the solid amine particles to 80° C. to 120° C. and maintaining the temperature for 2 h to 6 h; and / or,

[0023] In the step of placing the heated solid amine particles into a solution containing zeolite seed crystals for hot impregnation, the impregnation time is 5s to 60s.

[0024] Further, the binder includes at least one of an inorganic binder and an organic binder, the inorganic binder includes at least one of montmorillonite, dolomite powder and kaolin, and the organic binder includes copovidone; and / or,

[0025] The surfactant comprises at least one of polyethylene glycol borate, polyoxyethylene alkyl ether and polyglycerol; and / or,

[0026] The zeolite seed crystal is a NaA zeolite molecular crystal with a particle size less than 200 nm.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The embodiment of the present application discloses a shell-layer solid amine adsorbent, which includes a porous carrier and a pore shell coated on the outer surface of the porous carrier, wherein the organic amine is loaded in the pores of the porous carrier, and the size ratio of the pore size of the porous carrier to the organic amine is 2:1 to 10:1, thereby reducing the difficulty of the organic amine entering the pores of the porous carrier, making the organic amine have less resistance to entering the porous carrier and a greater entry depth, so that the reaction between the organic amine and the pore shell can be effectively avoided, thereby ensuring the adsorption activity and stability of the organic amine, thereby helping to improve the adsorption performance of the shell-layer solid amine adsorbent.

[0029] In addition, since the size of the organic amine is greater than the size of the pores of the pore shell and greater than the size of the carbon dioxide molecule, the carbon dioxide molecule can freely enter the pores of the pore shell, so that the organic amine can effectively capture carbon dioxide. And since the size of the organic amine is greater than the size of the pores of the pore shell and the depth of the organic amine entering the porous carrier is relatively high, the organic amine has high stability when loaded in the pores and can be protected by the pore shell, and it is difficult for the organic amine to enter the external environment from the pores of the pore shell, so that the pore shell can effectively inhibit the volatilization of the organic amine, thereby improving the stability of the shell solid amine adsorbent to a high degree, increasing the number of times it can be recycled, and thus effectively increasing the adsorption amount of carbon dioxide.

[0030] That is to say, through the shell solid amine adsorbent provided by the present application, by controlling the size ratio of the porous carrier to the organic amine, and gradually reducing the size of the organic amine, the pore size of the pore shell, and the size of the carbon dioxide molecule, not only can the adsorption amount of carbon dioxide by the shell solid amine adsorbent be increased, but the volatilization of the organic amine can also be effectively avoided, thereby improving the stability of the shell solid amine adsorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 It is a schematic diagram of the structure of a shell solid amine adsorbent provided in an embodiment of the present application;

[0033] Figure 2 It is a schematic diagram of a method for preparing a shell solid amine adsorbent provided in an embodiment of the present application. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] In the present invention, the directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "front", "back", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal" and the like are based on the directions or positional relationships shown in the drawings. These terms are mainly used to better describe the present invention and its embodiments, and are not used to limit the indicated devices, elements or components to have a specific direction, or to be constructed and operated in a specific direction.

[0036] In addition, some of the above terms may be used to express other meanings in addition to indicating orientation or positional relationship. For example, the term "on" may also be used to express a certain dependency or connection relationship in some cases. For those skilled in the art, the specific meanings of these terms in the present invention can be understood according to specific circumstances.

[0037] In addition, the terms "installed", "set", "provided with", "connected", and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral structure; it can be a mechanical connection, or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or it can be an internal connection between two devices, elements, or components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0038] In addition, the terms "first", "second", etc. are mainly used to distinguish different devices, elements or components (the specific types and structures may be the same or different), and are not used to indicate or imply the relative importance and quantity of the indicated devices, elements or components. Unless otherwise specified, "plurality" means two or more.

[0039] The technical solution provided by the present invention will be further described below in conjunction with embodiments and drawings.

[0040] Global warming is a global climate problem that needs to be solved urgently, and the carbon dioxide released by fossil fuel consumption is considered to be the culprit of global warming. The use of carbon dioxide capture and storage technology as a large-scale carbon dioxide emission reduction technology is of great strategic significance for effectively controlling carbon dioxide emissions and achieving carbon neutrality goals. Carbon capture technology can directly fix carbon dioxide and reduce the concentration of carbon dioxide in the atmosphere. Among them, solid amine materials have the advantages of large adsorption capacity, low energy consumption, and strong interaction with carbon dioxide, and have attracted the attention of many scholars.

[0041] Among them, the solid amine adsorbent needs to be desorbed at high temperature after adsorbing saturated carbon dioxide, so that the adsorbent can re-capture carbon dioxide and enter the next adsorption-desorption cycle to achieve recycling. However, during the cycle, the organic amine in the solid amine adsorbent will inevitably volatilize, resulting in a decrease in the amount of carbon dioxide captured and a decrease in the recycling efficiency of the solid amine adsorbent. Therefore, it is urgent to enhance the stability of the solid amine adsorbent.

[0042] Based on the above problems, an embodiment of the present application provides a shell-layer solid-state amine adsorbent, which can effectively increase the adsorption amount of carbon dioxide, avoid the volatilization of organic amines, and improve the stability of the shell-layer solid-state amine adsorbent.

[0043] In a first aspect, the present application discloses a shell-layer solid amine adsorbent, which comprises a porous carrier, a pore shell coated on the outer surface of the porous carrier, and an organic amine loaded on the porous carrier, wherein at least part of the organic amine is loaded in the pores of the porous carrier;

[0044] The size of the organic amine is greater than the pore size of the pore shell and greater than the size of the carbon dioxide molecule. The ratio of the pore size of the porous carrier to the size of the organic amine is (2:1) to (10:1).

[0045] In addition, the size of the organic amine and the size of the carbon dioxide molecule in this application refer to the characteristics of their structure. The molecular size of the structure can be obtained by theoretical calculation, by building a corresponding molecular model and directly measuring the diameter of the corresponding molecular model. Among them, the size of the carbon dioxide molecule is measured to be 0.2nm to 0.3nm. The pore size of the pore shell can be measured by physical adsorption.

[0046] The present application reduces the difficulty of the organic amine entering the pores of the porous carrier by controlling the pore size of the porous carrier and the size of the organic amine, and promotes the organic amine to enter to a greater depth, so that the reaction between the organic amine and the pore shell can be effectively avoided, and the adsorption activity and stability of the organic amine can be ensured, thereby helping to improve the adsorption performance and stability of the shell solid amine adsorbent. And, if Figure 1 As shown, since the size of the organic amine in the shell solid amine adsorbent of the present application is greater than the pore size of the pore shell and the size of the carbon dioxide molecule, the size of the organic amine is greater than the pore size of the pore shell and the penetration depth of the organic amine in the pores of the porous carrier is greater, the pore shell can serve as a barrier layer to effectively block the volatilization of the organic amine, and since the pore size of the pore shell is greater than the size of the carbon dioxide molecule, the carbon dioxide molecule can smoothly pass through the pores of the pore shell and will not affect the capture effect of the organic amine on carbon dioxide.

[0047] That is to say, the shell solid amine adsorbent provided by the present application can block the volatilization of organic amines to a high degree, improve the stability of the shell solid amine adsorbent, increase the number of times it can be recycled, and increase the adsorption amount of carbon dioxide.

[0048] Furthermore, since the pore volume of the porous carrier is greater than 1.2 cm 3 / g, so the pores of the porous carrier can accommodate a larger content of organic amines, so the shell solid amine adsorbent can provide more active sites, which helps to improve the adsorption capacity of carbon dioxide to a greater extent.

[0049] In addition, since the average thickness of the pore shell is 1μm to 10μm ， Under this thickness, not only can the risk of organic amine volatilization be increased due to the difficulty of the pore shell to play a blocking effect when the thickness is too thin, but also the risk of organic amine volatilization being affected due to the long transmission path of carbon dioxide when the thickness is too thick. In other words, when the thickness of the pore shell meets the above range, not only can the risk of organic amine volatilization be further avoided, but also the adsorption rate of carbon dioxide can be increased to a high degree.

[0050] Among them, when the pore size of the pore shell is 0.3nm-0.6nm and the size of the organic amine is 1nm-3nm, the pore size of the pore shell is significantly smaller than the size of the organic amine, so the pore shell can play a blocking effect, preventing the organic amine from volatilizing from the pores of the pore shell, thereby improving the stability of the organic amine. In addition, when the pore size of the pore shell meets the above range, the difficulty of carbon dioxide diffusion is reduced, allowing carbon dioxide to pass through the pore shell more smoothly, thereby improving the adsorption effect of the shell solid amine adsorbent to a high degree.

[0051] In addition, since organic amines are widely available, inexpensive, and have a high activity in capturing carbon dioxide, the capture cost per unit of carbon dioxide is reduced and the efficiency of carbon capture is improved. The organic amine includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, and polyethyleneimine; the porous carrier includes at least one of silicon oxide, aluminum oxide, resin, and MOFs; the pore shell includes a zeolite molecular sieve whose primary structural unit is a TO4 tetrahedron, wherein T includes at least one of silicon, aluminum, boron, phosphorus, gallium, beryllium, and tin. When the zeolite molecular sieve is used as the pore shell, the zeolite molecular sieve has sites for adsorbing carbon dioxide, thereby further improving the adsorption effect of carbon dioxide.

[0052] It is understood that the primary structural unit refers to the most basic framework unit constituting the zeolite molecular sieve.

[0053] In a second aspect, the present application provides a method for preparing a shell solid amine adsorbent, such as Figure 2 As shown, the preparation method comprises the following steps:

[0054] The organic amine, the porous carrier and the surfactant are mixed so that the organic amine is loaded in the pores of the porous carrier to obtain a solid amine powder;

[0055] The solid amine powder and the binder are mixed and then extruded and granulated to prepare solid amine particles, wherein the size of the solid amine particles is larger than the size of the solid amine powder;

[0056] The solid amine particles are coated with a pore shell to obtain a shell-layer solid amine adsorbent.

[0057] The preparation method adopted in the present application adds a surfactant in the step of preparing the solid amine powder, and uses the surfactant to reduce the surface tension, thereby reducing the barrier for the organic amine to enter the pores of the porous carrier, thereby promoting the organic amine to enter the pores of the porous carrier and making it enter to a higher depth. In addition, in the process of extruding and granulating the solid amine powder, the size of the prepared solid amine particles is larger than the size of the solid amine powder. Due to its larger particle size, the difficulty of coating the pore shell is reduced, so that the pore shell is more uniformly coated on the solid amine, and an effective barrier layer can be formed to block the volatilization of the organic amine, thereby improving the adsorption effect of the shell solid amine adsorbent to a higher degree.

[0058] In the step of preparing the solid amine powder, the porous carrier and the organic amine can be placed in a solvent at the same time for dissolution and mixing, and then a surfactant can be added during the mixing process. Alternatively, they can be dissolved in a solvent respectively, and then the solutions formed by the two substances are mixed, and then a surfactant is added during the mixing process. A mixed solution is formed first, and then a surfactant is added, so that the surfactant can fully act on the mixed solution, reducing the obstacles for the organic amine molecules to enter the pores of the porous carrier, thereby improving the stability of the shell solid amine adsorbent to a high degree. The solvent includes at least one of water and anhydrous methanol; the mixing method includes stirring with a stirring rod, ultrasound, or stirring with a magnetic stirring bar. The present application does not limit the mixing method and solvent, as long as the purpose of the present application can be achieved.

[0059] The surfactant includes at least one of polyethylene glycol borate, polyoxyethylene alkyl ether and polyglycerol. When the above surfactant types are used, the surface tension can be reduced well and the stability of the organic amine loading can be improved.

[0060] In addition, in the step of preparing solid amine particles, a screw granulator or a roller extrusion granulator can be used for extrusion granulation. The present application does not limit the method of extrusion granulation as long as the purpose of the present application can be achieved.

[0061] In an optional embodiment, the organic amine is loaded into the pores of the porous carrier by an impregnation method, wherein the impregnation temperature is 25° C. to 80° C., the wind speed is 1 m / s to 3 m / s, and the time is 2 h to 12 h.

[0062] Under the above impregnation conditions, the organic amine can be promoted to enter the pores in the porous carrier, and the depth of entry is relatively high, thereby avoiding reaction with the outer shell of the pores. In addition, due to the greater depth of entry, the volatilization path of the organic amine becomes longer, which may lead to higher resistance during volatilization. Therefore, impregnation under the above conditions can further ensure that the shell solid amine adsorbent has a higher stability and increase the number of times it can be recycled.

[0063] Furthermore, the mass ratio of the organic amine to the porous carrier is controlled to be (5:8) to (15:8), so that the content of the organic amine entering the pores of the porous carrier is appropriate, which can further ensure the adsorption effect of the shell solid amine adsorbent. It can avoid that the number of active sites of the shell solid amine adsorbent is small due to a small content, affecting the adsorption activity of the shell solid amine adsorbent; it can also avoid that the pores in the porous carrier are blocked to a high degree due to a large content, which hinders the diffusion of carbon dioxide and limits the adsorption of carbon dioxide by the organic amine, thereby adversely affecting the adsorption performance of the shell solid amine adsorbent.

[0064] Furthermore, when the mass ratio of the binder to the solid amine powder is (1:10) to (1:1), the prepared solid amine particles have a high structural stability, which is beneficial for the subsequent preparation of the channel shell. Specifically, when the mass ratio is within the above range, the adsorption effect of the binder on the organic amine is limited, which prevents the binder from taking the organic amine out of the pores of the porous carrier, further ensuring that the organic amine can be stably loaded in the pores of the porous carrier, and also helps to perform extrusion granulation, ensuring that the prepared solid amine particles have a high structural strength, so that in the subsequent process of wrapping the channel shell, the structure does not deform, thereby ensuring the coating effect of the channel shell.

[0065] Wherein, the binder includes at least one of an inorganic binder and an organic binder, the inorganic binder includes at least one of montmorillonite, dolomite powder and kaolin, and the organic binder includes copolyvidone. Preferably, when only an inorganic binder is used, the adsorption effect of the binder is suitable, which not only avoids the adsorption of organic amines from the porous carrier, but also ensures that the prepared solid amine particles have a higher structural stability, thereby reducing the difficulty of preparing the pore shell.

[0066] In an optional embodiment, the step of coating the solid amine particles with a pore shell includes: heating the solid amine particles, and placing the heated solid amine particles into a solution containing zeolite seeds to coat the zeolite seeds on the outer surface of the solid amine particles.

[0067] Among them, when zeolite is used as the pore shell, since the material has a nanometer-level pore size, and the pores are interconnected to form a channel and a network structure, the zeolite has a higher specific surface area, thereby further improving the adsorption effect of carbon dioxide. In other words, zeolite can not only serve as a barrier layer to block the volatilization of organic amines, but also as a carbon dioxide adsorption material to further increase the adsorption amount of carbon dioxide.

[0068] Furthermore, when the mass ratio of zeolite seeds to solid amine particles is (1:100) to (1:1), it can effectively ensure that the thickness of the pore shell coating the outside of the solid amine particles is appropriate, the coating is highly uniform, and the defects of the pore shell are relatively small, so that it can effectively prevent the volatilization of organic amines.

[0069] Furthermore, the step of heating the solid amine particles comprises: heating the solid amine particles to 80°C to 120°C and maintaining the temperature for 2h to 6h, wherein the temperature and the holding time of the solid amine particles are controlled within the above range, which can effectively remove the volatile substances on the surface of the solid amine particles, thereby ensuring that the solid amine particles have a high bonding force with the pore shell, and ensuring that the pore shell can be well coated on the surface of the solid amine particles. After multiple cycles of use, the structural integrity of the shell solid amine adsorbent is high, thereby increasing the number of times it is recycled.

[0070] Among them, when heating the solid amine particles, in order to prevent the solid amine particles from being oxidized, they can be heated in an inert gas atmosphere, and the inert gas includes at least one of helium and nitrogen. The present application does not limit the type of inert gas as long as the purpose of the present application can be achieved.

[0071] Furthermore, the heated solid amine particles are placed in a solution containing zeolite seeds for hot dipping, and the dipping time is 5s to 60s. By controlling the dipping time, the thickness of the pore shell coating is appropriate and can be evenly covered on the surface of the solid amine particles, which can effectively prevent the volatilization of organic amines.

[0072] In addition, when the zeolite seed is a NaA zeolite molecular crystal with a particle size of less than 200 nm, the material not only has a high carbon dioxide adsorption effect, but also helps to adhere to the surface of the solid amine particles, thereby improving the stability of the structure.

[0073] The technical solution of the present application will be further explained below in conjunction with more specific embodiments and experimental test results.

[0074] Embodiment 1:

[0075] The present invention provides a shell-layer solid amine adsorbent, wherein the ratio of the pore size of the porous carrier to the size of the organic amine in the shell-layer solid amine adsorbent is 7:1, and the pore volume is 2.0 cm 3 / g, the average thickness of the pore shell is 5μm, and the size of the organic amine is greater than the pore size of the pore shell and greater than the size of the carbon dioxide molecule, wherein the size of the organic amine is 2nm, the pore size of the pore shell is 0.4nm, and the size of the carbon dioxide molecule is 0.25nm.

[0076] The preparation method of the above-mentioned shell solid amine adsorbent comprises the following steps:

[0077] The steps for preparing solid amine powder include:

[0078] Add ethylenediamine and silica polyglycerol into a beaker containing deionized water, respectively, and disperse them under ultrasonic conditions to obtain a uniformly dispersed organic amine solution and silica suspension, wherein the mass ratio of ethylenediamine to silica polyglycerol is 10:8;

[0079] The above solutions were mixed and stirred, polyglycerol was added during the stirring process, and the mixture was reacted for 8 hours at a temperature of 60° C. and a wind speed of 2 m / s. The mixture was transferred to an oven and dried at 50° C. for 10 hours, and finally solid amine powder was collected.

[0080] The steps of preparing solid amine particles include:

[0081] The solid amine powder, dolomite powder and water are fully mixed and poured into an extrusion granulator to be extruded into solid amine particles with a shape and particle size, wherein the mass ratio of dolomite powder to solid amine particles is 5:10.

[0082] The steps of coating the solid amine particles with a pore shell include:

[0083] Under a nitrogen atmosphere, the solid amine particles were heated to 100°C and maintained for 4 hours, then taken out and quickly placed in a zeolite seed solution for hot dipping. After dipping for 40 seconds, they were taken out and dried at 80°C overnight to obtain solid amine particles wrapped in zeolite molecular membranes, wherein the mass ratio of zeolite seeds to solid amine particles was 1:20.

[0084] Embodiment 2:

[0085] Compared with Example 1, the difference between this embodiment and Example 1 is that in the step of preparing the solid amine powder, the immersion conditions are temperature 95° C., wind speed 5 m / s, and time 1 h.

[0086] Embodiment three:

[0087] Compared with Example 1, the difference between this embodiment and Example 1 is that in the step of preparing solid amine particles, an organic binder copolyvidone is used as the binder.

[0088] Embodiment 4:

[0089] Compared with Example 1, the difference between this embodiment and Example 1 is that in the step of preparing solid amine powder, the immersion conditions are temperature 95°C, wind speed 5m / s, and time 1h, and in the step of preparing solid amine particles, the binder used is organic binder copolyvidone.

[0090] Embodiment five:

[0091] Compared with Example 1, the difference between this embodiment and Example 1 is that the ratio of the pore size of the porous carrier to the size of the organic amine is 2:1.

[0092] Embodiment six:

[0093] Compared with Example 1, the difference between this embodiment and Example 1 is that the ratio of the pore size of the porous carrier to the size of the organic amine is 10:1.

[0094] Embodiment seven:

[0095] Compared with Example 1, the only difference between this example and Example 1 is that the pore volume of the porous carrier is 1.0 cm 3 / g.

[0096] Comparative Example 1:

[0097] Compared with Example 1, the difference between this embodiment and Example 1 is that the ratio of the pore size of the porous carrier to the size of the organic amine is 1:1.

[0098] Comparative Example 2:

[0099] Compared with Example 1, the difference between this embodiment and Example 1 is that the ratio of the pore size of the porous carrier to the size of the organic amine is 13:1.

[0100] Comparative Example 3:

[0101] Compared with Example 1, the difference between this embodiment and Example 1 is that in the step of preparing the solid amine powder, there is no surfactant in the preparation raw materials.

[0102] Test Results

[0103] In order to further verify the adsorption effect of the shell solid amine adsorbent on carbon dioxide in the embodiment of the present application, the present application uses a thermogravimetric analyzer to test the adsorption effect of the shell solid amine adsorbent on carbon dioxide and its stability in cyclic use.

[0104] Table 1 Adsorption performance of shell solid amine adsorbents in Examples and Comparative Examples

[0105]

[0106]

[0107] Analysis of the data of Example 1, Example 5, Example 6 and Comparative Examples 1 to 2 shows that the performance of the embodiments is better than that of Comparative Example 1. This is because the ratio of the pore size of the porous carrier of the embodiments to the size of the organic amine is larger, so the resistance of the organic amine entering the porous carrier is smaller and the entry depth is greater, thereby ensuring the adsorption activity and stability of the organic amine, thereby improving the adsorption performance of the shell solid amine adsorbent; the performance of the embodiments is better than that of Comparative Example 2. This is because the ratio of the pore size of the porous carrier of the embodiments to the size of the organic amine is smaller, so the content of organic amine entering the porous carrier is appropriate, avoiding the phenomenon of clogging the pores of the porous carrier, thereby improving the adsorption effect to a greater extent.

[0108] Analysis of the data of Example 1 and Comparative Example 3 shows that the performance of Example 1 is better than that of Comparative Example 3. This is because surfactants are added in the preparation method of Example 1, and the surfactants are used to reduce surface tension and reduce the barrier for organic amines to enter the pores of the porous carrier, thereby promoting the organic amines to enter the pores of the porous carrier, effectively ensuring the adsorption effect of the shell solid amine adsorbent.

[0109] Analysis of the data of Examples 1 to 4 shows that the performance of Example 1 is better than that of Examples 2 to 4. This is because the immersion temperature of Example 1 is within the range of 25°C to 80°C, the wind speed is within the range of 1m / s to 3m / s, the time is within the range of 2h to 12h, and the binder is an inorganic binder. The above-mentioned immersion conditions make the loading stability of the organic amine in the pores of the porous carrier higher, and the use of an inorganic binder can effectively avoid the organic amine from being taken out of the pores of the porous carrier, so that the organic amine can stably exist in the pores of the porous carrier, thereby further improving the adsorption effect of the solid amine.

[0110] Analysis of the data of Example 1 and Example 7 shows that the performance of Example 1 is better than that of Example 7. This is because the pore volume of Example 1 is higher, so the content of organic amine that can be loaded is higher, thereby improving the adsorption performance of the shell solid amine adsorbent to a greater extent.

[0111] The above is a detailed introduction to a shell solid amine adsorbent and a preparation method thereof disclosed in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand a shell solid amine adsorbent and a preparation method and application thereof. At the same time, for a general technician in this field, according to the idea of ​​the present invention, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims

1. A shell solid amine adsorbent, characterized in that: The shell solid amine adsorbent comprises a porous carrier, a pore shell coated on the outer surface of the porous carrier, and an organic amine supported on the porous carrier, at least part of the organic amine being supported in the pores of the porous carrier; The size of the organic amine is greater than the pore size of the pore shell and greater than the size of the carbon dioxide molecule. The ratio of the pore size of the porous carrier to the size of the organic amine is (2:1) to (10:1).

2. The shell solid amine adsorbent according to claim 1, characterized in that: The pore volume of the porous carrier is greater than 1.2 cm 3 / g.

3. The shell solid amine adsorbent according to claim 1, characterized in that: The average thickness of the pore shell is 1 μm to 10 μm.

4. The shell solid amine adsorbent according to claim 1, characterized in that: The pore size of the pore shell is 0.3nm-0.6nm, and the size of the organic amine is 1nm-3nm.

5. The shell solid amine adsorbent according to any one of claims 1 to 4, characterized in that: The organic amine includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine and polyethyleneimine; and / or, The porous carrier comprises at least one of silicon oxide, aluminum oxide, resin and MOFs; and / or, The pore shell comprises a zeolite molecular sieve whose primary structural unit is a TO4 tetrahedron, wherein T comprises at least one of silicon, aluminum, boron, phosphorus, gallium, beryllium and tin.

6. A method for preparing a shell solid amine adsorbent according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The organic amine, the porous carrier and a surfactant are mixed so that the organic amine is loaded in the pores of the porous carrier to obtain a solid amine powder; The solid amine powder and the binder are mixed and then extruded and granulated to prepare solid amine particles, wherein the size of the solid amine particles is larger than the size of the solid amine powder; The pore shell is coated on the outside of the solid amine particles to obtain the shell-layer solid amine adsorbent.

7. The preparation method according to claim 6, characterized in that: The organic amine is loaded into the pores of the porous carrier by an impregnation method, wherein the impregnation temperature is 25° C. to 80° C., the wind speed is 1 m / s to 3 m / s, and the time is 2 h to 12 h.

8. The preparation method according to claim 6, characterized in that: The mass ratio of the organic amine to the porous carrier is (5:8) to (15:8).

9. The preparation method according to claim 6, characterized in that: The mass ratio of the binder to the solid amine powder is (1:10) to (1:1).

10. The preparation method according to claim 6, characterized in that: The step of coating the pore shell on the outside of the solid amine particles comprises: heating the solid amine particles, and placing the heated solid amine particles into a solution containing zeolite seeds, so as to coat the zeolite seeds on the outer surface of the solid amine particles.

11. The preparation method according to claim 10, characterized in that: The mass ratio of the zeolite seed crystals to the solid amine particles is (1:100) to (1:1).

12. The preparation method according to claim 10, characterized in that: The step of heating the solid amine particles comprises: heating the solid amine particles to 80° C. to 120° C. and maintaining the temperature for 2 h to 6 h; and / or, In the step of placing the heated solid amine particles into a solution containing zeolite seed crystals for hot impregnation, the impregnation time is 5s to 60s.

13. The preparation method according to claim 10, characterized in that: The binder includes at least one of an inorganic binder and an organic binder, the inorganic binder includes at least one of montmorillonite, dolomite powder and kaolin, and the organic binder includes copolyvidone; and / or, The surfactant comprises at least one of polyethylene glycol borate, polyoxyethylene alkyl ether and polyglycerol; and / or, The zeolite seed crystal is a NaA zeolite molecular crystal with a particle size less than 200 nm.

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