Solid amine honeycomb adsorbent and preparation method and application thereof

Abstract

The present application belongs to the technical field of solid amine adsorbent preparation, and specifically relates to a solid amine honeycomb adsorbent and its preparation method and application. The preparation method comprises the following steps: subjecting a honeycomb carrier and an organic amine mixed solution to a loading treatment and then subjecting them to a synthetic reaction, and then subjecting them to impurities removal and drying to obtain a solid amine honeycomb adsorbent; wherein the organic amine mixed solution comprises: an organic amine, a silane, a surfactant and an organic solvent. The method can prepare the solid amine honeycomb adsorbent in one step, and the organic amine can be uniformly loaded on the honeycomb carrier in one step.

Description

Technical Field

[0001] The present application belongs to the technical field of solid amine adsorbent preparation, and specifically relates to a solid amine honeycomb adsorbent and a preparation method and application thereof. Background Art

[0002] Carbon capture, utilization and storage (CCUS) is generally considered to be a key technology to mitigate global warming and climate change. Carbon capture technology mainly separates CO2 from a mixed gas stream mainly composed of N2, CO2, H2O and their impurities to form a high-concentration CO2 product gas. Common adsorbents include activated carbon, silica gel, solid amines, alkali metal carbonates, zeolites, organic metal frameworks, etc. Among them, solid amines have the advantages of high CO2 adsorption capacity, good selectivity, fast adsorption and desorption rates, and low temperature difference regeneration, and are very suitable for adsorbents for CO2 capture by adsorption.

[0003] At present, the preparation process of solid amine adsorbent is to first prepare a porous material as a substrate, and then load the organic amine on the surface and pores of the porous material by an impregnation method to obtain the solid amine adsorbent. However, the substrate selected for the solid amine adsorbent in the prior art is silicon dioxide, aluminum oxide and other particles with a small particle size. The prepared solid amine adsorbent is easily affected by the airflow of the mixed gas and agglomerates, dust flies, and has excessive pressure resistance, and cannot be widely used in fixed beds and fluidized beds of adsorption towers. Summary of the invention

[0004] To solve the above problems, the present application proposes a solid amine honeycomb adsorbent and its preparation method and application. The preparation method loads the organic amine on the honeycomb substrate in a one-step process, achieves uniform loading and deep impregnation of the organic amine, and simplifies the material preparation steps.

[0005] This application is implemented through the following technical solutions:

[0006] One of the purposes of the present application is to provide a method for preparing a solid amine honeycomb adsorbent, comprising the following steps:

[0007] The honeycomb carrier and the organic amine mixed solution are subjected to a loading treatment and then subjected to a synthesis reaction, and then the mixture is subjected to impurity removal and drying to obtain a solid amine honeycomb adsorbent;

[0008] Wherein, the organic amine mixed solution comprises: organic amine, silane, surfactant and organic solvent.

[0009] The preparation method of the solid amine honeycomb adsorbent provided in the present application firstly impregnates the solution containing organic amine into the honeycomb carrier, and then synthesizes the honeycomb carrier loaded with the organic amine mixed solution. The method can prepare the solid amine honeycomb adsorbent in one step, and can evenly load the organic amine on the honeycomb carrier in one step.

[0010] In some possible implementations, the molar ratio of the surfactant, the organic solvent and the silane is: 1:(400-10000):(10-1000).

[0011] Furthermore, the concentration of the silane in the organic amine mixed solution is 0.1 mol / L to 100 mol / L. In this concentration range, the silane can be fully hydrolyzed and polycondensed into silicon dioxide under the catalytic effect of the alkaline solution.

[0012] In some possible implementations, the organic amine includes one or more of ethylenediamine, monoethanolamine, diethanolamine, polyethyleneimine, polyacrylamide, polyallylamine, aminopropyltrimethoxysilane, polyethyleneimine-trimethoxysilane, amide, tetraethylenepentamine, diethylenetriamine, diethyldiaminoethane, benzenesulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.

[0013] In some possible implementations, the silane includes one or more of triethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and methyltrimethoxysilane.

[0014] In some possible implementations, the surfactant includes one or more of sodium dodecyl sulfate, benzalkonium chloride, dodecyldimethylbenzyl ammonium chloride, quaternary ammonium salt, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraethylammonium bromide, hexadecylpyridinium chloride, hexadecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium chloride.

[0015] In some possible implementations, preparing the organic amine mixed solution includes the steps of: subjecting the surfactant to a first mixing treatment with a mixed system of an organic solvent and an organic silane to obtain a mixed solution; and subjecting the mixed solution to a second mixing treatment with an organic amine to obtain the organic amine mixed solution.

[0016] Furthermore, the mass ratio of the mixed solution to the organic amine is 10:(1-100). In this mass ratio range, since the mixed solution is a silica gel synthesis solution, the organic amine is added in the silica gel synthesis process within this mass ratio range, so that the synthesized silica gel particles can effectively load the organic amine without too little or too much loading.

[0017] In some possible implementations, the loading treatment step includes: immersing the honeycomb carrier in the organic amine mixed solution at room temperature or in a water bath for 1 min to 2 h, and drying after immersion to obtain a solid amine honeycomb adsorbent precursor.

[0018] In some possible implementations, the synthesis reaction step includes: mixing the solid amine honeycomb adsorbent precursor with an alkaline solution at room temperature or water bath heating (preferably the water bath temperature is 60°C to 100°C) for a mixing reaction time of 10 minutes to 4 hours to obtain a wet honeycomb adsorbent. The mixing reaction allows the organic amine to be synthesized on the honeycomb carrier to obtain a silica gel-based solid amine; when the mixing reaction is carried out at room temperature, the required mixing reaction time is 1 hour to 4 hours; when the mixing reaction is carried out under water bath heating (preferably the water bath temperature is 60°C to 100°C), the reaction time is shortened, generally 10 minutes to 2 hours.

[0019] Furthermore, the mass ratio of the solid amine honeycomb adsorbent precursor to the alkaline solution is 1:(1-10).

[0020] In some possible implementations, the drying step uses one of vacuum, freezing, and inert gas protection drying to dry the wet honeycomb adsorbent. Wherein, when vacuum drying the wet honeycomb adsorbent, the wet honeycomb adsorbent is placed in a drying furnace for heating, the drying temperature is 50℃~100℃, the drying time is 1h~10h, and the pressure in the furnace is less than 100Pa; when freezing drying the wet honeycomb adsorbent, the wet honeycomb adsorbent is placed in a freeze drying box, the drying temperature is -80℃~0℃, the drying time is 1h~10h, and the pressure in the drying box is less than 5Pa (i.e. vacuum, low oxygen); when inert gas (Ar, N2, He) protection drying is used, the inert gas temperature is 50℃~100℃, the drying time is 1h~10h, and the gas flow rate is 2L / min~20L / min. In this case, low-temperature drying can ensure the structural integrity of the organic amine and prevent it from volatilizing due to high temperature; moreover, drying can remove part of the alkaline solution and organic solvent filled in the adsorbent network structure, and protect the organic amine from volatilization and oxidation by oxygen in the air during the drying process, thereby improving the purity of the product.

[0021] The second object of the present application is to provide a solid amine honeycomb adsorbent prepared by the preparation method of the solid amine honeycomb adsorbent provided in the embodiment of the present application, wherein the solid amine honeycomb adsorbent comprises a honeycomb carrier, silica gel and an organic amine; the organic amine is loaded on the surface of the silica gel and in the pores of the honeycomb carrier to form a solid amine;

[0022] The loading amount of the solid amine is 50 kg / m3 ~200kg / m 3 .

[0023] The solid amine honeycomb adsorbent provided by the present application has organic amines loaded on the surface of silica gel and in the pores of the honeycomb carrier. While adsorbing CO2, it also plays a bridging role between silica gel particles. The organic amines and the silanol groups on the surface of silica gel can be hydrogen bonded, or they can react with the silanol groups to form covalent bonds, so that the solid amine honeycomb adsorbent has good stability. The saturated adsorption capacity of carbon dioxide at 90°C can reach 152mg / g.

[0024] The third object of the present application is to provide a solid amine honeycomb adsorbent prepared by a preparation method of the solid amine honeycomb adsorbent provided in the present application or an application of the solid amine honeycomb adsorbent provided in the present application in the field of carbon capture technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of a process for preparing a solid amine honeycomb adsorbent in an embodiment of the present application;

[0026] Figure 2 This is a schematic diagram of the adsorption capacity of carbon dioxide by the solid amine honeycomb adsorbent prepared in the examples of this application;

[0027] Figure 3a This is a schematic diagram of the adsorbent prepared in Example 1 of the present application;

[0028] Figure 3b for Figure 3a SEM schematic diagram of area A at 1000 times magnification;

[0029] Figure 3c for Figure 3a SEM diagram of area B at 10,000 times magnification. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solution and advantages of the present application clearer, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0031] On the contrary, the present application covers any substitution, modification, equivalent method and scheme made on the essence and scope of the present application as defined by the claims. Further, in order to make the public have a better understanding of the present application, some specific details are described in detail in the detailed description of the present application below. Those skilled in the art can fully understand the present application without the description of these details.

[0032] The following examples serve to illustrate the present application. In the examples, unless otherwise indicated, parts are by weight, percentages are by weight, and temperatures are in degrees Celsius. The relationship between parts by weight and parts by volume is the same as the relationship between grams and cubic centimeters.

[0033] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0034] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0035] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0036] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0037] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass described in the embodiment description of the present application can be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0038] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0039] The term "solid amine" refers to the solid amine in the embodiments of the present application, including organic amines supported on the surface of silica gel (ie, silica gel-based solid amines) and organic amines supported on a honeycomb carrier.

[0040] At present, the preparation of solid amines mainly adopts a two-step preparation process, first preparing a porous material as a substrate, and then loading the organic amine on the surface and pores of the porous material by an impregnation method.

[0041] For example, the organic amine functionalized macroporous silica adsorbent in the prior art first uses TEOS to prepare a porous silica material, then loads the organic amine onto the porous material by an impregnation method, and finally prepares a CO2 adsorbent with high adsorption capacity and strong adsorption stability. Therefore, the preparation of a solid amine honeycomb adsorbent requires three steps: the first step is to prepare a porous material, the second step is to prepare a solid amine material, and the third step is to prepare a solid amine honeycomb adsorbent. After two impregnations, the solid amine honeycomb adsorbent will lead to the defects of uneven organic amine loading and low adsorbent utilization. When preparing solid amines, the organic amine will not be deeply impregnated due to the surface tension of the pores.

[0042] For another example, in the prior art, carbon dioxide is introduced into a mixed solution of sodium aluminosilicate and sodium silicate for reaction, and the reaction product is calcined to obtain the porous material, which is a Si-Al porous material; and a solid amine active substance is loaded on the porous material to obtain the carbon dioxide adsorbent. This method requires first preparing a porous material carrier, and then loading the solid amine active substance to prepare a carbon dioxide adsorbent. The material preparation steps are divided into two steps, which is relatively cumbersome. Although the carrier can be enlarged in pore size and specific surface area according to the load requirements, it will increase the consumption of raw materials and production energy.

[0043] For example, a zeolite slurry is coated on a carrier; the composition of the zeolite slurry is calculated by weight, including 9 to 95 parts of a dispersant, 20 to 70 parts of zeolite fine powder, 0.5 to 8 parts of an additive and 50 to 800 parts of

[0044] of water. However, this method requires the preparation of zeolite slurry first, and then the impregnation of the honeycomb carrier to prepare the monolithic adsorbent. Due to the presence of small zeolite particles in the slurry, the depth of entering the honeycomb carrier is not enough, and the surface cannot be evenly loaded and the carrier cannot be deeply loaded. At the same time, the zeolite slurry is unstable, and the zeolite will settle in a short time and cannot be reused.

[0045] In order to effectively take into account the problems of uniform distribution of organic amines, maintaining the adsorption performance of adsorbents and saving energy consumption, the embodiments of the present application propose a solid amine honeycomb adsorbent and its preparation method and application. The preparation method uses an organic compound containing silane as a raw material, an organic amine as an additive, an alkaline solution as a catalyst, and a honeycomb substrate as a carrier. The organic silane and the organic amine are first loaded on the honeycomb carrier, and then the silicon dioxide is aggregated and nucleated on the honeycomb carrier to form a silica-based solid amine through an in-situ synthesis method, thereby achieving uniform loading and deep impregnation of the organic amine, simplifying the material preparation steps. The in-situ synthesis method is to hydrolyze silane under acidic or alkaline conditions to form silanols, which are further condensed to form Si-O-Si bonds, and finally generate SiO2.

[0046] For the convenience of explanation, the following embodiments of the present application are described by taking a solid amine honeycomb adsorbent and its preparation method and application as an example.

[0047] [A method for preparing a solid amine honeycomb adsorbent]

[0048] One of the purposes of the embodiments of the present application is to provide a method for preparing a solid amine honeycomb adsorbent, comprising the following steps:

[0049] S1. The honeycomb carrier and the organic amine mixed solution are subjected to a synthetic reaction after loading treatment, and then the mixture is removed and dried to obtain a solid amine honeycomb adsorbent;

[0050] The organic amine mixed solution comprises organic amine, silane, surfactant and organic solvent.

[0051] The preparation method of the solid amine honeycomb adsorbent provided in the embodiment of the present application first impregnates the solution containing organic amine into the honeycomb carrier, and then synthesizes the honeycomb carrier loaded with the mixed solution of organic amines. This method can prepare the solid amine honeycomb adsorbent in one step, and can evenly load the organic amine on the honeycomb carrier in one step.

[0052] In some embodiments, in the above step S1, the honeycomb carrier includes one or more of glass fiber, ceramic fiber, and cordierite honeycomb carrier. In some specific embodiments, the honeycomb carrier is glass fiber. These honeycomb carriers have deep pores, and the organic amine can penetrate into the internal space of the honeycomb carrier after solution impregnation, and then the silica gel-based solid amine is directly synthesized on the honeycomb carrier by an in-situ synthesis method, so that the solid amine is evenly distributed on the honeycomb carrier.

[0053] In some embodiments, in the above step S1, the molar ratio of the surfactant, the organic solvent and the silane is: 1:(400-10000):(10-1000). In the exemplary embodiment, it can be a typical but non-limiting molar ratio such as 1:400:150, 1:500:200 or a range between the molar ratios of any two substances.

[0054] In some embodiments, in the above step S1, the concentration of silane in the organic amine mixed solution is 0.1 mol / L to 100 mol / L, and in exemplary embodiments, it can be 0.1 mol / L, 1 mol / L, 10 mol / L, 100 mol / L, and other typical but non-limiting concentrations or a range between any two concentrations. In this concentration range, silane can be fully hydrolyzed and condensed into silicon dioxide under the catalytic action of the alkaline solution.

[0055] In some embodiments, in the above step S1, the organic amine includes one or more of ethylenediamine, monoethanolamine, diethanolamine, polyethyleneimine, polyacrylamide, polyallylamine, aminopropyltrimethoxysilane, polyethyleneimine-trimethoxysilane, amide, tetraethylenepentamine, diethylenetriamine, diethyldiaminoethane, benzenesulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.

[0056] In some embodiments, in the above step S1, the silane includes one or more of triethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and methyltrimethoxysilane.

[0057] In some embodiments, in the above step S1, the surfactant includes one or more of sodium dodecyl sulfate, benzalkonium chloride, dodecyldimethylbenzyl ammonium chloride, quaternary ammonium salt, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraethylammonium bromide, hexadecylpyridinium chloride, hexadecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium chloride.

[0058] In some embodiments, in the above step S1, the organic solvent includes one or more of methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, ethyl acetate, acetonitrile, and acetone.

[0059] In some embodiments, in the above step S1, preparing the organic amine mixed solution comprises the steps of:

[0060] S11. Performing a first mixing treatment on a mixed system of a surfactant, an organic solvent and an organic silane to obtain a mixed solution.

[0061] S12. Perform a second mixing treatment on the mixed solution and the organic amine to obtain an organic amine mixed solution.

[0062] In some specific embodiments, in the above step S11, the first mixing treatment step includes: stirring the mixing system for 10 minutes to 2 hours at room temperature or under ultrasonic or water bath heating (preferably 60°C to 100°C).

[0063] In some specific embodiments, in the above step S12, the second mixing treatment step includes: stirring the mixture of the mixed solution and the organic amine under the conditions of room temperature, ultrasound or water bath heating (60-100°C), and the stirring time is 30min-4h. In this case, stirring is performed under room temperature or ultrasound until the organic amine is completely dissolved, and the stirring time is 3h-4h; the organic amine mixed solution obtained by stirring is transparent and clear; and stirring is performed under the conditions of water bath (preferably 80°C-100°C) for 30min-3h; under the water bath conditions, due to the high water bath temperature, the viscosity of the organic amine mixed solution obtained by stirring is low.

[0064] In some specific embodiments, in the above step S12, the mass ratio of the mixed solution to the organic amine is 10:(1-100), and in the exemplary examples, it can be a typical but non-limiting mass ratio such as 10:1, 10:10, 10:50, 10:100, or a range between any two mass ratios. In this mass ratio range, since the mixed solution is a silica gel synthesis solution, the organic amine is added in the mass ratio range during the silica gel synthesis process, so that the synthesized silica gel particles can effectively load the organic amine.

[0065] In some embodiments, in the above step S1, the load treatment step includes: immersing the honeycomb carrier in an organic amine mixed solution at room temperature or water bath heating (preferably 60°C to 100°C) for 1 min to 2 h, and drying after immersion to obtain a solid amine honeycomb adsorbent precursor.

[0066] In some specific embodiments, the reaction equation for synthesizing silica-based solid amine from organic amine is as follows:

[0067] Silane hydrolyzes to produce orthosilicic acid. Take tetraethoxysilane as an example:

[0068] Si(OCH2CH3)4+4H2O—→→Si(OH)4+4C2H5OH

[0069] Reaction of orthosilicic acid with amino groups:

[0070] Si(OH)4+xR0-NH2—→→Si(OH) 4-x (O-NH-R0) x+xH2O

[0071] Si(OH)4+yR1-NH-R2—→→Si(OH) 4-y (ON-R1R2) y +yH2O

[0072] Take x=2 as an example, where For the synthesis of silica-based solid amine:

[0073]

[0074] In some embodiments, in the above step S1, the synthesis reaction step includes: mixing the solid amine honeycomb adsorbent precursor with the alkaline solution at room temperature or water bath heating (preferably the water bath temperature is 60°C to 100°C) for a mixing reaction time of 10min to 4h to obtain a wet honeycomb adsorbent. The mixing reaction completes the synthesis of the organic amine on the honeycomb carrier to obtain a solid amine after synthesis; when the mixing reaction is carried out at room temperature, the required mixing reaction time is 1h to 4h; when the mixing reaction is carried out under water bath heating (preferably the water bath temperature is 60°C to 100°C), the reaction time is shortened, generally 10min to 2h.

[0075] In some embodiments, the alkaline solution includes one or more of ammonia water, sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and sodium bicarbonate solution.

[0076] In some embodiments, the mass fraction of the solute in the alkaline solution is 5% to 50%, and in exemplary embodiments, it can be 5%, 20%, 30%, 40%, 50%, etc., which are typical but non-limiting mass fractions, or a range between any two mass fractions. In this mass fraction range, the silane can be catalyzed and a condensation reaction occurs quickly to eventually form a silica-based solid amine.

[0077] In some embodiments, the mass ratio of the solid amine honeycomb adsorbent precursor to the alkaline solution is 1:(1-10). In exemplary embodiments, it can be a typical but non-limiting mass ratio such as 1:1, 1:3, 1:5, 1:7, 1:10, or a range between any two mass ratios.

[0078] In other embodiments, the synthesis reaction step includes: spraying an alkaline solution on a solid amine honeycomb adsorbent precursor for 10 to 50 times; after spraying, reacting the mixture in a temperature atmosphere of 25°C to 80°C for 1 to 6 hours to obtain a wet honeycomb adsorbent.

[0079] In some embodiments, in the above step S1, the impurity removal step includes: washing the wet honeycomb adsorbent with a washing liquid, and the number of washing times is 1 to 10. In this case, the impurity removal mainly removes the excess alkaline solution in the wet honeycomb adsorbent, thereby increasing the life of the solid amine honeycomb adsorbent.

[0080] In some specific embodiments, the washing liquid is a mixture of an organic solvent and water; wherein the mass fraction of the organic solvent is 25% to 75%. In the exemplary embodiment, it can be a typical but non-limiting mass fraction such as 25%, 30%, 50%, 75%, or a range between any two mass fractions.

[0081] In some specific embodiments, the organic solvent in the washing liquid includes one or more of methanol, ethanol, isopropanol, n-butanol, and acetone.

[0082] In some embodiments, in the above step S1, the drying step uses one of vacuum, freezing, and inert gas protection drying to dry the wet honeycomb adsorbent. When vacuum drying the wet honeycomb adsorbent, the wet honeycomb adsorbent is placed in a drying furnace for heating, the drying temperature is 50°C to 100°C, the drying time is 1h to 10h, and the pressure in the furnace is less than 100Pa; when freezing drying the wet honeycomb adsorbent, the wet honeycomb adsorbent is placed in a freeze drying box, the drying temperature is -80°C to 0°C, the drying time is 1h to 10h, and the pressure in the drying box is less than 5Pa (i.e., vacuum, low oxygen); when inert gas (Ar, N2, He) is used for protection drying, the inert gas temperature is 50°C to 100°C, the drying time is 1h to 10h, and the gas flow rate is 2L / min to 20L / min. In this case, low-temperature drying can ensure the structural integrity of the organic amine and prevent it from volatilizing due to high temperature; moreover, drying can remove part of the alkaline solution and organic solvent filled in the adsorbent network structure, and protect the organic amine from volatilization and oxidation by oxygen in the air during the drying process, thereby improving the purity of the product.

[0083] The second purpose of the embodiment of the present application is to provide a solid amine honeycomb adsorbent prepared by the preparation method of the solid amine honeycomb adsorbent provided in the embodiment of the present application, the solid amine honeycomb adsorbent comprising a honeycomb carrier, silica gel and an organic amine;

[0084] The organic amine is loaded on the silica gel surface and in the pores of the honeycomb carrier to form a solid amine;

[0085] The loading capacity of solid amine is 50kg / m 3 ~200kg / m 3 .

[0086] The solid amine honeycomb adsorbent provided in the embodiment of the present application has organic amines loaded in the pores including silica gel channels, silica gel surfaces and honeycomb carriers. The organic amine loaded on the silica gel surface wraps and connects the silica particles in the silica gel to form a cluster structure. The organic amine is loaded on the silica gel surface and in the pores of the honeycomb carrier, playing a bridging role between the silica gel particles; the organic amine and the silanol groups on the silica gel surface can be hydrogen bonded, or they can react with the silanol groups to form covalent bonds, making the solid amine honeycomb adsorbent have better stability. The saturated adsorption capacity of carbon dioxide at 90°C can reach 152 mg / g.

[0087] In the embodiment, the loading amount of the solid amine can be 50 kg / m 3 , 55kg / m 3 、150kg / m 3 、156kg / m 3 、170kg / m 3 、172kg / m 3 , 200kg / m 3 Typical but non-limiting loads or ranges between any two loads.

[0088] The third purpose of the embodiments of the present application is to provide a solid amine honeycomb adsorbent prepared by the preparation method of the solid amine honeycomb adsorbent provided in the embodiments of the present application or the application of the solid amine honeycomb adsorbent provided in the embodiments of the present application in the field of carbon capture technology.

[0089] In the exemplary embodiment, the field of carbon capture technology includes but is not limited to steel, cement, power plants, air carbon capture and other fields.

[0090] The following describes the invention in conjunction with specific embodiments.

[0091] Example 1

[0092] Example 1 provides a method for preparing a solid amine honeycomb adsorbent, comprising the following steps:

[0093] (1) Preparation of a mixed solution: Mix sodium dodecyl sulfate with a mixed system of ethanol and methyltriethoxysilane in a water bath at 70° C. and stir for 1 h to obtain a mixed solution, wherein the molar ratio of sodium dodecyl sulfate, ethanol and methyltriethoxysilane is 1:400:150.

[0094] (2) Preparation of an organic amine mixed solution: Stirring the mixed solution and ethylenediamine mixture in a water bath at 90° C. with a mass ratio of 10:10 and a silane concentration of 2 mol / L for 2 h to obtain an organic amine mixed solution.

[0095] (3) Immersing: Immerse the honeycomb carrier in an organic amine mixed solution at room temperature for 1 hour, and then dry it to obtain a solid amine honeycomb adsorbent precursor.

[0096] (4) Synthesis reaction: Under room temperature, the solid amine honeycomb adsorbent precursor is immersed in ammonia water, the water bath temperature is 60°C, and the reaction time is 2h to obtain a wet honeycomb adsorbent, wherein the mass fraction of the solute in the ammonia water is 25%.

[0097] (5) Impurity removal: The wet honeycomb adsorbent was washed with 75% ethanol aqueous solution (washing liquid) for 5 times.

[0098] (6) Drying: The wet honeycomb adsorbent after impurity removal is dried in a vacuum drying oven to obtain a solid amine honeycomb adsorbent. The drying temperature is 50° C., the drying experiment is 2 h, and the pressure in the furnace is 100 Pa.

[0099] Example 1 also provides a solid amine honeycomb adsorbent, which is prepared by the preparation method of this example. The solid amine honeycomb adsorbent includes a honeycomb carrier and a solid amine;

[0100] The loading capacity of solid amine is: 172kg / m 3 .

[0101] Example 2

[0102] Example 2 proposes a method for preparing a solid amine honeycomb adsorbent, and the steps are basically the same as those of Example 1, except that:

[0103] The drying temperature in step (6) is -40°C and the pressure in the furnace is 5Pa.

[0104] Example 2 also provides a solid amine honeycomb adsorbent, which is prepared by the preparation method of this example. The solid amine honeycomb adsorbent includes a honeycomb carrier and a solid amine;

[0105] The loading capacity of solid amine is: 150kg / m 3 .

[0106] Example 3

[0107] Example 3 proposes a method for preparing a solid amine honeycomb adsorbent, and the steps are basically the same as those of Example 1, except that:

[0108] (1) A mixed solution is prepared by mixing sodium hexadecyl sulfate with a mixed system of ethanol and methyltriethoxysilane at room temperature for 10 minutes to obtain a mixed solution, wherein the molar ratio of sodium hexadecyl sulfate, ethanol and methyltriethoxysilane is 1:500:200.

[0109] (2) Preparation of an organic amine mixed solution: stirring a mixture of the mixed solution and polyacrylamide at a mass ratio of 1:1, a silane concentration of 2.5 mol / L, and a stirring time of 30 min under ultrasonic conditions at 60° C. to obtain an organic amine mixed solution.

[0110] Example 3 also provides a solid amine honeycomb adsorbent, which is prepared by the preparation method of this example. The solid amine honeycomb adsorbent includes a honeycomb carrier and a solid amine;

[0111] The loading capacity of solid amine is: 170kg / m 3 .

[0112] Example 4

[0113] Example 4 proposes a method for preparing a solid amine honeycomb adsorbent, and the steps are basically the same as those of Example 1, except that:

[0114] (1) Preparing a mixed solution: In a water bath at 70° C., tetraethylammonium bromide and a mixed system of ethanol and triethoxysilane were mixed and stirred for 1 hour to obtain a mixed solution, wherein the molar ratio of tetraethylammonium bromide, methanol and triethoxysilane was 1:400:150.

[0115] (2) Preparation of an organic amine mixed solution: Stirring the mixed solution and ethylenediamine mixture in a water bath at 90° C. with a mass ratio of 1:1 for 2 h to obtain an organic amine mixed solution.

[0116] Example 4 also provides a solid amine honeycomb adsorbent, which is prepared by the preparation method of this example. The solid amine honeycomb adsorbent includes a honeycomb carrier and a solid amine;

[0117] The loading capacity of solid amine is: 170kg / m 3 .

[0118] Example 5

[0119] Example 5 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the molar ratio of sodium hexadecyl sulfate, ethanol and methyltriethoxysilane is 1:10000:1000. The loading amount of the solid amine is: 165 kg / m 3 .

[0120] Example 6

[0121] Example 6 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the molar ratio of sodium hexadecyl sulfate, ethanol and methyltriethoxysilane is 1:400:1000. The loading amount of the solid amine is: 55 kg / m 3 .

[0122] Example 7

[0123] Example 7 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the mass ratio of the mixed solution to ethylenediamine is 10:1. The loading amount of the solid amine is 200 kg / m 3 .

[0124] Example 8

[0125] Example 8 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the mass ratio of the mixed solution to ethylenediamine is 10:100. The loading amount of the solid amine is: 156 kg / m 3 .

[0126] Comparative Example 1

[0127] Comparative Example 1 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the molar ratio of sodium hexadecyl sulfate, ethanol and methyltriethoxysilane is 1:300:150. The loading amount of the solid amine is: 162 kg / m 3 .

[0128] Comparative Example 2

[0129] Comparative Example 2 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the molar ratio of sodium hexadecyl sulfate, ethanol and methyltriethoxysilane is 1:400:8. The loading amount of the solid amine is: 180 kg / m 3 .

[0130] Comparative Example 3

[0131] Comparative Example 3 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the mass ratio of the mixed solution to ethylenediamine is 1:100. The loading amount of the solid amine is: 118 kg / m 3 .

[0132] Comparative Example 4

[0133] Comparative Example 4 proposes a method for preparing a solid amine honeycomb adsorbent, the steps are basically the same as those in Example 1, except that the mass ratio of the mixed solution to ethylenediamine is 10:0.8. The loading amount of the solid amine is: 184 kg / m 3 .

[0134] In order to verify the progress of the embodiments of the present application, the adsorbents prepared by the preparation methods of the above embodiments 1 to 8 and comparative examples 1 to 4 were subjected to a carbon dioxide adsorption experiment. The test steps are as follows:

[0135] The prepared adsorbent was first vacuum activated at 120°C for 6 hours and then placed in an analytical instrument for a CO2 isotherm adsorption test. The CO2 adsorption capacity of the adsorbent was reflected by comparing the equilibrium adsorption amount of the adsorbent at 100% CO2 concentration.

[0136] The loading amount of the adsorbent and the experimental results are shown in Table 1. The adsorption amount of carbon dioxide by the adsorbent is shown in Table 1 and Figure 2 The adsorption amount of carbon dioxide by the adsorbent is shown in Table 1. Figure 3a to 3c The solid amine honeycomb adsorbent prepared in Example 1 of the present application and its SEM image.

[0137] Table 1

[0138] <![CDATA[Load (kg / m 3 )]]> <![CDATA[CO2 adsorption capacity (mg / g)]]> <![CDATA[CO2 recovery rate (%)]]> <![CDATA[Enriched CO2 concentration (%)]]> Example 1 172 152 96 93 Example 2 150 89 92 88 Example 3 170 117 90 85 Example 4 170 81 88 82 Example 5 165 129 85 80 Example 6 55 5 80 78 Example 7 200 123 88 86 Example 8 156 72 87 70 Comparative Example 1 162 121 77 80 Comparative Example 2 180 45 86 82 Comparative Example 3 118 48 70 78 Comparative Example 4 184 80 72 76

[0139] According to Table 1 above and the instructions attached Figure 2 , 3a , 3b and 3c can at least draw the following conclusions:

[0140] (1) The saturated adsorption capacity of the solid amine honeycomb adsorbent of the embodiment of the present application at 90° C. can reach 152 mg / g.

[0141] (2) It can be seen from Example 1 and Comparative Examples 1 to 4 that the amount ratio of the surfactant, organic solvent and silane has a greater influence on the loading amount of the solid amine; and the higher the loading amount of the solid amine is, the better. For example, the loading amount of the solid amine in Comparative Example 2 is greater than that in Example 1, but the adsorption amount of CO2 is very low.

[0142] (3) By performing SEM analysis on the surface of the solid amine honeycomb adsorbent of Example 1, as shown in FIG. Figure 3a to Figure 3c As shown, by 3a~ Figure 3c It can be seen that the solid amine is evenly loaded on the surface of the glass fiber, and the organic amine connects and wraps the SiO2 particles.

[0143] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a solid amine honeycomb adsorbent, characterized in that: The steps include: The honeycomb carrier and the organic amine mixed solution are subjected to a loading treatment and then subjected to a synthesis reaction, and then the mixture is subjected to impurity removal and drying to obtain a solid amine honeycomb adsorbent; Wherein, the organic amine mixed solution comprises: organic amine, silane, surfactant and organic solvent; The preparation of the organic amine mixed solution comprises the steps of: Performing a first mixing treatment on a mixed system of the surfactant, an organic solvent and an organosilane to obtain a mixed solution; performing a second mixing process on the mixed solution and the organic amine to obtain the organic amine mixed solution; The synthesis reaction step comprises: mixing a solid amine honeycomb adsorbent precursor with an alkaline solution at room temperature or in a water bath for a reaction time of 10 minutes to 4 hours to obtain a wet honeycomb adsorbent.

2. The method for preparing a solid amine honeycomb adsorbent according to claim 1, characterized in that: The molar ratio of the surfactant, the organic solvent and the silane is 1:400-10000:10-1000.

3. The method for preparing a solid amine honeycomb adsorbent according to claim 1, characterized in that: The concentration of the silane in the organic amine mixed solution is 0.1 mol / L to 100 mol / L.

4. The method for preparing a solid amine honeycomb adsorbent according to claim 1, characterized in that: The mass ratio of the mixed solution to the organic amine is 10:1-100.

5. The method for preparing a solid amine honeycomb adsorbent according to claim 1, characterized in that: The loading treatment step comprises: immersing the honeycomb carrier in the organic amine mixed solution at room temperature or in a water bath for 1 min to 2 h, and drying after immersion to obtain a solid amine honeycomb adsorbent precursor.

6. The method for preparing a solid amine honeycomb adsorbent according to claim 1, characterized in that: The mass ratio of the solid amine honeycomb adsorbent precursor to the alkaline solution is 1:1-10.

7. A solid amine honeycomb adsorbent prepared by the method for preparing a solid amine honeycomb adsorbent according to any one of claims 1 to 6, characterized in that: The solid amine honeycomb adsorbent comprises a honeycomb carrier, silica gel and an organic amine; the organic amine is loaded on the surface of the silica gel and in the pores of the honeycomb carrier to form a solid amine; The loading amount of the solid amine is 50 kg / m 3 ~200kg / m 3 .

8. Use of a solid amine honeycomb adsorbent prepared by the preparation method of the solid amine honeycomb adsorbent according to any one of claims 1 to 6 or a solid amine honeycomb adsorbent according to claim 7 in the field of carbon capture technology.

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