Silica-based solid amine honeycomb adsorbents and methods of making same

Abstract

This invention provides a silicon-based solid amine honeycomb adsorbent and its preparation method. The preparation method of the silicon-based solid amine honeycomb adsorbent includes the following steps: organic adhesive modification: in a non-polar solvent, an organic adhesive is modified with a first coupling agent to obtain a modified organic adhesive; slurry preparation: silicon-based solid amine powder is mixed with water, a first dispersant and an antifoaming agent are added, and the mixture is stirred evenly; subsequently, the modified organic adhesive and an inorganic adhesive are added sequentially, and the mixture is stirred evenly to obtain a silicon-based solid amine slurry; film-forming system construction: a film-forming agent and a second dispersant are added to the silicon-based solid amine slurry, and the mixture is stirred to construct a film-forming system; substrate loading: the film-forming system is loaded onto a glass fiber substrate to obtain the silicon-based solid amine honeycomb adsorbent. This invention achieves uniform dispersion of silicon-based solid amine powder in the slurry through the synergistic stabilizing effect of the film-forming agent and the dispersant, providing a feasible solution for the low-cost, large-scale preparation of high-performance solid amine coating modules.

Description

Technical Field

[0001] This invention belongs to the field of solid amine adsorbent technology, and particularly relates to a silicon-based solid amine honeycomb adsorbent and its preparation method. Background Technology

[0002] Carbon dioxide is the most significant greenhouse gas, and controlling its emissions is an urgent issue in global environmental governance. Carbon capture technology is a key means of achieving emission reduction, and currently mainly includes liquid amine absorption and solid amine adsorption. Liquid amine technology is mature, but it suffers from problems such as high regeneration energy consumption and strong equipment corrosion. Solid amine adsorption, on the other hand, has advantages such as large adsorption capacity, good selectivity, mild operating conditions, and low energy consumption, and is considered to have greater potential for large-scale application.

[0003] Existing solid amine adsorbents are mostly in powder or granular form and are used in fixed or fluidized beds. These methods suffer from long diffusion paths and slow adsorption rates. To improve the removal rate, the bed thickness often needs to be increased, leading to increased system pressure resistance and energy consumption. To address this, the industry has developed a honeycomb coating module technology, which coats solid amine powder onto a structured substrate to improve material utilization efficiency and reduce pressure resistance.

[0004] Silicon-based solid amines are composite materials in which organic amines are supported on silica, offering advantages such as large specific surface area of ​​the support and low cost. However, during large-scale preparation, uneven mixing can easily lead to localized aggregation of organic amines, forming large-diameter particles that affect subsequent coating processes. Therefore, it is necessary to develop a coating and molding process suitable for large-diameter silicon-based solid amines. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a silicon-based solid amine honeycomb adsorbent and its preparation method. Through the synergistic effect of the film-forming agent and the dispersant, the problem of dispersion stability of silicon-based solid amine powder is solved. Therefore, uniform coating can be achieved without relying on complex pretreatments such as high-intensity mechanical stirring, opening up a new direction for the large-scale, low-cost preparation of high-performance solid amine coating modules.

[0006] To achieve the above objectives, the present invention provides a method for preparing a silicon-based solid amine honeycomb adsorbent, comprising the following steps:

[0007] Organic adhesive modification: In a non-polar solvent, an organic adhesive is modified with a first coupling agent to obtain a modified organic adhesive;

[0008] Slurry preparation: Mix the silicon-based solid amine powder with water, add the first dispersant and defoamer, and stir until homogeneous; then, add the modified organic adhesive and inorganic adhesive in sequence, and continue stirring until homogeneous to obtain the silicon-based solid amine slurry;

[0009] Film-forming system construction: A film-forming agent and a second dispersant were added to the silicon-based solid amine slurry, and the mixture was stirred to construct the film-forming system;

[0010] Matrix loading: The film-forming system is loaded onto a glass fiber matrix to prepare a silicon-based solid amine honeycomb adsorbent.

[0011] Optionally, the particle size of the silicon-based solid amine powder is 0.30-0.60 mm;

[0012] The carrier of the silicon-based solid amine powder is silicon dioxide, and the pore volume of the silicon dioxide is greater than 1.5 cm³. 3 / g, wherein the specific surface area of ​​the silica is 150-600 m² / g. 2 / g, wherein the hydroxyl content on the surface of the silica is 2-3 per nm. 2 ;

[0013] The silicon-based solid amine powder is obtained by modifying silicon dioxide with organic amine; wherein the mass ratio of the organic amine to the silicon dioxide is 30:(30-60).

[0014] Optionally, the silicon-based solid amine slurry comprises, by mass parts, the following components: 40-60 parts of silicon-based solid amine powder, 100-160 parts of water, 10-20 parts of a first dispersant, 0.1-1 parts of defoamer, 0.5-10 parts of modified organic adhesive, and 1-20 parts of inorganic adhesive.

[0015] Optionally, the first dispersant includes one or more of sulfates, phosphates, cellulose derivatives, polyethylene glycol, and silicone oil;

[0016] The defoamer includes one or more of the following: organosilicon-polyether (BYK-024), triacetyl phosphate, polyisoprene, and AFE-1520;

[0017] The inorganic adhesive includes one or more of the following: neutral silica sol, tetraethoxysilane, tetraisopropoxytitanium, and aluminum isopropoxide.

[0018] Optionally, the organic adhesive includes one or more of epoxy resin, acrylate, polyvinyl alcohol, polyurethane, phenolic resin, and polyvinylpyrrolidone;

[0019] The nonpolar solvent includes one or more of cyclohexane, toluene, 1,2-dichloroethane, ethyl acetate, and heptane;

[0020] The first coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents;

[0021] The mass ratio of the organic adhesive, the first coupling agent and the nonpolar solvent is (1-5):(1-10):(10-50).

[0022] Optionally, the film-forming agent includes one or more of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethylene glycol phenyl ether, dibutyl phthalate, dipropylene glycol butyl ether, isobutyl isobutyrate, dioctyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate, and triethyl citrate.

[0023] The second dispersant includes one or more of sulfates, phosphates, cellulose derivatives, polyethylene glycol, and silicone oil;

[0024] The mass ratio of the film-forming agent to the second dispersant is (1-10):(20-40).

[0025] Optionally, the glass fiber matrix is ​​a modified glass fiber matrix;

[0026] The preparation process of the modified glass fiber matrix includes: plasma treatment of the glass fiber matrix, followed by soaking in an ethanol aqueous solution containing a second coupling agent, air drying, and vacuum drying to obtain the modified glass fiber matrix.

[0027] Optionally, the plasma treatment conditions are: under an argon atmosphere, a power of 100-600W, and a treatment time of 1-20min;

[0028] The surface roughness Ra of the plasma-treated glass fiber matrix is ​​0.5-1 μm, and the surface hydroxyl density of the plasma-treated glass fiber matrix is ​​12-15 hydroxyl groups / nm. 2 .

[0029] Optionally, the second coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents;

[0030] In the ethanol-water solution containing the second coupling agent, the mass fraction of the second coupling agent is 0.2%-5%, and the mass ratio of ethanol to water is (3-5):(7-5).

[0031] In addition, the present invention also provides a silicon-based solid amine honeycomb adsorbent prepared by the above method.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) Improve the dispersibility and applicability of powder: Through the synergistic effect of film-forming agent and dispersant, the sedimentation and agglomeration of silicon-based solid amine powder in slurry are effectively solved, enabling it to form a uniform and stable coating slurry, which broadens the application range of non-uniform adsorbent materials and reduces the stringent requirements on the particle size of raw material powder.

[0034] (2) Enhanced coating uniformity and bonding strength: By constructing a dual structure of "coupling agent layer + nano silica film" on the substrate surface through coupling agent and inorganic adhesive, the bonding strength between the coating and the substrate is significantly improved. This structure not only effectively reduces the powder shedding rate of the coating, but also ensures the uniformity of the coating thickness and avoids problems such as cracking after drying, thereby improving the structural stability and service life of the coating module.

[0035] (3) Optimize gas diffusion path and reduce system pressure resistance: The uniform coating effectively prevents the pore blockage of the honeycomb substrate during the coating process, ensuring unobstructed gas adsorption channels. This significantly reduces the pressure resistance when the airflow passes through the module, which helps to achieve more efficient gas adsorption and lower system operating energy consumption.

[0036] (4) Achieving efficient utilization and performance improvement of the adsorbent: Through precise control of the slurry dispersion system, the active sites of organic amines in the solid amine powder are fully exposed and uniformly distributed. This not only improves the utilization rate of the adsorbent, but also ensures that the coating has excellent adsorption kinetics and carbon dioxide capture efficiency.

[0037] (5) Provides a universal process solution: This solution provides a low-energy process path that does not rely on complex pretreatment or high-intensity mechanical stirring, providing a new technical direction for the large-scale, low-cost preparation of high-performance solid amine coating modules. Detailed Implementation

[0038] To make the technical problems solved, the technical solutions, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0039] This invention provides a method for preparing a silicon-based solid amine honeycomb adsorbent, comprising the following steps:

[0040] Organic adhesive modification: In a non-polar solvent, an organic adhesive is modified with a first coupling agent to obtain a modified organic adhesive;

[0041] Slurry preparation: Mix the silicon-based solid amine powder with water, add the first dispersant and defoamer, and stir until homogeneous; then, add the modified organic adhesive and inorganic adhesive in sequence, and continue stirring until homogeneous to obtain the silicon-based solid amine slurry;

[0042] Film-forming system construction: A film-forming agent and a second dispersant were added to the silicon-based solid amine slurry, and the mixture was stirred to construct the film-forming system;

[0043] Matrix loading: The film-forming system is loaded onto a glass fiber matrix to prepare a silicon-based solid amine honeycomb adsorbent.

[0044] In this embodiment of the invention, the synergistic effect of the dispersant and the film-forming agent ensures the uniformity and stability of the slurry system, providing a foundation for the formation of a complete and dense coating.

[0045] In some embodiments, the particle size of the silicon-based solid amine powder is 0.30-0.60 mm. In exemplary embodiments, the particle size of the silicon-based solid amine powder can be 0.30 mm, 0.40 mm, 0.50 mm, or 0.60 mm.

[0046] In some embodiments, the carrier of the silicon-based solid amine powder is silicon dioxide, and the pore volume of the silicon dioxide is 1.5-2.0 cm³. 3 / g, wherein the specific surface area of ​​the silica is 150-600 m² / g. 2 / g, wherein the hydroxyl content on the surface of the silica is 2-3 per nm. 2 The tested conductivity was below 1500 μS / cm. In other embodiments, the tested conductivity was 800-1500 μS / cm.

[0047] In some embodiments, the silicon-based solid amine powder is obtained by modifying silica with an organic amine; wherein the mass ratio of the organic amine to the silica is 30:(30-60). In exemplary examples, the mass ratio of the organic amine to the silica can be 30:30, 30:40, 30:50, or 30:60. Within this mass ratio range, the silica can be effectively loaded with organic amine.

[0048] In some embodiments, the silicon-based solid amine slurry comprises, by mass parts, the following components: 40-60 parts silicon-based solid amine powder, 100-160 parts water, 10-20 parts first dispersant, 0.1-1 parts defoamer, 0.5-10 parts modified organic adhesive, and 1-20 parts inorganic adhesive.

[0049] In this embodiment of the invention, an ionic dispersant and a cellulose derivative dispersant are selected for compounding. The synergistic effect of the two can enhance the steric hindrance effect of the slurry, reduce the surface tension, and construct a stable three-dimensional barrier structure.

[0050] In some embodiments, the first dispersant includes one or more of sodium sulfate, ammonium sulfate, naphthol sulfate, sodium phosphate, sodium hydrogen phosphate, barium hexaphosphate, hydroxypropyl methylcellulose (HPC), hydroxypropyl cellulose (HPMC), polyethylene glycol (PEG), sodium dodecyl sulfate (SDS), and silicone oil (PDMS).

[0051] In some embodiments, the defoamer includes one or more of organosilicon-polyether (BYK-024), triacetyl phosphate, polyisoprene, and AFE-1520.

[0052] In some embodiments, the water is deionized water.

[0053] In some embodiments, the inorganic adhesive includes one or more of neutral silica sol, tetraethoxysilane, tetraisopropoxytitanium, and aluminum isopropoxide.

[0054] In some embodiments, the organic adhesive includes one or more of epoxy resin, acrylate, polyvinyl alcohol, polyurethane, phenolic resin, and polyvinylpyrrolidone.

[0055] In some embodiments, the nonpolar solvent includes one or more of cyclohexane, toluene, 1,2-dichloroethane, ethyl acetate, and heptane.

[0056] In some embodiments, the first coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents.

[0057] In some embodiments, the first coupling agent comprises one or more of γ-aminopropenetriethoxysilane, γ-ureapropenetriethoxysilane, γ-aminopropenetrimethoxysilane, N-β-(aminoethyl)-γ-aminopropenetriethoxysilane, N-(2-aminoethyl)-3-aminopropenetriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0058] In some embodiments, the mass ratio of the organic adhesive, the first coupling agent and the nonpolar solvent is (1-5):(1-10):(10-50). In an exemplary embodiment, the mass ratio of the organic adhesive, the first coupling agent and the nonpolar solvent can be (2-5):(3-9):(20-50).

[0059] In this embodiment of the invention, the film-forming agent forms a three-dimensional network structure through the synergistic effect of molecular chain entanglement, hydrogen bonding, and solvent evaporation, thereby constructing a continuous phase. The strongly polar solvent can penetrate the surface charge layer of the organic amine, effectively weakening the van der Waals forces between silica particles and preventing aggregation.

[0060] In some embodiments, the film-forming agent includes one or more of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethylene glycol phenyl ether, dibutyl phthalate, dipropylene glycol butyl ether, isobutyl isobutyrate, dioctyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate, and triethyl citrate.

[0061] In this embodiment of the invention, polyol ester film-forming agents (such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate) have good compatibility with silicon-based solid amine powder, which can lower the film-forming temperature, promote chain segment movement, and their long-chain ester groups can encapsulate particles and regulate surface potential, thereby enhancing suspension stability. Ether film-forming agents (such as ethylene glycol phenyl ether, dipropylene glycol butyl ether, and tripropylene glycol butyl ether) act as high-boiling-point solvents, delaying volatilization to avoid skinning and reducing pinholes and cracks. Plasticizing esters (such as dibutyl phthalate, dioctyl adipate, and triethyl citrate) can insert into the molecular chain to lower the glass transition temperature and improve flexibility; the combination of dioctyl adipate and triethyl citrate further promotes low-temperature flow and spreading, reducing stress and porosity. Synergistic esters (such as isobutyl isobutyrate and diethylene glycol butyl ether acetate) volatilize in the later stages of film formation and form a transition layer, optimizing adhesion. In addition, the amphiphilic structure of the film-forming agent helps to reduce surface tension, prevent agglomeration, and regulate rheology, jointly achieving stable dispersion of the slurry and high-quality film formation.

[0062] In some embodiments, the second dispersant includes one or more of sulfates, phosphates, cellulose derivatives, polyethylene glycol, and silicone oils.

[0063] In some embodiments, the second dispersant comprises one or more of sodium sulfate, ammonium sulfate, naphthol sulfate, sodium phosphate, sodium hydrogen phosphate, barium hexaphosphate, hydroxypropyl methylcellulose (HPC), hydroxypropyl cellulose (HPMC), polyethylene glycol (PEG), sodium dodecyl sulfate (SDS), and silicone oil (PDMS).

[0064] In some embodiments, the mass ratio of the film-forming agent to the second dispersant is (1-10):(20-40), and in an exemplary embodiment, the mass ratio of the film-forming agent to the second dispersant may be (3-10):(20-35).

[0065] In some embodiments, the glass fiber matrix is ​​a modified glass fiber matrix.

[0066] In some embodiments, the preparation process of the modified glass fiber matrix includes: plasma treatment of the glass fiber matrix, followed by soaking in an ethanol aqueous solution containing a second coupling agent, air drying, and vacuum drying to obtain the modified glass fiber matrix.

[0067] In this embodiment of the invention, plasma treatment of the glass fiber matrix effectively increases its surface roughness and hydroxyl group distribution density. This pretreatment process significantly improves the grafting efficiency of the subsequent silane coupling agent. The epoxy groups contained in the silane coupling agent can undergo a condensation reaction with the hydroxyl groups on the glass fiber surface, and further heat treatment promotes the completion of the reaction, thereby constructing a stable Si-O-Si covalent bond layer at the interface, achieving a chemical anchoring effect on the silicon-based solid amine powder, making it more uniform and stable in distribution on the substrate surface. Although plasma treatment causes a slight increase in surface energy, the film-forming agent introduced into the system effectively alleviates stress concentration caused by differences in interface properties, improving the overall compatibility and stability of the coating.

[0068] Furthermore, in this embodiment of the invention, a second coupling agent is used to achieve chemical anchoring and molecular bridging on the substrate surface, thereby guiding the in-situ growth of nano-silica films. A strong and tough bonding interface is formed through organic-inorganic hybridization, enhancing coating adhesion and cohesive strength while reducing powder shedding. Simultaneously, the amphiphilicity of the film-forming agent promotes the directional alignment of organic amine molecules, and the synergistic effect of the coordination adsorption of inorganic acid anions and the steric hindrance at the polar end of the film-forming agent inhibits particle agglomeration, achieving uniform dispersion and fixation of highly loaded functional particles.

[0069] In some embodiments, the plasma treatment conditions are: under an argon atmosphere, a power of 100-600W, and in exemplary cases, the power can be 100W, 200W, 300W, 400W, 500W, or 600W; and a treatment time of 1-20 minutes.

[0070] In some embodiments, the surface roughness Ra of the plasma-treated glass fiber matrix is ​​0.5-1 μm, and the surface hydroxyl density of the plasma-treated glass fiber matrix is ​​12-15 hydroxyl groups / nm. 2 .

[0071] In some embodiments, the second coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents.

[0072] In some embodiments, the second coupling agent comprises one or more of γ-aminopropenetriethoxysilane, γ-ureapropenetriethoxysilane, γ-aminopropenetrimethoxysilane, N-β-(aminoethyl)-γ-aminopropenetriethoxysilane, N-(2-aminoethyl)-3-aminopropenetriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0073] In some embodiments, the mass fraction of the second coupling agent in the ethanol-water solution containing the second coupling agent is 0.2%-5%. In exemplary embodiments, the mass fraction of the second coupling agent can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. The mass ratio of ethanol to water is (3-5):(7-5). In exemplary embodiments, the mass ratio of ethanol to water can be 3:7, 4:7, 5:7, 3:6, 4:6, 5:6, 3:5, 4:5, or 5:5.

[0074] In some embodiments, the fiberglass matrix has a corrugated structure, and the ratio of the corrugated height to the width is 1.6cm / 3.2cm;

[0075] The size of the fiberglass matrix is ​​50mm×50mm×50mm, 100mm×100mm×100mm to 10000mm×10000mm×10000mm.

[0076] In addition, embodiments of this application also provide a silicon-based solid amine honeycomb adsorbent prepared by the above method.

[0077] To further illustrate the technical effects of the present invention, the following specific embodiments are also provided.

[0078] Example 1:

[0079] Example 1 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of this adsorbent includes the following steps:

[0080] The specific steps for S1 glass fiber matrix pretreatment and surface modification are as follows:

[0081] First, soak the 50mm×50mm×50mm glass fiber substrate in ethanol for about 5 minutes to remove surface grease and particles, and then dry it in a drying oven for later use.

[0082] Subsequently, the glass fiber matrix was treated for 8 minutes under conditions of an argon to oxygen volume ratio of 4:1, a vacuum degree of 10-30 Pa, and an RF power of 150 W. This process utilizes argon ions to etch the substrate surface to increase roughness, while simultaneously using oxygen plasma to introduce polar functional groups such as hydroxyl and carboxyl groups.

[0083] Next, 6-7 parts by weight of ethanol and 10-12 parts by weight of deionized water are mixed and stirred evenly. Then, 0.5-1 parts by weight of the second coupling agent (γ-aminopropylenetriethoxysilane) are added to prepare an ethanol-water solution containing the second coupling agent (γ-aminopropylenetriethoxysilane). The plasma-treated glass fiber matrix is ​​then immersed in the ethanol-water solution containing the second coupling agent (γ-aminopropylenetriethoxysilane) for 30 minutes. After removal, it is dried at 60-90°C to finally obtain the modified glass fiber matrix.

[0084] The specific steps for modifying S2 organic adhesive are as follows:

[0085] First, the organic adhesive (polyvinyl alcohol), the first coupling agent (γ-aminopropylenetriethoxysilane), and the non-polar solvent (cyclohexane) are placed in a reactor at a mass ratio of 5:7:20. The reactor is placed in a 50°C water bath, and the mixture is continuously stirred at a magnetic stirring speed of 250 r / min until the mixture forms a uniform and transparent gel-like liquid, which is the modified organic adhesive.

[0086] The specific steps for preparing S3 slurry are as follows:

[0087] At 50°C, 50 parts by weight of silicon-based solid amine powder with a particle size of 0.30-0.60 mm were added to 160 parts by weight of deionized water. Then, 10 parts by weight of the first dispersant (sodium sulfate) and 1 part by weight of the defoamer (triacetyl phosphate) were added, and the mixture was magnetically stirred for 1 hour to obtain a preliminarily dispersed slurry. Next, 10 parts by weight of modified organic adhesive and 20 parts by weight of inorganic adhesive (neutral silica sol) were added to the slurry in sequence, mixed, heated to 80°C, and stirred at a shear rate of 300 r / min for 1 hour to finally obtain a uniform and stable silicon-based solid amine slurry.

[0088] The S4 film-forming system was constructed using the following specific steps:

[0089] In step S3, 10 parts by weight of film-forming agent (2,2,4-trimethyl) are added sequentially to the silicon-based solid amine slurry. The film-forming system was obtained by stirring 1,3-pentanediol monoisobutyrate and 20 parts by mass of the second dispersant (sodium sulfate) at 45°C and a shear rate of 300 r / min.

[0090] S5 substrate loading, the specific steps are as follows:

[0091] The modified glass fiber matrix obtained in step S1 is immersed in the film-forming system prepared in step S4 for 20 minutes, and then pulled up at a uniform speed of 10 mm / s to ensure uniform coating. If the coating amount needs to be increased, the immersion can be repeated, with each immersion time being approximately 10 minutes, while maintaining the same pulling speed. After coating, the modified glass fiber matrix is ​​suspended to drain until no obvious droplets fall, and the blockage of the internal pores is observed. If blockage occurs, it can be treated by uniformly blowing at a wind speed of 2 m / s. Subsequently, the drained modified glass fiber matrix coated with the film-forming system is placed in a drying oven for gradient temperature drying: 50℃ for 1 hour, 80℃ for 1 hour, and 120℃ for 30 minutes. After drying, the silicon-based solid amine honeycomb adsorbent is obtained.

[0092] Example 2:

[0093] Example 2 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Example 2 is basically the same as that of Example 1, except that:

[0094] The coupling agent used is γ-glycidoxypropyltrimethoxysilane, the dispersant is hydroxypropyl methylcellulose, and the film-forming agent is dibutyl phthalate.

[0095] Example 3:

[0096] Example 3 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Example 3 is basically the same as that of Example 1, except that:

[0097] The coupling agent used is γ-methacryloxypropyltrimethoxysilane, the dispersant is sodium phosphate, and the film-forming agent is a mixture of dioctyl adipate and triethyl citrate.

[0098] Example 4:

[0099] Example 4 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Example 4 is basically the same as that of Example 1, except that:

[0100] The coupling agent used is γ-aminopropylenetrimethoxysilane, the non-polar solvent used is toluene, the dispersant is sodium dodecyl sulfate, and the film-forming agent is isobutyl isobutyrate.

[0101] Example 5:

[0102] Example 5 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Example 5 is basically the same as that of Example 1, except that:

[0103] The coupling agent used is γ-glycidyl etheroxypropyltrimethoxysilane, the dispersant is barium hexaphosphate, the defoamer is polyisoprene, and the film-forming agent is dipropylene glycol butyl ether.

[0104] Comparative Example 1

[0105] Comparative Example 1 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that no dispersant is added in step S3.

[0106] Comparative Example 2

[0107] Comparative Example 2 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that no film-forming agent is added in step S4.

[0108] Comparative Example 3

[0109] Comparative Example 3 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Comparative Example 3 is basically the same as that of Example 1, except that no dispersant is added in steps S3 and S4.

[0110] Comparative Example 4

[0111] Comparative Example 4 provides a silicon-based solid amine honeycomb adsorbent. The preparation method of Comparative Example 4 is basically the same as that of Example 1, except that no dispersant is added in steps S3 and S4, and no film-forming agent is added in step S4.

[0112] To verify the progressiveness of the embodiments of the present invention, the silicon-based solid amine honeycomb adsorbents prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to piezoresistive tests, pore blockage depth tests, powder shedding rate tests, and carbon dioxide adsorption capacity tests. The specific performance test results are shown in Table 1.

[0113] (1) Piezoresistive test: The prepared silicon-based solid amine honeycomb adsorbent was loaded into a self-made 50×50×50 mm alloy test pipe. The pressure difference before and after the airflow passed through the adsorbent bed was measured using a pressure sensor, and the piezoresistive value was tested. Based on the gas flow rate and the cross-sectional area of ​​the pipe, the gas velocity under the test conditions was calculated to be 4 m / s.

[0114] (2) Pore depth test: Check whether there is pore blockage at the bottom of the silicon-based solid amine honeycomb adsorbent. For adsorbents with blockage, cut them open along the corrugation direction, measure the length of the blockage powder on the side wall, and take this length as the pore depth.

[0115] (3) Powder shedding rate test: Lay a piece of white paper flat on the table, drop the silicon-based solid amine honeycomb adsorbent vertically from a height of 50 cm above the horizontal table, observe the powder shedding, collect the fallen powder, weigh it and calculate the powder shedding rate.

[0116] (4) Carbon dioxide adsorption capacity test: The carbon dioxide adsorption capacity of the solid amine adsorbent was determined by gravimetric method. Before the test, the sample needs to be pretreated: firstly, it is vacuum dried at 60–90℃ for 1 h, and then purged to room temperature in a nitrogen flow of 300 mL / min to ensure complete desorption. The pretreated sample is placed in an air trapping platform for carbon dioxide adsorption experiment to determine the adsorption capacity.

[0117] Table 1 Performance Tests of Silicon-Based Solid Amine Cellular Adsorbents

[0118]

[0119] Table 1 shows that the silicon-based solid amine honeycomb adsorbent prepared in the embodiments of the present invention is significantly superior to the comparative examples in all aspects: Comparative Example 1, which does not add a dispersant in step S3; Comparative Example 2, which does not add a film-forming agent in step S4; Comparative Example 3, which does not add a dispersant in both steps S3 and S4; and Comparative Example 4, which does not add a dispersant in steps S3 and S4 and does not add a film-forming agent in step S4. This result empirically demonstrates that the synergistic effect of the film-forming agent and the dispersant effectively improves the dispersion stability of silicon-based solid amine powder (especially large-particle-size silicon-based solid amine powder >50 mesh), thus achieving uniform coating without relying on complex pretreatment such as high-intensity mechanical stirring. This provides a new path for the large-scale, low-cost preparation of high-performance solid amine coating modules.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] This invention solves the dispersion stability problem of silicon-based solid amine powder through the synergistic effect of film-forming agents and dispersants, achieving uniform coating without the need for high-intensity mechanical stirring. The dual-interface structure of "coupling agent + inorganic adhesive" significantly enhances coating adhesion and uniformity, effectively preventing powder shedding and cracking. This process ensures unobstructed gas channels, reduces system pressure resistance, thereby improving adsorption efficiency and module lifespan, providing an innovative and universal solution for the large-scale, low-cost preparation of high-performance solid amine adsorbents.

[0122] Specific embodiments of the present invention have been described. It should be understood that the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for preparing a silicon-based solid amine honeycomb adsorbent, characterized in that, Includes the following steps: Organic adhesive modification: In a non-polar solvent, an organic adhesive is modified with a first coupling agent to obtain a modified organic adhesive; The organic adhesive includes one or more of epoxy resin, acrylate, polyvinyl alcohol, polyurethane, phenolic resin, and polyvinylpyrrolidone; The first coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents; The mass ratio of the organic adhesive, the first coupling agent, and the nonpolar solvent is (1-5):(1-10):(10-50). Slurry preparation: Mix the silicon-based solid amine powder with water, add the first dispersant and defoamer, and stir until homogeneous; then, add the modified organic adhesive and inorganic adhesive in sequence, and continue stirring until homogeneous to obtain the silicon-based solid amine slurry; The silicon-based solid amine powder is obtained by modifying silicon dioxide with organic amines, and the carrier of the silicon-based solid amine powder is silicon dioxide; The first dispersant includes one or more of sulfates, phosphates, cellulose derivatives, polyethylene glycol, and silicone oil; The inorganic adhesive includes one or more of the following: neutral silica sol, tetraethoxysilane, tetraisopropoxytitanium, and aluminum isopropoxide. The silicon-based solid amine slurry comprises, by weight, the following components: 40-60 parts silicon-based solid amine powder, 100-160 parts water, 10-20 parts first dispersant, 0.1-1 parts defoamer, 0.5-10 parts modified organic adhesive, and 1-20 parts inorganic adhesive; Film-forming system construction: A film-forming agent and a second dispersant were added to the silicon-based solid amine slurry, and the mixture was stirred to construct the film-forming system; The film-forming agent includes one or more of the following: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethylene glycol phenyl ether, dibutyl phthalate, dipropylene glycol butyl ether, isobutyl isobutyrate, dioctyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate, and triethyl citrate. The second dispersant includes one or more of sulfates, phosphates, cellulose derivatives, polyethylene glycol, and silicone oil; The mass ratio of the film-forming agent to the second dispersant is (1-10):(20-40); Matrix loading: The film-forming system is loaded onto a glass fiber matrix to prepare a silicon-based solid amine honeycomb adsorbent; The glass fiber matrix is ​​a modified glass fiber matrix; The preparation process of the modified glass fiber matrix includes: plasma treatment of the glass fiber matrix, followed by soaking in an ethanol aqueous solution containing a second coupling agent, air drying, and vacuum drying to obtain the modified glass fiber matrix; The second coupling agent includes one or more of aminosilane coupling agents, epoxysilane coupling agents, and methacryloxysilane coupling agents.

2. The method for preparing the silicon-based solid amine honeycomb adsorbent according to claim 1, characterized in that, The particle size of the silicon-based solid amine powder is 0.30-0.60 mm; The silica has a pore volume greater than 1.5 cm³. 3 / g, wherein the specific surface area of ​​the silica is 150-600 m² / g. 2 / g, wherein the hydroxyl content on the surface of the silica is 2-3 per nm. 2 ; The mass ratio of the organic amine to the silicon dioxide is 30:(30-60).

3. The method for preparing the silicon-based solid amine honeycomb adsorbent according to claim 1, characterized in that, The defoamer includes one or more of organosilicon polyether BYK-024, triacetyl phosphate, polyisoprene, and AFE-1520.

4. The method for preparing the silicon-based solid amine honeycomb adsorbent according to claim 1, characterized in that, The nonpolar solvent includes one or more of cyclohexane, toluene, 1,2-dichloroethane, ethyl acetate, and heptane.

5. The method for preparing the silicon-based solid amine honeycomb adsorbent according to claim 1, characterized in that, The conditions for plasma treatment are: under an argon atmosphere, with a power of 100-600W and a treatment time of 1-20min; The surface roughness Ra of the plasma-treated glass fiber matrix is ​​0.5-1 μm, and the surface hydroxyl density of the plasma-treated glass fiber matrix is ​​12-15 hydroxyl groups / nm. 2 .

6. The method for preparing the silicon-based solid amine honeycomb adsorbent according to claim 1, characterized in that, In the ethanol-water solution containing the second coupling agent, the mass fraction of the second coupling agent is 0.2%-5%, and the mass ratio of ethanol to water is (3-5):(7-5).

7. A silicon-based solid amine honeycomb adsorbent, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 6.

Images