Composite adsorbent and preparation method thereof, adsorption separation device and method

Abstract

The present invention belongs to the technical field of gas separation and purification materials, and specifically relates to a composite adsorbent and its preparation method, an adsorption separation device and method. The raw materials of the composite adsorbent include a carrier and an active material; the active material includes NO x adsorption material, water adsorption material and CO2 adsorption material; the NO x The mass ratio of the adsorption material, the water adsorption material and the CO2 adsorption material is 5-15:7-18:10. The composite adsorbent provided by the present invention can achieve NO x , synergistic adsorption of H2O and CO2.

Description

Technical Field

[0001] The present invention relates to the technical field of gas separation and purification materials, and in particular to a composite adsorbent and a preparation method thereof, and an adsorption separation device and method. Background Art

[0002] Flue gas contains NO x , H2O, and CO2 are typically removed in a sequential order of denitrification, decarbonization, and dehydration during flue gas treatment prior to emission. Denitrification primarily utilizes oxidative adsorption, decarbonization primarily utilizes chemical absorption, and denitrification primarily utilizes physical adsorption. While these methods allow for targeted adsorption and separation of gas components, the step-by-step removal approach presents numerous challenges.

[0003] The distributed removal process is cumbersome and the equipment components are complex, which leads to increased operating energy consumption. The desorption temperatures of adsorbents for different gases overlap significantly. During the gas desorption process, the flue gas often undergoes multiple heating and cooling processes of heating, cooling, heating again, and cooling again, resulting in heat waste. Therefore, an adsorbent that can simultaneously adsorb and desorb three gases is needed to solve these problems. However, from the perspective of adsorption and desorption principles, preparation, and materials, the adsorption materials for the three gases cannot be integrated to obtain an adsorbent that can simultaneously adsorb and desorb three gases.

[0004] From the principle of adsorption and desorption, the strong adsorption of H2O will occupy NO x , CO2 adsorption sites, leading to NO x , the adsorption capacity of CO2 is greatly reduced, while NO x Mainly NO, NO x , N2O and other gases, CO2 molecular properties (such as molecular diameter, boiling point, melting point, dipole moment, polarity, etc.) are between these NO x In the gas, it is difficult to convert NO x and CO2 separation.

[0005] From the perspective of material preparation, composite coating requires higher slurry properties than traditional single adsorbents, making it difficult to ensure slurry stability, both microscopically and macroscopically. Microscopically, differences in the zeta potential of different adsorbent molecules produce a flocculation effect, leading to affinity aggregation in the slurry. This results in layer-by-layer stacking of different adsorbents after coating, causing problems such as easy shedding, powder loss, and low strength. Macroscopically, due to the different particle sizes of various adsorbents, they easily agglomerate, resulting in reduced dispersibility and uniformity of the slurry, which in turn causes adsorbent sedimentation and makes effective coating difficult. Summary of the Invention

[0006] In order to solve the above problems, the present invention provides a composite adsorbent and its preparation method, adsorption separation device and method. The composite adsorbent solves the problem of NO x , the technical problem that H2O and CO2 cannot be adsorbed synergistically.

[0007] One of the purposes of the present invention is to provide a composite adsorbent, the raw materials of which include a carrier and an active material;

[0008] The active material includes NO x Adsorption materials, water adsorption materials and CO2 adsorption materials;

[0009] The NO x The mass ratio of the adsorption material, the water adsorption material and the CO2 adsorption material is 5~15:7~18:10.

[0010] A second object of the present invention is to provide a method for preparing the composite adsorbent, comprising the following steps:

[0011] coating the mixed coating slurry and the carrier;

[0012] The mixed coating slurry contains the active material, dispersant, pH regulator, defoaming agent, sol and solvent.

[0013] A third object of the present invention is to provide a rotary adsorption separation device, wherein the adsorbent used includes the above-mentioned composite adsorbent.

[0014] A fourth object of the present invention is to provide a separation method for the above-mentioned rotary adsorption separation device, comprising the following steps:

[0015] The above composite adsorbent is used to perform adsorption separation on the gas.

[0016] A fifth object of the present invention is to provide a fixed bed adsorption separation device, wherein the adsorbent used includes the above-mentioned composite adsorbent.

[0017] A sixth object of the present invention is to provide an adsorption separation method for the fixed bed adsorption separation device, comprising the following steps:

[0018] The above composite adsorbent is used to perform adsorption separation on the gas.

[0019] The composite adsorbent and preparation method, gas separation device and method provided by the present invention have at least the following beneficial technical effects compared with the prior art:

[0020] (1) The composite adsorbent provided by the present invention can achieve NO x , synergistic adsorption of H2O and CO2.

[0021] (2) The preparation method of the composite adsorbent provided by the present invention can x Adsorption materials, water adsorption materials and CO2 adsorption materials are reasonably loaded on the carrier, and the prepared composite adsorbent can achieve NO x , synergistic adsorption of H2O and CO2. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of the preparation process of the mixed coating slurry in an embodiment of the present invention;

[0023] Figure 2 Schematic diagram of the rotor structure of the rotor adsorption separation device in an embodiment of the present invention;

[0024] Figure 3 Schematic diagram of gas flow during zoned desorption of a composite adsorbent in a gas adsorption separation method of a rotary adsorption separation device according to an embodiment of the present invention;

[0025] Figure 4 Schematic diagram of the principle of zoned desorption of a composite adsorbent in a gas adsorption separation method of a rotary adsorption separation device according to an embodiment of the present invention;

[0026] Figure 5 Schematic diagram of the placement of the composite adsorbent in the fixed bed adsorption separation device according to an embodiment of the present invention;

[0027] Figure 6 Schematic diagram of the structure of the composite adsorbent prepared in Example 1-2 of the present invention;

[0028] Figure 7 is a SEM image of the composite adsorbent prepared in Example 1-2 of the present invention;

[0029] Figure 8 Schematic diagram of the structure of the composite adsorbent prepared in Example 2-2 of the present invention;

[0030] Figure 9 Schematic diagram of the structure of the composite adsorbent prepared in Example 3-2 of the present invention.

[0031] Explanation of reference numerals: 1-mixed adsorption zone, 2-NO x Desorption zone, 3-H2O desorption zone, 4-CO2 desorption zone, 5-cooling zone, 6-composite adsorbent, 7-MOR zeolite, 8-ZSM-35 zeolite, 9-3A zeolite, 10-silica sol, 11-glass fiber, 12-4A zeolite, 13-NaY zeolite, 14-ZSM-5 zeolite, 10-silica sol, 11-glass fiber, 15-Beta zeolite, 16-Ti-MCM-41, 17-NaX zeolite. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the implementation of this application clearer, the technical solutions in the embodiments of this application will be described in more detail below in conjunction with the drawings in the embodiments of this application. In the drawings, the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The described embodiments are part of the embodiments of this application, not all of the embodiments. The embodiments described below with reference to the drawings are exemplary and are intended to be used to explain this application, and should not be understood as limitations on this application. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application. The embodiments of this application are described in detail below in conjunction with the drawings.

[0033]

Composite adsorbent

[0034] A first aspect of an embodiment of the present invention provides a composite adsorbent, wherein the raw materials include a carrier and an active material;

[0035] The active material includes NO x Adsorption materials, water adsorption materials and CO2 adsorption materials;

[0036] NO x The mass ratio of the adsorption material, the water adsorption material and the CO2 adsorption material is (5~15):(7~18):10.

[0037] The composite adsorbent provided by the embodiment of the present invention, NO x The adsorption material, water adsorption material and CO2 adsorption material are evenly distributed on the carrier, and the adsorbed H2O is used to promote the conversion of CO2 and NO x The dissolution and reaction of NO x , synergistic adsorption of CO2 and H2O to improve the adsorption efficiency.

[0038] In some embodiments, NO x The adsorption material includes at least one of ZSM-35 zeolite, ZSM-5 zeolite, Beta zeolite, SAPO-34 zeolite, and SSZ-13 zeolite.

[0039] In some embodiments, the water adsorption material includes at least one of 3A, 4A, and Ti-MCM-41.

[0040] In some embodiments, the CO 2 adsorption material includes at least one of Y zeolite, X zeolite, and MOR zeolite.

[0041] In some embodiments, the Y zeolite includes at least one of NaY zeolite and KY zeolite.

[0042] In some embodiments, the X zeolite includes at least one of NaX zeolite and KX zeolite.

[0043] In some embodiments, the material of the carrier includes glass fiber and ceramic fiber.

[0044] In some embodiments, the glass fiber has an aspect ratio of 1 to 10:1.

[0045] In some embodiments, the aspect ratio of the ceramic fiber is 1-10:1.

[0046] In some embodiments, the support structure is a honeycomb adsorbent structure or a layered adsorbent structure.

[0047]

Preparation method of composite adsorbent

[0048] A second aspect of an embodiment of the present invention provides a method for preparing a composite adsorbent, comprising the following steps:

[0049] S10. The mixed coating slurry and the carrier are coated;

[0050] The mixed coating slurry contains active material, first dispersant, second dispersant, sol and auxiliary agent.

[0051] The preparation method of the composite adsorbent provided by the embodiment of the present invention comprises the following steps: the first dispersant reduces surface tension and exerts a dispersing effect, and has both dispersing and surface active functions; the second dispersant ensures the uniformity and stability of molecular distribution in the slurry through charge repulsion and steric hindrance, constructs a particle dispersion system, and mainly plays the role of molecular dispersion, but has no surface activity; under the joint action of the first dispersant and the second dispersant, the prepared mixed coating slurry is stable, uniform and highly dispersible, and the active material in the slurry state ensures that the adsorbent material molecules coexist and are evenly distributed, and the same adsorbent material molecules aggregate in the same layer but do not agglomerate, and no apparent sedimentation occurs; the mixed coating slurry containing the active material is coated on a carrier, and the obtained composite adsorbent can achieve NO x , synergistic adsorption of H2O and CO2.

[0052] In some embodiments, in the above step S10, the volume ratio of the mixed coating slurry and the carrier is (2-5):1.

[0053] In some embodiments, in step S10, the pH value of the mixed coating slurry is 8 to 11. Within this pH range, the adsorbent material can better exert its adsorption effect and avoid material deactivation. Moreover, due to the charge effect, the uniformity of the distribution of the active material is also ensured.

[0054] In some embodiments, in step S10, the viscosity of the mixed coating slurry is 10 mPa·s to 200 mPa·s. This viscosity range ensures the stability and dispersibility of the slurry; too low a viscosity will reduce the loading capacity, and too high a viscosity will cause pore blocking.

[0055] In some embodiments, in step S10, the viscosity of the mixed coating slurry is 30 mPa·s to 150 mPa·s. Within this viscosity range, the slurry has good stability and dispersibility.

[0056] In some embodiments, in step S10, the viscosity of the mixed coating slurry is 30 mPa·s to 80 mPa·s. This viscosity range ensures both slurry stability and dispersibility, while achieving the best coating loading and coating effect of the active material, with virtually no powdering, pore clogging, or other adverse effects on adsorption.

[0057] In some embodiments, in the above step S10, the mass of the first dispersant is 0.05% to 2% of the active material.

[0058] In some embodiments, in step S10, the first dispersant includes at least one of polyether-modified polydimethylsiloxane, sodium lauryl sulfate, ethoxylated fatty acid methyl ester, heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonamide. In this case, polyether-modified polydimethylsiloxane has both the hydrophobic structure of the polysiloxane chain and the hydrophilic structure of the polyether chain, sodium lauryl sulfate has both the hydrophobic structure of the long-chain alkyl group and the hydrophilic structure of the sulfate group, ethoxylated fatty acid methyl ester has both the hydrophobic structure of the fatty acid ester and the hydrophilic structure of the polyethylene oxide chain, and heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonamide in the fluorinated surfactant have both the hydrophobic and oleophobic structures of the fluorocarbon chain and the hydrophilic structure of polar functional groups such as carboxyl and hydroxyl groups.

[0059] In some embodiments, the polyether-modified polydimethylsiloxane comprises 10% to 40% of the polydimethylsiloxane.

[0060] In some embodiments, in the above step S10, the mass of the second dispersant is 0.05% to 2% of the active material.

[0061] In some embodiments, in step S10, the second dispersant includes at least one of sodium methylene bisnaphthalene sulfonate, polyvinyl pyrrolidone, ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate. In this case, sodium methylene bisnaphthalene sulfonate provides a negative charge through the methylene group, and the sulfonic acid group in polyvinyl pyrrolidone provides a hydrogen bond. Ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate provide electrostatic repulsion through the charge carried by the ammonium or sodium ions in the side chains to disperse the particles.

[0062] In some embodiments, polyvinylpyrrolidone has a CAS number of 9003-39-8.

[0063] In some embodiments, the CAS number of ammonium polymethacrylate is 25949-70-8.

[0064] In some embodiments, the CAS number of sodium polymethacrylate is 54193-36-1.

[0065] In some embodiments, sodium polyacrylate has a CAS number of 27599-56-0.

[0066] In some embodiments, in the above step S10, the sol includes at least one of silica sol and aluminum sol.

[0067] In some embodiments, the mass concentration of the silica sol is 10% to 40%.

[0068] In some embodiments, the mass concentration of the aluminum sol is 20% to 60%.

[0069] In some embodiments, in the above step S10, the mass of the sol is 20% to 60% of the active material.

[0070] In some embodiments, in the above step S10, the auxiliary agent includes a pH regulator, a defoaming agent, a viscosity regulator and a solvent.

[0071] In some embodiments, in the above step S10, the pH adjuster includes at least one of sodium hydroxide, sodium carbonate, phosphoric acid, and citric acid;

[0072] In some embodiments, in the above step S10, the defoaming agent includes at least one of polyoxyethylene (POE) and polyoxypropylene (POP);

[0073] In some embodiments, the mass of the defoaming agent is 0.01% to 0.1% of the active material.

[0074] In some embodiments, the polyoxyethylene has a CAS number of 25322-68-3.

[0075] In some embodiments, the polyoxypropylene has a CAS number of 9003-11-6.

[0076] In some embodiments, the viscosity modifier includes at least one of hydroxyethyl cellulose, sodium carboxymethyl cellulose, methyl hydroxyethyl cellulose, and ethyl hydroxyethyl cellulose. In this case, the viscosity modifier adjusts the viscosity based on the molecular properties and substituent characteristics of the cellulose. The molecular properties herein primarily include factors such as hydrogen bonds, functional groups, molecular chain length, and molecular chain orientation, which increase or decrease the transverse shear force and intermolecular forces of the slurry, thereby adjusting the viscosity. The substituents primarily function based on the degree of substitution of their hydroxyl groups, with changes in the degree of substitution causing changes in the intermolecular forces, thereby adjusting the viscosity.

[0077] In some embodiments, the hydroxyethyl cellulose has a CAS number of 9004-62-0.

[0078] In some embodiments, the CAS number of sodium carboxymethylcellulose is 9004-32-4.

[0079] In some embodiments, the methyl hydroxyethyl cellulose has a CAS number of 9032-42-2.

[0080] In some embodiments, the ethyl hydroxyethyl cellulose has a CAS number of 9004-57-3.

[0081] In some embodiments, the solvent includes at least one of deionized water and alcohol.

[0082] In some embodiments, the alcohol comprises at least one of methanol, ethanol, and propanol.

[0083] In some embodiments, in the above step S10, the preparation of the mixed coating slurry includes the following steps:

[0084] S101. A first slurry, a CO2 adsorption material, a first dispersant and a second auxiliary agent are subjected to a first mixing process to obtain a second slurry; the first slurry contains a water adsorption material, a sol and a first auxiliary agent.

[0085] S102. Second slurry, NO x The adsorption material, the second dispersant and the third auxiliary agent are subjected to a second mixing process to obtain a third slurry.

[0086] S103. The third slurry is mixed to obtain the mixed coating slurry.

[0087] In some embodiments, in the above step S101, the preparation of the first slurry includes the following steps:

[0088] S1011. At a constant temperature of 50°C to 60°C, the water adsorption material, the sol and the first auxiliary agent are stirred and mixed, and then ultrasonically dispersed.

[0089] In the preparation of the first slurry, due to the hydrophilicity of the water-absorbing material, the water-absorbing material can be better dispersed in the slurry mainly through the action of the sol, and the slurry has better dispersibility by stirring and mixing at 50°C~60°C; ultrasonic dispersion is used to improve the uniformity of the slurry.

[0090] In some embodiments, in the above step S101, the pH value of the first slurry is 8-11.

[0091] In some embodiments, in the above step S101 , the viscosity of the first slurry is 10 mPa·s to 200 mPa·s.

[0092] In some embodiments, in the above step S101 , the viscosity of the first slurry is 30 mPa·s to 150 mPa·s.

[0093] In some embodiments, in the above step S101 , the viscosity of the first slurry is 30 mPa·s to 80 mPa·s.

[0094] In some embodiments, in step S1011, the first additive includes a solvent, a pH adjuster, and a viscosity adjuster. In this case, the solvent is used to dilute the concentration of the adsorbent material, the pH adjuster adjusts the pH value of the slurry, and the viscosity adjuster adjusts the viscosity of the slurry, so that the pH value and viscosity of the first slurry meet the requirements.

[0095] In some embodiments, in step S1011, the amount of solvent in the first slurry is 100% to 300% of the amount of the water-absorbing material. It should be noted that the amount of pH adjuster and viscosity adjuster is adjusted based on the actual pH and viscosity of the slurry, as long as the required pH and viscosity of the first slurry are achieved, and is not particularly limited herein.

[0096] In some embodiments, in the above step S1011, the stirring and mixing is carried out for 8 hours to 12 hours.

[0097] In some embodiments, in the above step S1011, during the stirring and mixing, the stirring speed is 200 rpm to 400 rpm.

[0098] In some embodiments, in the above step S1011, the ultrasonic dispersion time is 30 min to 60 min.

[0099] In some embodiments, in step S101, the second additive includes a solvent, a pH adjuster, and a viscosity adjuster. In this case, the solvent is used to dilute the concentration of the adsorbent material, the pH adjuster adjusts the pH value of the slurry, and the viscosity adjuster adjusts the viscosity of the slurry, so that the pH value and viscosity of the second slurry meet the requirements.

[0100] In some embodiments, the amount of solvent in the second slurry is 100% to 300% of the amount of the CO adsorbent material. It should be noted that the amount of pH adjuster and viscosity adjuster is adjusted based on the actual pH and viscosity of the slurry, as long as the required pH and viscosity of the second slurry are achieved, and is not particularly limited herein.

[0101] In some embodiments, in the above step S101, the first mixing process includes the following steps:

[0102] S1012. The first slurry, CO2 adsorption material, first dispersant and second auxiliary agent are stirred and mixed and then ultrasonically dispersed.

[0103] In the above-mentioned first mixing treatment, the water adsorption material is hydrophilic, while the CO2 adsorption material is hydrophobic, and the first dispersant has hydrophilic and lipophilic properties, so that the first dispersant can achieve specific combination with the water adsorption material and the CO2 adsorption material respectively, thereby achieving dispersion between the water adsorption material and the CO2 adsorption material.

[0104] In some embodiments, in the above step S1012, the stirring and mixing time is 12 hours to 16 hours.

[0105] In some embodiments, in the above step S1012, the stirring and mixing speed is 200 rpm to 600 rpm.

[0106] In some embodiments, in the above step S1012, the ultrasonic dispersion time is 60 min to 120 min.

[0107] In some embodiments, in the above step S102, the pH value of the second slurry is 8-11.

[0108] In some embodiments, in the above step S102 , the viscosity of the second slurry is 10 mPa·s to 200 mPa·s.

[0109] In some embodiments, in step S102, the temperature of the second slurry is room temperature (25°C-30°C). In this case, the second slurry prepared in step S101 can be quickly cooled to room temperature using a water bath or an ice bath to ensure that the positions of the water-adsorbing material molecules in the second slurry are stable, achieving the effect of aggregation but not agglomeration of the same adsorbent.

[0110] In some embodiments, in step S102, the third additive includes a solvent, a pH adjuster, and a viscosity adjuster. In this case, the solvent is used to dilute the concentration of the adsorbent material, the pH adjuster adjusts the pH value of the slurry, and the viscosity adjuster adjusts the viscosity of the slurry, so that the pH value and viscosity of the third slurry meet the requirements.

[0111] In some embodiments, in the above step S102, the amount of solvent in the third slurry is NO x It should be noted that the amount of pH adjuster and viscosity adjuster is adjusted according to the actual pH and viscosity of the slurry, as long as the pH value and viscosity requirements of the third slurry are met, and there is no special limitation here.

[0112] In some embodiments, in the above step S102, the second mixing process includes the following steps:

[0113] S1021. Second slurry, NO x The adsorption material, the second dispersant and the third auxiliary agent are stirred and mixed and then ultrasonically dispersed.

[0114] In the second mixing process, since the CO2 adsorption material is in a cubic structure (such as X molecular sieve), the water adsorption material is in a cubic lattice structure (such as 3A molecular sieve), and the NO x The oxidative adsorption material (such as ZSM-5 molecular sieve) has a long strip structure. The three adsorption materials have different structures and molecular particle sizes. The first dispersant cannot maintain the stability of the slurry, while the second dispersant has charge repulsion and steric hindrance to play a dispersing role. The second dispersant and the first dispersant can achieve a uniform and stable distribution of the three active materials in the slurry, and achieve the effect of coexistence and uniform distribution between different active substances, and the same substances aggregate in the same layer but do not agglomerate.

[0115] In some embodiments, in the above step S1021, the stirring and mixing time is 12 hours to 24 hours.

[0116] In some embodiments, in the above step S1021, the stirring and mixing speed is 400 rpm to 800 rpm.

[0117] In some embodiments, in the above step S1021, the ultrasonic dispersion time is 90 min to 180 min.

[0118] In some embodiments, in the above step S103, the pH value of the third slurry is 8-11.

[0119] In some embodiments, in the above step S103 , the viscosity of the third slurry is 10 mPa·s to 200 mPa·s.

[0120] In some embodiments, in step S103, the temperature of the third slurry is room temperature (25°C-30°C). In this case, the third slurry prepared in step S101 can be quickly cooled to room temperature using a water bath or an ice bath to ensure that the positions of the water-adsorbing material molecules in the third slurry are stable, achieving the effect of aggregation but not agglomeration of the same adsorbent.

[0121] In some embodiments, in the above step S103, the third mixing process includes the following steps:

[0122] S1031. The third slurry and the defoaming agent are mixed and ball-milled.

[0123] In the above mixing process, ball milling is used to eliminate the problems of sedimentation and strong force aggregation caused by different particle sizes, thereby improving the stability of the slurry; and defoaming agents are used to avoid the occurrence of pore blocking during the coating process.

[0124] In some embodiments, in the above step S1031, the mixing and ball milling time is 0.5h~2h.

[0125] In some embodiments, in the above step S1031, the rotation speed of the mixing ball mill is 600-1200 rpm.

[0126] In some embodiments, in the above step S10, the carrier is a pre-treated carrier. In this case, the surface roughness and hydroxyl density of the carrier can be increased to facilitate the subsequent loading of amino functional groups, NO x Oxidation adsorbents and other adsorbent materials.

[0127] In some embodiments, the preparation of the pretreated carrier comprises the following steps:

[0128] S102. Perform acid etching or alkaline etching on the carrier.

[0129] In some embodiments, in the above step S102 , during the acid etching, the acid includes at least one of nitric acid and hydrochloric acid.

[0130] In some embodiments, the mass concentration of nitric acid is 3% to 10%.

[0131] In some embodiments, the mass concentration of hydrochloric acid is 3% to 10%.

[0132] In some embodiments, in the above step S102 , in the alkaline etching, the alkali includes one of a sodium hydroxide solution and a potassium hydroxide solution.

[0133] In some embodiments, the concentration of the sodium hydroxide solution is 5% to 15%.

[0134] In some embodiments, the concentration of the potassium hydroxide solution is 5% to 15%.

[0135] In some embodiments, in step S102, the average pore size of the carrier is 1 mm to 3 mm. In some embodiments, in step S102, the porosity of the carrier is greater than 80%. In this case, the carrier can have both high air permeability and mechanical strength.

[0136] In some embodiments, in the above step S10, the coating process includes the following steps:

[0137] S103. The carrier is subjected to pulling, purging and drying treatments.

[0138] In some embodiments, in the above step S103, the pulling process is performed 3 to 5 times.

[0139] In some embodiments, the interval between two adjacent pulling operations is 5 min to 20 min.

[0140] In some embodiments, during the pulling process, the soaking time of a single pulling is 1 min to 2 min.

[0141] In some embodiments, in the above step S103 , during the purging process, the purging speed is 3 L / min to 10 L / min.

[0142] In some embodiments, in the above step S103 , during the purging process, the air gun pressure is 0.2 MPa to 0.4 MPa.

[0143] In some embodiments, in the above step S103, during the purge process, the purge time is 5 minutes to 20 minutes.

[0144] In some embodiments, in the above step S103, during the drying process, the drying device includes one of a vacuum drying oven, an oven, a hot plate, a heating hood, a muffle furnace, and a tube furnace.

[0145] In some embodiments, the vacuum degree in the vacuum drying oven is 0 MPa to 0.1 MPa.

[0146] In some embodiments, in the above step S103 , during the drying process, the drying temperature is 80° C. to 150° C.

[0147] In some embodiments, in the above step S103 , during the drying process, the drying time is 12 hours to 24 hours.

[0148]

Rotary adsorption separation device

[0149] A third aspect of an embodiment of the present invention provides a rotary adsorption separation device, wherein the adsorbent includes the composite adsorbent provided by an embodiment of the present invention.

[0150] In some embodiments, please refer to Figure 2 In the rotary adsorption separation device, the rotary wheel includes a mixed adsorption zone 1, a CO2 desorption zone 2, a H2O desorption zone 3, a NO x Desorption zone 4 and cooling zone 5.

[0151] In some embodiments, the mixed adsorption zone 1, NOx The area ratio of desorption zone 4, H2O desorption zone 3, CO2 desorption zone 2 and cooling zone 5 is (1~2):(1~1.6):(0.8~1.2):(0.8~1.2):1.

[0152] [Gas adsorption separation method of rotary adsorption separation device]

[0153] The fourth aspect of the present invention provides a rotary adsorption separation method, please refer to Figure 3 , including the following steps:

[0154] Z10. Use the composite adsorbent provided in the embodiment of the present invention to perform rotary adsorption and rotary desorption on the gas.

[0155] In some embodiments, in the above step Z10, the wheel adsorption includes the following steps:

[0156] Z101. The mixed gas enters the mixed adsorption zone for adsorption.

[0157] In some embodiments, in the above step Z101, the mixed gas includes at least one of flue gas, thermal power generation exhaust gas, coking plant exhaust gas, diesel vehicle exhaust gas, and chemical production exhaust gas.

[0158] In some embodiments, in the above step Z101, the wheel adsorption temperature is 20°C to 60°C.

[0159] In some embodiments, in the above step Z10, the wheel desorption comprises the following steps:

[0160] Z102. Composite adsorbent for zoned desorption.

[0161] In the above adsorption separation, the composite adsorbent is subjected to temperature increase and desorption, and the temperature increase mode is such that the desorbed composite adsorbent is cooled to 20°C by passing a cold source such as 0°C to 5°C gas; the rotor then enters the mixed adsorption zone to achieve NO x , temperature gradient desorption of H2O, CO2 and cyclic adsorption and desorption of the next group.

[0162] In some embodiments, in the above step Z102, please refer to Figure 4 , partition desorption includes the following steps:

[0163] Z1021. Desorbed gas enters NO x Desorption zone, H2O desorption zone, CO2 desorption zone.

[0164] In the above partition desorption step, the desorbed gas enters NO xIn the desorption zone, H2O desorption zone, and CO2 desorption zone, since the heating and heat transfer time of the desorption gas to the three desorption zones is different, there is a natural temperature difference in the three desorption zones, that is, the three desorption zones are heated to different temperatures by the desorption gas, thereby realizing the desorption of different gases in different zones.

[0165] In some embodiments, in the above step Z1021, the temperature of the desorbed gas is 350°C to 400°C.

[0166] Please refer to Figure 4 In some embodiments, in the above step Z1021, the temperature of the CO2 desorption zone for desorbing CO2 is 80°C~150°C.

[0167] Please refer to Figure 4 In some embodiments, in the above step Z1021, the temperature of the H2O desorption zone for desorbing H2O is 160°C to 250°C.

[0168] Please refer to Figure 4 In some embodiments, in the above step Z1021, NO x Desorption zone desorbs NO x The temperature is 260℃~320℃.

[0169] In some embodiments, in the above step Z1021, the desorption gas includes at least one of flue gas purification gas, nitrogen, and argon.

[0170] It should be noted that the cooling of the adsorbent in the cooling zone of the rotor is conventional in the art and is not particularly limited in the embodiments of the present invention.

[0171]

Fixed bed adsorption separation device

[0172] A fifth aspect of the present invention provides a fixed bed adsorption separation device, such as Figure 5 As shown, the adsorbent includes the composite adsorbent provided by an embodiment of the present invention.

[0173] [Gas adsorption separation method of fixed bed adsorption separation device]

[0174] A fifth aspect of an embodiment of the present invention provides a fixed bed adsorption separation method, comprising the following steps:

[0175] G10. Use the composite adsorbent provided in an embodiment of the present invention to perform fixed-bed adsorption and fixed-bed desorption on the gas.

[0176] In some embodiments, in the above step G10, the pressure of the fixed bed adsorption is 0 mPa to 0.6 mPa.

[0177] In some embodiments, in the above step G10, the temperature of the fixed bed adsorption is 20°C to 60°C.

[0178] In some embodiments, in the above step G10, the fixed bed desorption pressure is -100 kPa to 0 kPa.

[0179] In some embodiments, in step G10 above, fixed bed desorption includes the following steps:

[0180] G101. Under vacuum conditions, the composite adsorbent is subjected to the first removal, the second removal and the third removal.

[0181] In the above-mentioned desorption steps, the composite adsorbent is subjected to the first removal, the second removal and the third removal, so that carbon dioxide, water and nitrogen oxides can be removed step by step. In this way, the direct separation of multi-component gases of carbon dioxide, water and nitrogen oxides is achieved in a single heating process, thereby reducing equipment investment and energy consumption.

[0182] In some embodiments, in step G101 above, the first removal comprises the following steps:

[0183] G1011. Heat the composite adsorbent to 80°C~150°C at a heating rate of 2k / min~10k / min and then perform the first insulation.

[0184] In the first removal step, the composite adsorbent is heated to 80°C~150°C, so that CO2 can be removed therefrom. Since the removed CO2 can be extracted from the adsorbent system at any time under vacuum, the high-concentration CO2 can be pressurized and liquefied for storage by a pressure pump.

[0185] In some embodiments, in the above step G1011, the first insulation time is 10 to 30 minutes.

[0186] In some embodiments, in step G101 above, the second removal comprises the following steps:

[0187] G1012. Heat the composite adsorbent from 80°C to 150°C to 160°C to 250°C at a heating rate of 2k / min to 10k / min, and then perform a second heat preservation.

[0188] In the second removal step, the composite adsorbent is heated to 160°C to 250°C, so that H2O can be removed therefrom. Since the adsorbent is under vacuum, the removed H2O can be extracted from the adsorbent system at any time.

[0189] In some embodiments, in the above step G1012, the second insulation time is 10 minutes to 30 minutes.

[0190] In some embodiments, in step G101 above, the third removal comprises the following steps:

[0191] G1013. Heat the composite adsorbent from 160°C to 250°C to 260°C to 320°C at a heating rate of 2k / min to 10k / min, and then perform the third insulation.

[0192] In the third removal step, the composite adsorbent is heated to 260°C to 320°C to remove nitrogen oxides. Since the removed nitrogen oxides can be extracted from the adsorbent system at any time under vacuum, the high-concentration nitrogen oxides can be pressurized and liquefied for storage using a pressure pump.

[0193] In some embodiments, in the above step G1013, the third insulation time is 10 minutes to 30 minutes.

[0194] The following is further described with reference to specific embodiments.

[0195] For ease of description, the following examples and comparative examples involve a carrier that is a pretreated honeycomb glass fiber (with an aspect ratio of 5:1), an average pore diameter of 2 mm, and a porosity of 90%. The pretreatment steps are as follows:

[0196] The honeycomb glass fiber was etched with hydrochloric acid having a mass concentration of 6% and the etching time was 1 min.

[0197] When the following examples and comparative examples involve adjusting the pH value and viscosity, they are all carried out under stirring. The stirring method is conventional in the art and is not particularly limited in the examples of the present invention.

[0198] The following examples and comparative examples involve the desorption gas being nitrogen.

[0199] The coating and drying involved in the following comparative examples are conventional in the art and are not particularly limited.

[0200] Example 1-1

[0201] Example 1-1 provides a composite adsorbent, the raw materials of which are composed of ZSM-35, 3A, and MOR.

[0202] Among them, the mass ratio of ZSM-35, 3A and MOR is 8:12:10.

[0203] Example 1-2

[0204] Example 1-2 provides a method for preparing the composite adsorbent provided in Example 1-1, and the steps are as follows:

[0205] E10. Preparation of the first slurry: 3A, silica sol, and water were stirred and dispersed by ultrasonication at a constant temperature of 60°C. The pH and viscosity were adjusted with sodium carbonate and sodium carboxymethyl cellulose, respectively, to obtain a first slurry. The first slurry was cooled to room temperature using an ice bath.

[0206] Among them, the amount of silica sol is 40% of the total mass and the mass concentration is 30%;

[0207] The amount of water used is 200% of the quality of 3A;

[0208] The pH value of the first slurry was 9.72 and the viscosity was 63.8 mPa·s;

[0209] The stirring time was 12 h and the speed was 400 rpm;

[0210] The ultrasonic dispersion time was 60 min.

[0211] E20. The first slurry, MOR zeolite, polyether-modified polydimethylsiloxane and water were stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a second slurry. The second slurry was cooled to room temperature using an ice bath.

[0212] Wherein, based on the total mass of ZSM-35, 3A and MOR zeolite being 100%, the amount of polyether-modified polydimethylsiloxane is 0.1% of the total mass;

[0213] The amount of water used is 200% of the mass of MOR zeolite;

[0214] The pH value of the second slurry was 10.15 and the viscosity was 69.3 mPa·s;

[0215] The stirring time was 14 h and the rotation speed was 600 rpm;

[0216] The ultrasonic dispersion time was 100 min.

[0217] E30. The second slurry, ZSM-35, sodium polymethacrylate and water were stirred and mixed and ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a third slurry. The third slurry was cooled to room temperature using an ice bath.

[0218] Wherein, based on the total mass of ZSM-35, 3A and MOR zeolite being 100%, the amount of sodium polymethacrylate is 0.1% of the total mass;

[0219] The amount of water used is 200% of the mass of ZSM-35;

[0220] The pH value of the third slurry was 10.39 and the viscosity was 106.3 mPa·s;

[0221] The stirring time was 24 h and the rotation speed was 800 rpm;

[0222] The ultrasonic dispersion time was 140 min.

[0223] E40. The third slurry and polyethylene oxide were mixed and ball-milled to obtain a mixed coating slurry;

[0224] Among them, the amount of polyoxyethylene is 0.2% of the total mass and the mass concentration is 0.1%;

[0225] The ball milling time was 1 h, and the ball milling speed was 600 rpm.

[0226] E50. The glass fiber and the mixed coating slurry are subjected to a pulling process, a purging process, and a drying process;

[0227] The volume ratio of the mixed coating slurry to the glass fiber is 3:1;

[0228] In the pulling treatment, the number of pulling times was 3, the interval between two adjacent pulling times was 5 min, and the soaking time of a single pulling time was 2 min;

[0229] During the purge treatment, the purge speed is 5L / min and the purge time is 10min;

[0230] During the drying process, a vacuum drying oven was used for drying, with a vacuum degree of -0.1 MPa, a drying temperature of 100°C, and a drying time of 24 h;

[0231] The relative position structure diagram of the prepared composite adsorbent is shown in FIG. Figure 6 As shown in the SEM images Figure 7 As shown;

[0232] Figure 6 Among them, 7 is MOR zeolite; 8 is ZSM-35 zeolite; 9 is 3A zeolite; 10 is silica sol; and 11 is glass fiber.

[0233] Examples 1-3

[0234] Example 1-3 provides a rotary adsorption separation device, the rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, a H2O desorption zone, a NO x It consists of desorption zone and cooling zone;

[0235] The adsorbent in the rotor is the composite adsorbent provided in Example 1-1;

[0236] Among them, mixed adsorption zone, CO2 desorption zone, H2O desorption zone, NO x The area ratio of the desorption zone and the cooling zone is 2:1:1:1.2:1.

[0237] This embodiment also provides a gas adsorption separation method for the rotary adsorption separation device of this embodiment, the steps of which are as follows:

[0238] E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 25°C.

[0239] E21. The desorbed gas enters the CO2 desorption zone, H2O desorption zone, NO x Desorption zone, for partitioning and desorbing the composite adsorbent;

[0240] The temperature of the desorbed gas is 370°C.

[0241] Examples 1-4

[0242] Example 1-4 provides a fixed bed adsorption separation device, and the adsorbent is the composite adsorbent provided in Example 1-1.

[0243] This embodiment also provides a gas adsorption separation method of a fixed bed adsorption separation device, the steps of which are as follows:

[0244] E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ;

[0245] The adsorption pressure is 0.1 mPa.

[0246] E22. Desorption

[0247] E221. Under vacuum conditions, heat the composite adsorbent to 150°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0248] E222. Under vacuum conditions, the composite adsorbent was heated from 150°C to 220°C at a heating rate of 2 k / min and then kept at this temperature for 30 min.

[0249] E223. Under vacuum conditions, the composite adsorbent was heated from 220°C to 285°C at a heating rate of 2 k / min and then kept at this temperature for 30 min.

[0250] Example 2-1

[0251] Example 2-1 provides a composite adsorbent, the raw materials of which are composed of ZSM-5, 4A, and NaY.

[0252] Among them, the mass ratio of ZSM-5, 4A and NaY is 10:12:10.

[0253] Example 2-2

[0254] Example 2-2 provides a method for preparing the composite adsorbent provided in Example 2-1, and the steps are as follows:

[0255] E10. Preparation of the first slurry: 4A, silica sol, and water were stirred and dispersed by ultrasonication at a constant temperature of 60°C. The pH and viscosity were adjusted with sodium carbonate and sodium carboxymethyl cellulose, respectively, to obtain a first slurry. The first slurry was cooled to room temperature using an ice bath.

[0256] Among them, the amount of silica sol is 30% of the total mass and the mass concentration is 30%;

[0257] The amount of water used is 200% of the quality of 3A;

[0258] The pH value of the first slurry was 10.21 and the viscosity was 47.2 mPa·s;

[0259] The stirring time was 10 h and the rotation speed was 400 rpm;

[0260] The ultrasonic dispersion time was 60 min.

[0261] E20. The first slurry, NaY zeolite, heptafluorobutyric acid and water were stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a second slurry. The second slurry was cooled to room temperature using an ice bath.

[0262] Wherein, based on the total mass of ZSM-35, 4A and NaY being 100%, the amount of heptafluorobutyric acid used is 0.3% of the total mass;

[0263] The amount of water used is 200% of the mass of MOR zeolite;

[0264] The pH of the second slurry was 10.43 and the viscosity was 52.7 mPa·s;

[0265] The stirring time was 16 h and the rotation speed was 500 rpm;

[0266] The ultrasonic dispersion time was 120 min.

[0267] E30. The second slurry, ZSM-35, ammonium polymethacrylate and water were stirred and mixed and ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a third slurry. The third slurry was cooled to room temperature using an ice bath.

[0268] Wherein, based on the total mass of ZSM-35, 4A and NaY being 100%, the amount of sodium polymethacrylate is 0.1% of the total mass;

[0269] The amount of water used is 200% of the mass of ZSM-35;

[0270] The pH value of the third slurry was 10.67 and the viscosity was 72.6 mPa·s;

[0271] The stirring time was 22 h and the rotation speed was 700 rpm;

[0272] The ultrasonic dispersion time was 180 min.

[0273] E40. The third slurry and polyethylene oxide were mixed and ball-milled to obtain a mixed coating slurry;

[0274] Among them, the amount of polyoxyethylene is 2% of the total mass and the mass concentration is 0.1%;

[0275] The ball milling time was 1 h, and the ball milling speed was 600 rpm.

[0276] E50. The glass fiber and the mixed coating slurry are subjected to a pulling process, a purging process, and a drying process;

[0277] The volume ratio of the mixed coating slurry to the glass fiber is 5:1;

[0278] In the pulling treatment, the number of pulling times was 3, the interval between two adjacent pulling times was 5 min, and the soaking time of a single pulling time was 2 min;

[0279] During the purge treatment, the purge speed is 5L / min and the purge time is 10min;

[0280] During the drying process, a vacuum drying oven was used for drying, with a vacuum degree of -0.1 MPa, a drying temperature of 100°C, and a drying time of 24 h;

[0281] The relative position structure diagram of the prepared composite adsorbent is shown in FIG. Figure 8 As shown;

[0282] Figure 8 Among them, 12 is 4A zeolite; 13 is NaY zeolite; 14 is ZSM-5 zeolite; 10 is silica sol; and 11 is glass fiber.

[0283] Example 2-3

[0284] Example 2-3 provides a rotary adsorption separation device, the rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, a H2O desorption zone, a NO x It consists of desorption zone and cooling zone;

[0285] The adsorbent in the rotor is the composite adsorbent provided in Example 2-1;

[0286] Among them, mixed adsorption zone, CO2 desorption zone, H2O desorption zone, NO x The area ratio of the desorption zone and the cooling zone is 2:1:1:1.4:1.

[0287] This embodiment also provides a gas adsorption separation method of a rotary adsorption separation device, the steps of which are as follows:

[0288] E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 25°C.

[0289] E21. The desorbed gas enters the CO2 desorption zone, H2O desorption zone, NO xDesorption zone, for partitioning and desorbing the composite adsorbent;

[0290] The temperature of the desorbed gas is 360°C.

[0291] Examples 2-4

[0292] Example 2-4 provides a fixed bed adsorption separation device, and the adsorbent is the composite adsorbent provided in Example 2-1.

[0293] This embodiment also provides a gas adsorption separation method of a fixed bed adsorption separation device, the steps of which are as follows:

[0294] E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ;

[0295] The adsorption pressure is 0.2 mPa.

[0296] E22. Under vacuum conditions, heat the composite adsorbent to 150°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0297] E32. Under vacuum conditions, heat the composite adsorbent from 150°C to 250°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0298] E42. Under vacuum conditions, heat the composite adsorbent from 250°C to 290°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0299] Example 3-1

[0300] Example 3-1 provides a composite adsorbent, the raw materials of which are Beta zeolite, Ti-MCM-41, and NaX zeolite.

[0301] The mass ratio of Beta zeolite, Ti-MCM-41 and NaX zeolite is 12:15:10.

[0302] Example 3-2

[0303] Example 3-2 provides a method for preparing the composite adsorbent provided in Example 3-1, and the steps are as follows:

[0304] E10. Preparation of the first slurry: Ti-MCM-41, silica sol, and water were stirred and dispersed by ultrasonication at a constant temperature of 50°C. The pH and viscosity were adjusted using sodium carbonate and sodium carboxymethyl cellulose, respectively, to obtain a first slurry. The first slurry was cooled to room temperature using an ice bath.

[0305] Among them, the amount of silica sol is 60% of the total mass and the mass concentration is 40%;

[0306] The amount of water used is 300% of the mass of Ti-MCM-41;

[0307] The pH value of the first slurry was 10.32 and the viscosity was 73.9 mPa·s;

[0308] The stirring time was 12 h and the speed was 300 rpm;

[0309] The ultrasonic dispersion time was 30 min.

[0310] E20. The first slurry, NaX zeolite, sodium lauryl sulfate and water were stirred and mixed, and then ultrasonically dispersed. Sodium phosphate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a second slurry. The second slurry was cooled to room temperature using an ice bath.

[0311] Among them, Beta zeolite, Ti-MCM-41 and NaX zeolite, the amount of sodium lauryl sulfate is 0.05% of the total mass;

[0312] The amount of water used is 300% of the mass of NaX zeolite;

[0313] The amount of phosphoric acid used is 0.2% of the total mass and the mass concentration is 0.5%;

[0314] The pH value of the second slurry was 9.61 and the viscosity was 83.0 mPa·s;

[0315] The stirring time was 16 h and the rotation speed was 600 rpm;

[0316] The ultrasonic dispersion time was 120 min.

[0317] E30. The second slurry, Beta zeolite, polyvinyl pyrrolidone and water were stirred and mixed and ultrasonically dispersed, and the pH and viscosity were adjusted by phosphoric acid and sodium carboxymethyl cellulose to obtain a third slurry, and the third slurry was cooled to room temperature using an ice bath;

[0318] Wherein, based on the total mass of Beta zeolite, Ti-MCM-41 and NaX zeolite being 100%, the amount of polyvinyl pyrrolidone used is 0.05% of the total mass;

[0319] The amount of water used is 300% of the mass of Beta zeolite;

[0320] The amount of phosphoric acid used is 0.2% of the total mass and the mass concentration is 0.5%;

[0321] The pH value of the third slurry was 10.11 and the viscosity was 113.6 mPa·s;

[0322] The stirring time was 24 h and the rotation speed was 800 rpm;

[0323] The ultrasonic dispersion time was 160 min.

[0324] E40. The third slurry and polyoxypropylene are mixed and ball-milled to obtain a mixed coating slurry;

[0325] Among them, the amount of polyoxypropylene is 0.2% of the total mass and the mass concentration is 0.1%;

[0326] The ball milling time was 1 h, and the ball milling speed was 600 rpm.

[0327] E50. The glass fiber and the mixed coating slurry are subjected to a pulling process, a purging process, and a drying process;

[0328] The volume ratio of the mixed coating slurry to the glass fiber is 4:1;

[0329] In the pulling treatment, the number of pulling times was 5, the interval between two adjacent pulling times was 10 min, and the soaking time of a single pulling time was 2 min;

[0330] During the purge treatment, the purge speed is 10L / min and the purge time is 20min;

[0331] During the drying process, a vacuum drying oven was used for drying, with a vacuum degree of -0.1 MPa, a drying temperature of 120°C, and a drying time of 12 h;

[0332] The relative position structure diagram of the prepared composite adsorbent is shown in FIG. Figure 9 As shown;

[0333] Figure 9 Among them, 15 is Beta zeolite; 16 is Ti-MCM-41; 17 is NaX zeolite; 10 is silica sol; and 11 is glass fiber.

[0334] Example 3-3

[0335] Example 3-3 provides a rotary adsorption separation device, the rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, a H2O desorption zone, a NO x It consists of desorption zone and cooling zone;

[0336] The adsorbent in the rotor is the composite adsorbent provided in Example 3-1;

[0337] Among them, mixed adsorption zone, CO2 desorption zone, H2O desorption zone, NO x The area ratio of the desorption zone and the cooling zone is 2:1.2:1.2:1.6:1.

[0338] This embodiment also provides a gas adsorption separation method of a rotary adsorption separation device, the steps of which are as follows:

[0339] E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 30°C.

[0340] E21. The desorbed gas enters the CO2 desorption zone, H2O desorption zone, NO x Desorption zone, for partitioning and desorbing the composite adsorbent;

[0341] The temperature of the desorbed gas is 380°C.

[0342] Examples 3-4

[0343] Example 3-4 provides a fixed bed adsorption separation device, and the adsorbent is the composite adsorbent provided in Example 3-1.

[0344] This embodiment also provides a gas adsorption separation method of a fixed bed adsorption separation device, the steps of which are as follows:

[0345] E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ;

[0346] The adsorption pressure is 0.3 mPa.

[0347] E22. Under vacuum conditions, heat the composite adsorbent to 150°C at a heating rate of 5 k / min and keep the temperature for 20 min.

[0348] E32. Under vacuum conditions, heat the composite adsorbent from 150°C to 250°C at a heating rate of 5 k / min and keep the temperature for 20 min.

[0349] E42. Under vacuum conditions, heat the composite adsorbent from 250°C to 275°C at a heating rate of 5 k / min and keep the temperature for 20 min.

[0350] Example 4-1

[0351] Example 4-1 provides a composite adsorbent, the raw materials of which are composed of SAPO-34, 3A and NaY.

[0352] The mass ratio of SAPO-34, 3A and NaY zeolite is 11:12:10.

[0353] Example 4-2

[0354] Example 4-2 provides a method for preparing the composite adsorbent provided in Example 4-1, and the steps are as follows:

[0355] E10. Preparation of the first slurry: 3A, silica sol, and water were stirred and dispersed by ultrasonication at a constant temperature of 60°C. The pH and viscosity were adjusted with sodium carbonate and sodium carboxymethyl cellulose, respectively, to obtain a first slurry. The first slurry was cooled to room temperature using an ice bath.

[0356] Among them, the amount of silica sol is 40% of the total mass and the mass concentration is 30%;

[0357] The amount of water used is 200% of the quality of 3A;

[0358] The pH value of the first slurry was 8.93 and the viscosity was 38.5 mPa·s;

[0359] The stirring time was 8 h and the speed was 400 rpm;

[0360] The ultrasonic dispersion time was 60 min.

[0361] E20. The first slurry, NaY zeolite, perfluoroundecanoic acid and water were stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a second slurry. The second slurry was cooled to room temperature using an ice bath.

[0362] Wherein, based on the total mass of SAPO-34, 3A and NaY zeolite being 100%, the amount of perfluoroundecanoic acid used is 0.1% of the total mass;

[0363] The amount of water used is 200% of the mass of NaY zeolite;

[0364] The pH value of the second slurry was 9.42 and the viscosity was 47.9 mPa·s;

[0365] The mixing time was 14 h and the rotation speed was 500 rpm;

[0366] The ultrasonic dispersion time was 80 min.

[0367] E30. The second slurry, SAPO-34, sodium polymethacrylate and water were stirred and mixed and ultrasonically dispersed. Sodium carbonate and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a third slurry. The third slurry was cooled to room temperature using an ice bath.

[0368] Wherein, based on the total mass of SAPO-34, 3A and NaY zeolite being 100%, the amount of sodium polymethacrylate is 0.1% of the total mass;

[0369] The amount of water used is 200% of the mass of SAPO-34;

[0370] The third slurry had a pH of 9.85 and a viscosity of 53.8 mPa·s;

[0371] The stirring time was 20 h and the rotation speed was 600 rpm;

[0372] The ultrasonic dispersion time was 180 min.

[0373] E40. The third slurry and polyethylene oxide were mixed and ball-milled to obtain a mixed coating slurry;

[0374] Among them, the amount of polyoxyethylene is 0.2% of the total mass and the mass concentration is 0.1%;

[0375] The ball milling time was 1 h, and the ball milling speed was 600 rpm.

[0376] E50. The glass fiber and the mixed coating slurry are subjected to a pulling process, a purging process, and a drying process;

[0377] The volume ratio of the mixed coating slurry to the glass fiber is 4:1;

[0378] In the pulling treatment, the number of pulling times was 3, the interval between two adjacent pulling times was 5 min, and the soaking time of a single pulling time was 2 min;

[0379] During the purge treatment, the purge speed is 5L / min and the purge time is 10min;

[0380] During the drying process, a vacuum drying oven was used for drying, with a vacuum degree of -0.1 MPa, a drying temperature of 100°C, and a drying time of 24 h.

[0381] Example 4-3

[0382] Example 4-3 provides a rotary adsorption separation device, the rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, a H2O desorption zone, a NO x It consists of desorption zone and cooling zone;

[0383] The adsorbent in the rotor is the composite adsorbent provided in Example 4-1;

[0384] Among them, mixed adsorption zone, CO2 desorption zone, H2O desorption zone, NO x The area ratio of the desorption zone and the cooling zone is 2:1:1:1.2:1.

[0385] This embodiment also provides a gas adsorption separation method for the rotary adsorption separation device of this embodiment, the steps of which are as follows:

[0386] E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 25°C.

[0387] E21. The desorbed gas enters the CO2 desorption zone, H2O desorption zone, NO x Desorption zone, for partitioning and desorbing the composite adsorbent;

[0388] The temperature of the desorbed gas is 350°C.

[0389] Example 4-4

[0390] Example 4-4 provides a fixed bed adsorption separation device, and the adsorbent adopts the composite adsorbent provided in Example 4-1.

[0391] This embodiment also provides a gas adsorption separation method of a fixed bed adsorption separation device, the steps of which are as follows:

[0392] E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ;

[0393] The adsorption pressure is 0.2 mPa.

[0394] E22. Desorption

[0395] E221. Under vacuum conditions, heat the composite adsorbent to 150°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0396] E222. Under vacuum conditions, the composite adsorbent was heated from 150°C to 220°C at a heating rate of 2 k / min and then kept at this temperature for 30 min.

[0397] E223. Under vacuum conditions, the composite adsorbent was heated from 220°C to 315°C at a heating rate of 2 k / min and then kept at this temperature for 30 min.

[0398] Example 5-1

[0399] Example 5-1 provides a composite adsorbent, the raw materials of which are composed of SSZ-13, 3A and NaY zeolites.

[0400] Among them, the mass ratio of SSZ-13, 3A and NaY is 12:12:10.

[0401] Example 5-2

[0402] Example 5-2 provides a method for preparing the composite adsorbent provided in Example 5-1, and the steps are as follows:

[0403] E10. Preparation of the first slurry: 3A, silica sol, and water were stirred and dispersed by ultrasonication at a constant temperature of 55°C. The pH and viscosity were adjusted with sodium carbonate and sodium carboxymethyl cellulose, respectively, to obtain a first slurry. The first slurry was cooled to room temperature using an ice bath.

[0404] Among them, the amount of silica sol is 30% of the total mass and the mass concentration is 30%;

[0405] The amount of water used is 200% of the quality of 3A;

[0406] The pH value of the first slurry was 9.17 and the viscosity was 68.3 mPa·s;

[0407] The stirring time was 12 h and the speed was 200 rpm;

[0408] The ultrasonic dispersion time was 40 min.

[0409] E20. The first slurry, NaY zeolite, ethoxylated fatty acid methyl ester and water were stirred and mixed and ultrasonically dispersed. Sodium hydroxide and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a second slurry. The second slurry was cooled to room temperature using an ice bath.

[0410] Wherein, based on the total mass of SSZ-13, 3A and NaY zeolite being 100%, the amount of ethoxylated fatty acid methyl ester is 0.3% of the total mass;

[0411] The amount of water used is 200% of the mass of NaY zeolite;

[0412] The pH value of the second slurry was 9.84 and the viscosity was 81.9 mPa·s;

[0413] The stirring time was 16 h and the rotation speed was 600 rpm;

[0414] The ultrasonic dispersion time was 120 min.

[0415] E30. The second slurry, SSZ-13, ammonium polymethacrylate and water were stirred and dispersed ultrasonically, and sodium hydroxide and sodium carboxymethyl cellulose were used to adjust the pH and viscosity to obtain a third slurry, and the third slurry was cooled to room temperature using an ice bath;

[0416] Wherein, based on the total mass of SSZ-13, 3A and NaY zeolite being 100%, the amount of ammonium polymethacrylate is 0.3% of the total mass;

[0417] The amount of water used is 200% of the mass of SSZ-13;

[0418] The pH value of the third slurry was 10.37 and the viscosity was 126,4 mPa·s;

[0419] The stirring time was 24 h and the rotation speed was 800 rpm;

[0420] The ultrasonic dispersion time was 180 min.

[0421] E40. The third slurry and polyoxypropylene are mixed and ball-milled to obtain a mixed coating slurry;

[0422] Among them, the amount of polyoxypropylene is 0.2% of the total mass and the mass concentration is 0.1%;

[0423] The ball milling time was 1 h, and the ball milling speed was 1000 rpm.

[0424] E50. The glass fiber and the mixed coating slurry are subjected to a pulling process, a purging process, and a drying process;

[0425] The volume ratio of the mixed coating slurry to the glass fiber is 3:1;

[0426] In the pulling treatment, the number of pulling times was 3, the interval between two adjacent pulling times was 5 min, and the soaking time of a single pulling time was 2 min;

[0427] During the purge treatment, the purge speed is 5L / min and the purge time is 10min;

[0428] During the drying process, a vacuum drying oven was used for drying, with a vacuum degree of -0.1 MPa, a drying temperature of 100°C, and a drying time of 24 h.

[0429] Example 5-3

[0430] Example 5-3 provides a rotary adsorption separation device, the rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, a H2O desorption zone, a NO x It consists of desorption zone and cooling zone;

[0431] The adsorbent in the rotor is the composite adsorbent provided in Example 5-1;

[0432] Among them, mixed adsorption zone, CO2 desorption zone, H2O desorption zone, NO x The area ratio of the desorption zone and the cooling zone is 2:1.2:1.2:1.4:1.

[0433] This embodiment also provides a gas adsorption separation method of a rotary adsorption separation device, the steps of which are as follows:

[0434] E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 25°C.

[0435] E21. The desorbed gas enters the CO2 desorption zone, H2O desorption zone, NO x Desorption zone, for partitioning and desorbing the composite adsorbent;

[0436] The temperature of the desorbed gas is 350°C.

[0437] Example 5-4

[0438] Example 5-4 provides a fixed bed adsorption separation device, and the adsorbent adopts the composite adsorbent provided in Example 5-1.

[0439] This embodiment also provides a gas adsorption separation method of a fixed bed adsorption separation device, the steps of which are as follows:

[0440] E12. Adsorption stage: The composite adsorbent simultaneously adsorbs H2O, CO2 and NO in the gasx ;

[0441] The adsorption pressure is 0.2 mPa.

[0442] E22. Under vacuum conditions, heat the composite adsorbent to 150°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0443] E32. Under vacuum conditions, heat the composite adsorbent from 150°C to 220°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0444] E42. Under vacuum conditions, heat the composite adsorbent from 180°C to 300°C at a heating rate of 2 k / min and keep the temperature for 30 min.

[0445] Comparative Example 1

[0446] Comparative Example 1 provides a mixed adsorbent consisting of NO x The honeycomb type adsorbent, the H2O honeycomb type adsorbent and the CO2 honeycomb type adsorbent are mixed.

[0447] This comparative example provides a method for preparing the mixed adsorbent provided in this comparative example, and the steps are as follows:

[0448] D10.NO x Preparation of honeycomb adsorbent

[0449] The ZSM-35 slurry and glass fiber are mixed and coated and then dried;

[0450] Among them, the ZSM-35 slurry consists of ZSM-35 and water, and the mass of water is 200% of ZSM-35;

[0451] The volume ratio of ZSM-35 slurry to glass fiber is 3:1.

[0452] Preparation of D20.H2O honeycomb adsorbent

[0453] 3A slurry and glass fiber are mixed and coated and then dried;

[0454] Among them, 3A slurry is composed of 3A and water, and the mass of water is 200% of 3A;

[0455] The volume ratio of 3A slurry to glass fiber is 3:1.

[0456] Preparation of D30.CO2 honeycomb adsorbent

[0457] The MOR slurry and glass fiber are mixed and coated and then dried;

[0458] Among them, MOR slurry consists of MOR and water, and the mass of water is 200% of MOR;

[0459] The volume ratio of MOR slurry to glass fiber is 3:1.

[0460] The mass ratio of ZSM-35, 3A and MOR is 8:12:10.

[0461] Comparative Example 2

[0462] Comparative Example 2 provides a gas adsorption separation method for a fixed bed adsorption separation device provided in Examples 1-4, and the steps are substantially the same as those in Examples 1-4, except that:

[0463] The desorption steps of step E22 are as follows:

[0464] Under vacuum conditions, the composite adsorbent was heated to 285 °C at a heating rate of 2 k / min and then kept at this temperature for 90 min.

[0465] In order to verify the advancement of the composite adsorbent and its preparation method, adsorption separation device and method provided in the embodiments of the present invention, the mixed adsorbent provided in Comparative Example 1 was subjected to fixed bed adsorption test and rotary adsorption test under the adsorption and desorption conditions of Examples 2-3 and 2-4, respectively. The results of the rotary adsorption test are shown in Table 1 below, and the results of the fixed bed test are shown in Table 2 below. The desorbed NO x The concentrations of the enriched gas, CO2 enriched gas, and H2O enriched gas are shown in Table 3 below.

[0466] Table 1

[0467]

[0468] Table 2

[0469]

[0470] Table 3

[0471]

[0472] It can be seen from the above table:

[0473] (1) The composite adsorbent provided by the embodiment of the present invention can achieve NO x , synergistic adsorption of H2O and CO2.

[0474] (2) The preparation method of the composite adsorbent provided in the embodiment of the present invention can x Adsorption material, water adsorption material and CO2 adsorption material are reasonably loaded on the carrier, and the prepared composite adsorbent can achieve NO x , synergistic adsorption of H2O and CO2.

[0475] (3) In Table 3, it can be seen from the gas enrichment concentrations of the embodiment and the comparative example that the rotary adsorption separation device provided by the embodiment of the present invention has a low NO x , H2O, CO2 by temperature gradient desorption, NO x , H2O, and CO2 enrichment.

[0476] (4) The fixed bed adsorption separation device provided in the embodiment of the present invention uses the composite adsorbent provided in the embodiment of the present invention, and during desorption, the NO x , H2O, CO2 by temperature gradient desorption, NO x , H2O, and CO2 enrichment.

[0477] The above description is merely a preferred embodiment of the composite adsorbent and preparation method, gas separation device and method of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A composite adsorbent, characterized in that: Raw materials include carriers and active materials; The active material includes NO x Adsorption materials, water adsorption materials and CO2 adsorption materials; The NO x The mass ratio of the adsorption material, the water adsorption material and the CO2 adsorption material is 5-15:7-18:10; The water adsorption material includes at least one of 3A, 4A, and Ti-MCM-41; The CO2 adsorption material includes at least one of Y zeolite, X zeolite, and MOR zeolite; The NO x The adsorption material includes at least one of ZSM-35 zeolite, ZSM-5 zeolite, Beta zeolite, SAPO-34 zeolite, and SSZ-13 zeolite; The preparation method of the composite adsorbent comprises the following steps: coating the mixed coating slurry and the carrier; The mixed coating slurry comprises the active material, a first dispersant, a second dispersant, a sol and an auxiliary agent; The preparation of the mixed coating slurry comprises the following steps: The first slurry, the CO2 adsorbent, the first dispersant and the auxiliary agent are subjected to a first mixing process to obtain a second slurry; the first slurry contains the water adsorbent, the sol and the auxiliary agent; The second slurry, the NO x The adsorption material, the second dispersant and the auxiliary agent are subjected to a second mixing process to obtain a third slurry; The third slurry is subjected to a third mixing process to obtain the mixed coating slurry; The third mixing process comprises the following steps: mixing the third slurry and the defoaming agent and ball milling; The first dispersant comprises at least one of polyether-modified polydimethylsiloxane, sodium lauryl sulfate, ethoxylated fatty acid methyl ester, heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonamide; The second dispersant includes at least one of sodium methylene bisnaphthalene sulfonate, polyvinyl pyrrolidone, ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate.

2. The composite adsorbent according to claim 1, characterized in that The material of the carrier includes at least one of glass fiber and ceramic fiber.

3. A method for preparing the composite adsorbent according to claim 1 or 2, characterized in that: The steps include: coating the mixed coating slurry and the carrier; The mixed coating slurry comprises the active material, a first dispersant, a second dispersant, a sol and an auxiliary agent; The preparation of the mixed coating slurry comprises the following steps: The first slurry, the CO2 adsorbent, the first dispersant and the auxiliary agent are subjected to a first mixing process to obtain a second slurry; the first slurry contains the water adsorbent, the sol and the auxiliary agent; The second slurry, the NO x The adsorption material, the second dispersant and the auxiliary agent are subjected to a second mixing process to obtain a third slurry; The third slurry is subjected to a third mixing process to obtain the mixed coating slurry; The third mixing process comprises the following steps: mixing the third slurry and the defoaming agent and ball milling; The first dispersant comprises at least one of polyether-modified polydimethylsiloxane, sodium lauryl sulfate, ethoxylated fatty acid methyl ester, heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonamide; The second dispersant includes at least one of sodium methylene bisnaphthalene sulfonate, polyvinyl pyrrolidone, ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate.

4. The method for preparing the composite adsorbent according to claim 3, wherein: The mass of the first dispersant is 0.05% to 2% of the active material.

5. The method for preparing the composite adsorbent according to claim 3, wherein: The mass of the second dispersant is 0.05% to 2% of the active material.

6. The method for preparing the composite adsorbent according to claim 3, characterized in that: The mass of the sol is 20% to 60% of the active material.

7. The method for preparing the composite adsorbent according to claim 3, characterized in that: The sol includes at least one of silica sol and aluminum sol.

8. The method for preparing the composite adsorbent according to claim 3, characterized in that: The auxiliary agents include a pH regulator, a defoaming agent, a viscosity regulator and a solvent.

9. The method for preparing the composite adsorbent according to claim 3, characterized in that: The pH value of the mixed coating slurry is 8-11.

10. The method for preparing the composite adsorbent according to claim 3, characterized in that: The viscosity of the mixed coating slurry is 10 mPa·s to 200 mPa·s.

11. The method for preparing a composite adsorbent according to any one of claims 3 to 10, characterized in that: The coating process comprises the following steps: The carrier is subjected to pulling treatment, purging treatment and drying treatment.

12. A rotary adsorption separation device, characterized in that: The adsorbent used includes the composite adsorbent as claimed in claim 1 or 2.

13. A separation method of the rotary adsorption separation device according to claim 12, characterized in that: The steps include: The composite adsorbent is used to perform rotary adsorption and rotary desorption on gas.

14. A fixed bed adsorption separation device, characterized in that: The adsorbent used includes the composite adsorbent as claimed in claim 1 or 2.

15. An adsorption separation method using a fixed bed adsorption separation device according to claim 14, characterized in that: The steps include: The composite adsorbent is used to perform fixed-bed adsorption and fixed-bed desorption on the gas.

Images