Composite adsorbent and preparation method thereof as well as adsorption separation device and method

Abstract

The invention belongs to the technical field of gas separation and purification materials, and particularly relates to a composite adsorbent, a preparation method thereof, an adsorption separation device and an adsorption separation method. Raw materials of the composite adsorbent comprise a carrier and an active material, the active material comprises a NOx adsorption material, a water adsorption material and a CO2 adsorption material; the mass ratio of the NOx adsorption material to the water adsorption material to the CO2 adsorption material is (5-15): (7-18): 10. The composite adsorbent provided by the invention can realize synergistic adsorption of NOx, H2O and CO2.

Description

Technical Field

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

[0002] Flue gas contains NO x , H2O and CO2. In the treatment before flue gas emission, it is usually removed step by step in the order of denitrification, decarbonization, and dehydration. Among them, denitrification mainly uses the oxidation adsorption method, decarbonization mainly uses the chemical absorption method, and dewashing mainly uses the physical adsorption method. Although this method can perform targeted adsorption separation on the gas components therein, there are many problems with the step-by-step removal method.

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

[0004] In terms of the adsorption and desorption principle, the strong adsorption of H2O will occupy the adsorption sites of NO x , CO2, resulting in a significant reduction in the adsorption capacity of NO x , CO2. And NO x mainly includes gases such as NO, NO x , N2O, etc. The molecular properties (such as molecular diameter, boiling point, melting point, dipole moment, polarity, etc.) of CO2 are between these NO x gases, and it is difficult to separate NO x and CO2.

[0005] In terms of the preparation process of the material, compared with traditional single adsorbents, the slurry characteristics required for composite coating molding are higher. Whether microscopically or macroscopically, it is difficult to ensure the stability of the slurry. Microscopically, due to the difference in the zeta potential of different adsorbent molecules, a flocculation effect occurs, and affinity aggregation will appear in the distribution in the slurry, resulting in stacking of different adsorbents layer by layer after coating molding, causing problems such as easy shedding, easy powdering, and low strength; macroscopically, due to different particle sizes of various adsorbents, agglomeration is extremely likely to occur, resulting in a decrease in the dispersibility and uniformity of the slurry, and further leading to sedimentation of the adsorbent, making it difficult to effectively perform coating molding. Summary of the Invention

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

[0007] One object of the present invention is to provide a composite adsorbent, the raw materials of which include a carrier and an active material; The active material includes a NO x adsorption material, a water adsorption material and a CO2 adsorption material; The mass ratio of the NO x adsorption material, the water adsorption material and the CO2 adsorption material is 5-15:7-18:10.

[0008] Another object of the present invention is to provide a preparation method of the above composite adsorbent, which includes the following steps: Performing a coating treatment on the mixed coating slurry and the carrier; The mixed coating slurry contains the active material, a dispersant, a pH regulator, an antifoaming agent, a sol and a solvent.

[0009] Another object of the present invention is to provide a rotary wheel adsorption separation device, and the adsorbent used includes the above composite adsorbent.

[0010] Another object of the present invention is to provide a separation method of the above rotary wheel adsorption separation device, which includes the following steps: Using the above composite adsorbent to perform adsorption separation on the gas.

[0011] Another object of the present invention is to provide a fixed bed adsorption separation device, and the adsorbent used includes the above composite adsorbent.

[0012] Another object of the present invention is to provide an adsorption separation method of the above fixed bed adsorption separation device, which includes the following steps: Using the above composite adsorbent to perform adsorption separation on the gas.

[0013] The composite adsorbent, the preparation method, the gas separation device and the method provided by the present invention have at least the following beneficial technical effects compared with the prior art: (1) The composite adsorbent provided by the present invention can achieve the synergistic adsorption of NO x , H2O and CO2.

[0014] (2) The preparation method of the composite adsorbent provided by the present invention can reasonably load the NO x adsorption material, the water adsorption material and the CO2 adsorption material on the carrier, and the prepared composite adsorbent can achieve NO x、Co - adsorption of H2O and CO2. Brief Description of the Drawings

[0015] Figure 1 Schematic flow chart of the preparation steps of the mixed coating slurry in the embodiments of the present invention; Figure 2 Schematic diagram of the structure of the rotor in the rotor adsorption separation device in the embodiments of the present invention; Figure 3 Schematic diagram of the gas flow direction for the partitioned desorption of the composite adsorbent in the gas adsorption separation method of the rotor adsorption separation device in the embodiments of the present invention; Figure 4 Schematic diagram of the principle of partitioned desorption of the composite adsorbent in the gas adsorption separation method of the rotor adsorption separation device in the embodiments of the present invention; Figure 5 Schematic diagram of the placement position of the composite adsorbent in the fixed - bed adsorption separation device in the embodiments of the present invention; Figure 6 Schematic diagram of the structure of the composite adsorbent prepared in Examples 1 - 2 of the present invention; Figure 7 SEM image of the composite adsorbent prepared in Examples 1 - 2 of the present invention; Figure 8 Schematic diagram of the structure of the composite adsorbent prepared in Examples 2 - 2 of the present invention; Figure 9 Schematic diagram of the structure of the composite adsorbent prepared in Examples 3 - 2 of the present invention.

[0016] Description of the 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 of the Invention

[0017] To make the objectives, technical solutions, and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described in more detail below with reference to the accompanying drawings in the embodiments of the present application. In the drawings, the same or similar reference numerals denote the same or similar elements or elements with the same or similar functions from beginning to end. The described embodiments are some, but not all, of the embodiments of the present application. The embodiments described below by referring to the accompanying drawings are exemplary and are intended to explain the present application, and should not be construed as a limitation on the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts fall within the scope of protection of the present application. The embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0018]

Composite adsorbent

[0019] For the composite adsorbent provided in the embodiments of the present invention, the NO x adsorbent material, water adsorbent material, and CO2 adsorbent material are uniformly distributed on the carrier, and the adsorbed H2O is used to promote the dissolution and reaction of CO2 and NO x , and the co-adsorption of NO x , CO2, and H2O can be realized, and the adsorption efficiency can be improved.

[0020] In some embodiments, the NO x adsorbent material includes at least one of ZSM-35 zeolite, ZSM-5 zeolite, Beta zeolite, SAPO-34 zeolite, and SSZ-13 zeolite.

[0021] In some embodiments, the water adsorbent material includes at least one of 3A, 4A, and Ti-MCM-41.

[0022] In some embodiments, the CO2 adsorbent material includes at least one of Y zeolite, X zeolite, and MOR zeolite.

[0023] In some embodiments, the Y zeolite includes at least one of NaY zeolite and KY zeolite.

[0024] In some embodiments, the X zeolite includes at least one of NaX zeolite and KX zeolite.

[0025] In some embodiments, the material of the carrier includes glass fiber and ceramic fiber.

[0026] In some embodiments, the aspect ratio of the glass fiber is 1 to 10:1.

[0027] In some embodiments, the aspect ratio of the ceramic fiber is 1 to 10:1.

[0028] In some embodiments, the carrier structure is a honeycomb adsorbent structure or a layered adsorbent structure.

[0029]

Preparation Method of Composite Adsorbent

[0030] In the preparation method of the composite adsorbent provided by the embodiments of the present invention, the first dispersant not only reduces the surface tension but also plays a dispersing role, combining the functions of dispersion and surface activity; the second dispersant ensures the uniformity and stability of the molecular distribution in the slurry through charge repulsion and steric hindrance, constructing a particle dispersion system, mainly responsible for molecular dispersion, but having no surface activity; under the combined action of the first dispersant and the second dispersant, the prepared mixed coating slurry has stable properties, uniformity and high dispersibility, and the active material ensures the coexistence and uniform distribution of the adsorbent molecules in the slurry state. The same adsorbent molecules aggregate in the same layer but do not agglomerate, and there is no apparent sedimentation phenomenon; coating the mixed coating slurry containing the active material on the carrier, the obtained composite adsorbent can achieve the synergistic adsorption of NO x , H2O and CO2.

[0031] In some embodiments, in the above step S10, the volume ratio of the mixed coating slurry to the carrier is (2 to 5):1.

[0032] In some embodiments, in the above step S10, the pH value of the mixed coating slurry is 8 to 11. Within this pH range, it can ensure that the adsorbent material plays a more effective adsorption role, avoiding material inactivation, and also ensuring the uniformity of the distribution of the active material due to the charge effect.

[0033] In some embodiments, in the above step S10, the viscosity of the mixed coating slurry is 10 mPa·s to 200 mPa·s. This viscosity range can ensure the stability and dispersibility of the slurry; too low viscosity will reduce the loading amount, and too high viscosity will cause pore blockage.

[0034] In some embodiments, in the above-mentioned step S10, the viscosity of the mixed coating slurry is 30 mPa·s to 150 mPa·s. Within this viscosity range, the stability and dispersibility of the slurry are relatively good.

[0035] In some embodiments, in the above-mentioned step S10, the viscosity of the mixed coating slurry is 30 mPa·s to 80 mPa·s. Within this viscosity range, both the stability and dispersibility of the slurry can be ensured, and the coating loading amount and coating effect of the active material are the best, and almost no phenomena unfavorable to adsorption such as powder shedding and pore blockage occur.

[0036] In some embodiments, in the above-mentioned step S10, the mass of the first dispersant is 0.05% to 2% of the active material.

[0037] In some embodiments, in the above-mentioned step S10, the first dispersant includes at least one of polyether-modified polydimethylsiloxane, sodium dodecyl sulfate, ethoxylated fatty acid methyl ester, heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropanesulfonic acid, and perfluorobutanesulfonamide. In this case, polyether-modified polydimethylsiloxane has both the hydrophobic structure of the polysiloxane chain and the hydrophilic structure of the polyether chain, sodium dodecyl 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 polyoxyethylene chain, and heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropanesulfonic acid, and perfluorobutanesulfonamide in the fluorosurfactant have both the hydrophobic and oleophobic structures of the fluorocarbon chain and the hydrophilic structures of polar functional groups such as carboxyl groups and hydroxyl groups.

[0038] In some embodiments, in polyether-modified polydimethylsiloxane, the proportion of polydimethylsiloxane is 10% to 40%.

[0039] In some embodiments, in the above-mentioned step S10, the mass of the second dispersant is 0.05% to 2% of the active material.

[0040] In some embodiments, in the above-mentioned step S10, the second dispersant includes at least one of sodium methylenebis(naphthalenesulfonate), polyvinylpyrrolidone, ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate. In this case, sodium methylenebis(naphthalenesulfonate) is connected by a methylene group, and the sulfonic acid group provides negative charges; the lactam structure in polyvinylpyrrolidone provides hydrogen bond action; ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate provide electrostatic repulsion to disperse particles through the charges carried by the ammonium ions or sodium ions in the side chains.

[0041] In some embodiments, the CAS number of polyvinylpyrrolidone is 9003-39-8.

[0042] In some embodiments, the CAS number of ammonium polymethacrylate is 25949-70-8.

[0043] In some embodiments, the CAS number of sodium polymethacrylate is 54193-36-1.

[0044] In some embodiments, the CAS number of sodium polyacrylate is 27599-56-0.

[0045] In some embodiments, in the above step S10, the sol includes at least one of silica sol and alumina sol.

[0046] In some embodiments, the mass concentration of silica sol is 10% - 40%.

[0047] In some embodiments, the mass concentration of alumina sol is 20% - 60%.

[0048] In some embodiments, in the above step S10, the mass of the sol is 20% - 60% of the active material.

[0049] In some embodiments, in the above step S10, the additives include a pH regulator, an antifoaming agent, a viscosity modifier, and a solvent In some embodiments, in the above step S10, the pH regulator includes at least one of sodium hydroxide, sodium carbonate, phosphoric acid, and citric acid; In some embodiments, in the above step S10, the antifoaming agent includes at least one of polyoxyethylene (POE) and polyoxypropylene (POP); In some embodiments, the mass of the antifoaming agent is 0.01% - 0.1% of the active material.

[0050] In some embodiments, the CAS number of polyoxyethylene is 25322-68-3.

[0051] In some embodiments, the CAS number of polyoxypropylene is 9003-11-6.

[0052] 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 characteristics and substituent characteristics of cellulose. The molecular characteristics mainly 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 achieving viscosity adjustment; the substituents mainly act according to their degree of hydroxy substitution. By changing the degree of substitution, the intermolecular forces change, thereby adjusting the viscosity.

[0053] In some embodiments, the CAS number of hydroxyethyl cellulose is 9004-62-0.

[0054] In some embodiments, the CAS number of sodium carboxymethyl cellulose is 9004-32-4.

[0055] In some embodiments, the CAS number of methyl hydroxyethyl cellulose is 9032-42-2.

[0056] In some embodiments, the CAS number of ethyl hydroxyethyl cellulose is 9004-57-3.

[0057] In some embodiments, the solvent includes at least one of deionized water and alcohol.

[0058] In some embodiments, the alcohol includes at least one of methanol, ethanol, and propanol.

[0059] In some embodiments, in the above step S10, the preparation of the mixed coating slurry includes the following steps: S101. Perform a first mixing process on the first slurry, the CO2 adsorption material, the first dispersant, and the second auxiliary agent to obtain a second slurry; the first slurry contains a water adsorption material, a sol, and a first auxiliary agent.

[0060] S102. Perform a second mixing process on the second slurry, the NO x adsorption material, the second dispersant, and the third auxiliary agent to obtain a third slurry.

[0061] S103. Perform a mixing process on the third slurry to obtain the above-mentioned mixed coating slurry.

[0062] In some embodiments, in the above step S101, the preparation of the first slurry includes the following steps: S1011. At a constant temperature of 50°C to 60°C, stir and mix the water adsorption material, the sol, and the first auxiliary agent, and then perform ultrasonic dispersion.

[0063] In the preparation of the above first slurry, due to the hydrophilic characteristics of the water adsorption material, the water adsorption material can be better dispersed in the slurry mainly through the action of the sol, and the slurry has good dispersibility when stirred and mixed at 50°C to 60°C; ultrasonic dispersion is used to improve the uniformity of the slurry.

[0064] In some embodiments, in the above step S101, the pH value of the first slurry is 8 to 11.

[0065] In some embodiments, in the above step S101, the viscosity of the first slurry is 10 mPa·s to 200 mPa·s.

[0066] In some embodiments, in the above step S101, the viscosity of the first slurry is 30 mPa·s to 150 mPa·s.

[0067] In some embodiments, in the above step S101, the viscosity of the first slurry is 30 mPa·s to 80 mPa·s.

[0068] In some embodiments, in the above step S1011, the first auxiliary agent includes a solvent, a pH regulator, and a viscosity modifier. In this case, the solvent is used to dilute the concentration of the adsorbent material, the pH regulator adjusts the pH value of the slurry, and the viscosity modifier adjusts the viscosity of the slurry so that the pH value and viscosity of the first slurry meet the requirements.

[0069] In some embodiments, in the above step S1011, in the first slurry, the amount of the solvent used is 100% to 300% of the water adsorbent material. It should be noted that the amounts of the pH regulator and the viscosity modifier are adjusted according to the actual pH and viscosity of the slurry, as long as the pH value and viscosity requirements of the first slurry are met, and no special limitation is made here.

[0070] In some embodiments, in the above step S1011, during the stirring and mixing, the stirring time is 8 h to 12 h.

[0071] In some embodiments, in the above step S1011, during the stirring and mixing, the stirring speed is 200 rpm to 400 rpm.

[0072] In some embodiments, in the above step S1011, the ultrasonic dispersion time is 30 min to 60 min.

[0073] In some embodiments, in the above step S101, the second auxiliary agent includes a solvent, a pH regulator, and a viscosity modifier. In this case, the solvent is used to dilute the concentration of the adsorbent material, the pH regulator adjusts the pH value of the slurry, and the viscosity modifier adjusts the viscosity of the slurry so that the pH value and viscosity of the second slurry meet the requirements.

[0074] In some embodiments, in the second slurry, the amount of the solvent used is 100% to 300% of the CO2 adsorbent material. It should be noted that the amounts of the pH regulator and the viscosity modifier are adjusted according to the actual pH and viscosity of the slurry, as long as the pH value and viscosity requirements of the second slurry are met, and no special limitation is made here.

[0075] In some embodiments, in the above step S101, the first mixing process includes the following steps: S1012. After the first slurry, the CO2 adsorbent material, the first dispersant, and the second auxiliary agent are stirred and mixed, ultrasonic dispersion is performed.

[0076] In the above first mixing process, the water adsorption material is hydrophilic, while the CO2 adsorption material is hydrophobic. 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 realizing the dispersion between the water adsorption material and the CO2 adsorption material.

[0077] In some embodiments, in the above step S1012, the stirring and mixing time is 12h to 16h.

[0078] In some embodiments, in the above step S1012, the stirring and mixing speed is 200rpm to 600rpm.

[0079] In some embodiments, in the above step S1012, the ultrasonic dispersion time is 60min to 120min.

[0080] In some embodiments, in the above step S102, the pH value of the second slurry is 8 to 11.

[0081] In some embodiments, in the above step S102, the viscosity of the second slurry is 10mPa·s to 200mPa·s.

[0082] In some embodiments, in the above step S102, the temperature of the second slurry is room temperature (25°C to 30°C). In this case, the second slurry prepared in step S101 can be quickly cooled to room temperature by using a water bath or an ice bath, which ensures the stable position between the water adsorption material molecules in the second slurry and achieves the effect of aggregation but not agglomeration among the same adsorbents.

[0083] In some embodiments, in the above step S102, the third auxiliary agent includes a solvent, a pH regulator, and a viscosity modifier. In this case, the solvent is used to dilute the concentration of the adsorption material, the pH regulator adjusts the pH value of the slurry, and the viscosity modifier adjusts the viscosity of the slurry to make the pH value and viscosity of the third slurry meet the requirements.

[0084] In some embodiments, in the above step S102, in the third slurry, the dosage of the solvent is NO x 100% to 300% of the adsorption material. It should be noted that the dosages of the pH regulator and the viscosity modifier are 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 no special limitation is made here.

[0085] In some embodiments, in the above step S102, the second mixing process includes the following steps: S1021. The second slurry, NO x The adsorption material, the second dispersant, and the third auxiliary agent are stirred and mixed and then ultrasonically dispersed.

[0086] In the above second mixing process, since the CO2 adsorption material has a cubic structure (such as X zeolite), the water adsorption material has a cubic lattice structure (such as 3A zeolite), and the NO x oxidation adsorption material (such as ZSM-5 zeolite) has a strip structure, the structures of the three adsorption materials are different, and the molecular particle sizes are different. The first dispersant cannot maintain the stability of the slurry, while the second dispersant plays a dispersing role through charge repulsion and steric hindrance. The second dispersant and the first dispersant can achieve uniform and stable distribution of the three active materials in the slurry, and achieve the effect of mutual coexistence and uniform distribution among different active substances, and the same substances aggregate in the same layer but do not agglomerate.

[0087] In some embodiments, in the above step S1021, the stirring and mixing time is 12h to 24h.

[0088] In some embodiments, in the above step S1021, the stirring and mixing speed is 400rpm to 800rpm.

[0089] In some embodiments, in the above step S1021, the ultrasonic dispersion time is 90min to 180min.

[0090] In some embodiments, in the above step S103, the pH value of the third slurry is 8 to 11.

[0091] In some embodiments, in the above step S103, the viscosity of the third slurry is 10mPa·s to 200mPa·s.

[0092] In some embodiments, in the above step S103, the temperature of the third slurry is normal temperature (25°C to 30°C). In this case, the third slurry prepared in step S101 can be quickly cooled to normal temperature by using a water bath or an ice bath, which ensures the stable position between the water adsorption material molecules in the third slurry and achieves the effect of aggregation but not agglomeration between the same adsorbents.

[0093] In some embodiments, in the above step S103, the third mixing process includes the following steps: S1031. Mixing and ball milling the third slurry and the defoamer.

[0094] In the above mixing process, by means of ball milling, problems such as sedimentation and strong force aggregation caused by different particle sizes are eliminated, and the stability of the slurry is improved; the defoamer is used to avoid the occurrence of hole plugging during the coating process.

[0095] In some embodiments, in the above step S1031, the mixing and ball milling time is 0.5h to 2h.

[0096] In some embodiments, in the above step S1031, the rotational speed of the hybrid ball milling is 600 - 1200 rpm In some embodiments, in the above step S10, the carrier is a pretreated carrier. In this case, the surface roughness and hydroxyl density of the carrier can be increased to facilitate subsequent loading of amino functional groups, NO x oxidation adsorbents and other adsorbent materials.

[0097] In some embodiments, the preparation of the pretreated carrier includes the following steps: S102. Acid etching or alkali etching is performed on the carrier.

[0098] In some embodiments, in the above step S102, in acid etching, the acid includes at least one of nitric acid and hydrochloric acid.

[0099] In some embodiments, the mass concentration of nitric acid is 3% - 10%.

[0100] In some embodiments, the mass concentration of hydrochloric acid is 3% - 10%.

[0101] In some embodiments, in the above step S102, in alkali etching, the alkali includes one of sodium hydroxide solution and potassium hydroxide solution.

[0102] In some embodiments, the concentration of sodium hydroxide solution is 5% - 15%.

[0103] In some embodiments, the concentration of potassium hydroxide solution is 5% - 15%.

[0104] In some embodiments, in the above step S102, the average pore diameter of the carrier is 1 mm - 3 mm. In some embodiments, in the above step S102, the porosity of the carrier is more than 80%. In this case, the carrier can have both high gas permeability and mechanical strength.

[0105] In some embodiments, in the above step S10, the coating treatment includes the following steps: S103. The carrier is subjected to lifting treatment, purging treatment, and drying treatment.

[0106] In some embodiments, in the above step S103, in the lifting treatment, the number of lifting times is 3 - 5 times.

[0107] In some embodiments, the interval between two adjacent liftings is 5 min - 20 min.

[0108] In some embodiments, in the lifting treatment, the soaking duration for a single lifting is 1 min - 2 min.

[0109] In some embodiments, in the above step S103, during the purging process, the purging speed is 3 L / min to 10 L / min.

[0110] In some embodiments, in the above step S103, during the purging process, the air gun pressure is 0.2 MPa to 0.4 MPa.

[0111] In some embodiments, in the above step S103, during the purging process, the purging duration is 5 min to 20 min.

[0112] 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.

[0113] In some embodiments, in the vacuum drying oven, the vacuum degree is 0 MPa to 0.1 MPa.

[0114] In some embodiments, in the above step S103, during the drying process, the drying temperature is 80 °C to 150 °C.

[0115] In some embodiments, in the above step S103, during the drying process, the drying time is 12 h to 24 h.

[0116]

Rotary wheel adsorption separation device

[0117] In some embodiments, please refer to Figure 2 , in the rotary wheel adsorption separation device, the rotary wheel includes a mixed adsorption zone 1, a CO2 desorption zone 2, an H2O desorption zone 3, a NO x desorption zone 4, and a cooling zone 5.

[0118] In some embodiments, the area ratio of the mixed adsorption zone 1, the NO x desorption zone 4, the H2O desorption zone 3, the CO2 desorption zone 2, and the cooling zone 5 is (1 to 2):(1 to 1.6):(0.8 to 1.2):(0.8 to 1.2):1.

[0119]

Gas adsorption separation method of rotary wheel adsorption separation device

[0120] In some embodiments, in the above step Z10, the rotary wheel adsorption includes the following steps: Z101. The mixed gas enters the mixed adsorption zone for adsorption.

[0121] In some embodiments, in the above step Z101, the mixed gas includes at least one of flue gas, thermal power generation tail gas, coking plant tail gas, diesel vehicle tail gas, and chemical production tail gas.

[0122] In some embodiments, in the above step Z101, the wheel adsorption temperature is 20°C to 60°C.

[0123] In some embodiments, in the above step Z10, the wheel desorption includes the following steps: Z102. The composite adsorbent is desorbed in zones.

[0124] In the above adsorption separation, the composite adsorbent is heated for desorption. The heating method is such that in the final cooling zone, a gas at 0°C to 5°C is introduced by a cold source to cool the desorbed composite adsorbent to 20°C; the wheel then enters the mixed adsorption zone to achieve temperature gradient desorption of NO x , H2O, and CO2 and the cyclic adsorption and desorption of the next group.

[0125] In some embodiments, in the above step Z102, please refer to Figure 4 , and the zonal desorption includes the following steps: Z1021. The desorbing gas enters the NO x desorption zone, H2O desorption zone, and CO2 desorption zone.

[0126] In the above zonal desorption steps, the desorbing gas enters the NO x desorption zone, H2O desorption zone, and CO2 desorption zone. Since the heating and heat transfer durations of the desorbing gas in the three desorption regions are 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 desorbing gas respectively, so as to achieve desorption of different gases in different regions.

[0127] In some embodiments, in the above step Z1021, the temperature of the desorbing gas is 350°C to 400°C.

[0128] Please refer to Figure 4 In some embodiments, in the above step Z1021, the temperature for desorbing CO2 in the CO2 desorption zone is 80°C to 150°C.

[0129] Please refer to Figure 4 In some embodiments, in the above step Z1021, the temperature for desorbing H2O in the H2O desorption zone is 160°C to 250°C.

[0130] Please refer to Figure 4 In some embodiments, in the above step Z1021, NO xDesorption of NO in the desorption zone x The temperature is 260°C to 320°C.

[0131] In some embodiments, in the above step Z1021, the desorbed gas includes at least one of flue gas purification gas, nitrogen, and argon.

[0132] It should be noted that the cooling of the adsorbent in the cooling zone of the rotating wheel is conventional in the art and is not particularly limited in the embodiments of the present invention.

[0133]

Fixed bed adsorption separation device

[0134]

Gas adsorption separation method of fixed bed adsorption separation device

[0135] In some embodiments, in the above step G10, the pressure of the fixed bed adsorption is 0 mPa to 0.6 mPa.

[0136] In some embodiments, in the above step G10, the temperature of the fixed bed adsorption is 20°C to 60°C.

[0137] In some embodiments, in the above step G10, the fixed bed desorption pressure is -100 kPa to 0 kPa.

[0138] In some embodiments, in the above step G10, the fixed bed desorption includes the following steps: G101. Under vacuum conditions, perform the first removal, the second removal, and the third removal on the composite adsorbent.

[0139] In the above desorption steps, performing the first removal, the second removal, and the third removal on the composite adsorbent can perform stepwise removal of carbon dioxide, water, and nitrogen oxides. In this way, direct separation of multi-component gases of carbon dioxide, water, and nitrogen oxides is achieved during one heating process, reducing equipment investment and energy consumption levels.

[0140] In some embodiments, in the above step G101, the first removal includes the following steps: G1011. Heat the composite adsorbent at a heating rate of 2 k / min to 10 k / min to 80°C to 150°C and then perform the first heat preservation.

[0141] In the above first removal step, the composite adsorbent is heated to 80°C to 150°C, so that CO2 can be removed therefrom. Since it is under vacuum, the removed CO2 can be pumped out of the adsorbent system at any time, and the high-concentration CO2 can be pressurized and liquefied for storage through a pressure pump.

[0142] In some embodiments, in the above step G1011, the time for the first heat preservation is 10 to 30 minutes.

[0143] In some embodiments, in the above step G101, the second removal includes the following steps: G1012. Heat the composite adsorbent from 80°C to 150°C to 160°C to 250°C at a heating rate of 2°C / min to 10°C / min, and then perform the second heat preservation.

[0144] In the above second removal step, heating the composite adsorbent to 160°C to 250°C can remove H2O therefrom. Since it is under vacuum, the removed H2O can be pumped out of the adsorbent system at any time.

[0145] In some embodiments, in the above step G1012, the time for the second heat preservation is 10 minutes to 30 minutes.

[0146] In some embodiments, in the above step G101, the third removal includes the following steps: G1013. Heat the composite adsorbent from 160°C to 250°C to 260°C to 320°C at a heating rate of 2°C / min to 10°C / min, and then perform the third heat preservation.

[0147] In the above third removal step, heating the composite adsorbent to 260°C to 320°C can remove nitrogen oxides therefrom. Since it is under vacuum, the removed nitrogen oxides can be pumped out of the adsorbent system at any time, and the high-concentration nitrogen oxides can be pressurized and liquefied for storage through a pressure pump.

[0148] In some embodiments, in the above step G1013, the time for the third heat preservation is 10 minutes to 30 minutes.

[0149] This will be further described below with specific examples.

[0150] For the convenience of description, the following examples and comparative examples involve a carrier of pretreated honeycomb-shaped fiberglass (aspect ratio of 5:1), an average pore diameter of 2 mm, and a porosity of 90%; the pretreatment steps are as follows: Etch the honeycomb-shaped fiberglass with hydrochloric acid with a mass concentration of 6% for 1 minute.

[0151] When adjusting the pH value and viscosity in the following examples and comparative examples, the operations 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.

[0152] In the following examples and comparative examples, the desorbed gas is nitrogen.

[0153] The coating and drying involved in the following comparative examples are conventional in the art and are not particularly limited.

[0154] Example 1-1 Example 1-1 provides a composite adsorbent, the raw materials of which are composed of ZSM-35, 3A, and MOR.

[0155] Among them, the mass ratio of ZSM-35, 3A, and MOR is 8:12:10.

[0156] Example 1-2 Example 1-2 provides a preparation method of the composite adsorbent provided by Example 1-1, and the steps are as follows: E10. Preparation of the first slurry: At a constant temperature of 60 °C, 3A, silica sol, and water are stirred and mixed and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the first slurry, and the first slurry is cooled to room temperature by using an ice bath; Among them, the dosage of silica sol is 40% of the total mass and the mass concentration is 30%; The dosage of water is 200% of the mass of 3A; The pH value of the first slurry is 9.72 and the viscosity is 63.8 mPa·s; The time of stirring and mixing is 12 h and the rotation speed is 400 rpm; The time of ultrasonic dispersion is 60 min.

[0157] E20. The first slurry, MOR zeolite, polyether-modified polydimethylsiloxane, and water are stirred and mixed and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the second slurry, and the second slurry is cooled to room temperature by using an ice bath; Among them, based on the total mass of ZSM-35, 3A, and MOR zeolite being 100%, the dosage of polyether-modified polydimethylsiloxane is 0.1% of the total mass; The dosage of water is 200% of the mass of MOR zeolite; The pH value of the second slurry is 10.15 and the viscosity is 69.3 mPa·s; The time of stirring and mixing is 14 h and the rotation speed is 600 rpm; The time of ultrasonic dispersion is 100 min.

[0158] The second slurry, ZSM-35, sodium polymethacrylate and water are stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the third slurry, and the third slurry is cooled to room temperature by means of an ice bath. Among them, based on the total mass of ZSM-35, 3A and MOR zeolites being 100%, the dosage of sodium polymethacrylate is 0.1% of the total mass. The dosage of water is 200% of the mass of ZSM-35. The pH value of the third slurry is 10.39, and the viscosity is 106.3 mPa·s. The stirring and mixing time is 24 h, and the rotation speed is 800 rpm. The ultrasonic dispersion time is 140 min.

[0159] E40. The third slurry and polyoxyethylene are mixed and ball-milled to obtain a mixed coating slurry. Among them, the dosage of polyoxyethylene is 0.2% of the total mass, and the mass concentration is 0.1%. The ball-milling time is 1 h, and the ball-milling rotation speed is 600 rpm.

[0160] E50. The glass fiber and the mixed coating slurry are subjected to a pulling treatment, a purging treatment and a drying treatment. Among them, the volume ratio of the mixed coating slurry to the glass fiber is 3:1. In the pulling treatment, the number of pulling times is 3, the interval between two adjacent pullings is 5 min, and the infiltration duration of a single pulling is 2 min. In the purging treatment, the purging speed is 5 L / min, and the purging duration is 10 min. In the drying treatment, vacuum drying is carried out in a vacuum drying oven, the vacuum degree is -0.1 MPa, the drying temperature is 100 °C, and the time is 24 h. The relative position structure schematic diagram of the prepared composite adsorbent is as Figure 6 shown, and the SEM diagram is as Figure 7 shown; Figure 6 In, 7 is MOR zeolite; 8 is ZSM-35 zeolite; 9 is 3A zeolite; 10 is silica sol; 11 is glass fiber.

[0161] Examples 1-3 Examples 1-3 provide a rotary adsorption separation device, and the rotor is composed of a mixed adsorption zone, a CO2 desorption zone, an H2O desorption zone, a NO x desorption zone and a cooling zone; The adsorbent in the rotor adopts the composite adsorbent provided in Example 1-1; Among them, the mixed adsorption zone, the CO2 desorption zone, the H2O desorption zone, the NO xThe area ratio of the desorption zone to the cooling zone is 2:1:1:1.2:1.

[0162] This embodiment also provides a gas adsorption and separation method for the rotary wheel adsorption and separation device of this embodiment, and the steps are as follows: E11. The mixed gas enters the mixed adsorption zone for adsorption, wherein the adsorption temperature is 25°C.

[0163] E21. The desorbed gas enters the CO2 desorption zone, the H2O desorption zone, and the NO x desorption zone to perform zoned desorption on the composite adsorbent; Among them, the temperature of the desorbed gas is 370°C.

[0164] Examples 1-4 Examples 1-4 provide a fixed bed adsorption and separation device, and the adsorbent uses the composite adsorbent provided in Examples 1-1.

[0165] This embodiment also provides a gas adsorption and separation method for the fixed bed adsorption and separation device, and the steps are as follows: E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O, and NO in the gas x ; Among them, the adsorption pressure is 0.1 mPa.

[0166] E22. Desorption E221. Under vacuum conditions, the composite adsorbent is heated to 150°C at a heating rate of 2 k / min and then held for 30 min.

[0167] E222. Under vacuum conditions, the composite adsorbent is heated from 150°C to 220°C at a heating rate of 2 k / min and then held for 30 min.

[0168] E223. Under vacuum conditions, the composite adsorbent is heated from 220°C to 285°C at a heating rate of 2 k / min and then held for 30 min.

[0169] Example 2-1 Example 2-1 provides a composite adsorbent, and the raw materials are composed of ZSM-5, 4A, and NaY.

[0170] Among them, the mass ratio of ZSM-5, 4A, and NaY is 10:12:10.

[0171] Example 2-2 Example 2-2 provides a preparation method for the composite adsorbent provided in Example 2-1, and the steps are as follows: E10. First slurry preparation: At a constant temperature of 60 °C, 4A, silica sol and water are stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the first slurry, which is cooled to room temperature by an ice bath. Among them, the dosage of silica sol is 30% of the total mass and the mass concentration is 30%; The dosage of water is 200% of the mass of 3A. The pH value of the first slurry is 10.21 and the viscosity is 47.2 mPa·s; The stirring and mixing time is 10 h and the rotation speed is 400 rpm; The ultrasonic dispersion time is 60 min.

[0172] E20. The first slurry, NaY zeolite, heptafluorobutyric acid and water are stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the second slurry, which is cooled to room temperature by an ice bath. Among them, based on the total mass of ZSM-35, 4A and NaY being 100%, the dosage of heptafluorobutyric acid is 0.3% of the total mass; The dosage of water is 200% of the mass of MOR zeolite; The pH value of the second slurry is 10.43 and the viscosity is 52.7 mPa·s; The stirring and mixing time is 16 h and the rotation speed is 500 rpm; The ultrasonic dispersion time is 120 min.

[0173] E30. The second slurry, ZSM-35, ammonium polymethacrylate and water are stirred and mixed, and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the third slurry, which is cooled to room temperature by an ice bath. Among them, based on the total mass of ZSM-35, 4A and NaY being 100%, the dosage of sodium polymethacrylate is 0.1% of the total mass; The dosage of water is 200% of the mass of ZSM-35; The pH value of the third slurry is 10.67 and the viscosity is 72.6 mPa·s; The stirring and mixing time is 22 h and the rotation speed is 700 rpm; The ultrasonic dispersion time is 180 min.

[0174] E40. The third slurry and polyoxyethylene are mixed and ball-milled to obtain a mixed coating slurry; Among them, the dosage of polyoxyethylene is 2% of the total mass and the mass concentration is 0.1%; The ball-milling time is 1 h and the ball-milling rotation speed is 600 rpm.

[0175] The glass fiber and the mixed coating slurry are subjected to lifting treatment, purging treatment and drying treatment; Among them, the volume ratio of the mixed coating slurry to the glass fiber is 5:1; In the lifting treatment, the number of lifting times is 3 times, the interval between two adjacent liftings is 5 min, and the infiltration time for a single lifting is 2 min; In the purging treatment, the purging speed is 5 L / min and the purging duration is 10 min; In the drying treatment, vacuum drying oven is used for drying, the vacuum degree is -0.1 MPa, the drying temperature is 100 °C, and the time is 24 h; The schematic diagram of the relative position structure of the prepared composite adsorbent is as Figure 8 shown; Figure 8 In it, 12 is 4A zeolite; 13 is NaY zeolite; 14 is ZSM-5 zeolite; 10 is silica sol; 11 is glass fiber.

[0176] Examples 2-3 Examples 2-3 provide a rotary adsorption separation device, and the rotor consists of a mixed adsorption zone, a CO2 desorption zone, an H2O desorption zone, a NO x desorption zone and a cooling zone; The adsorbent in the rotor uses the composite adsorbent provided in Example 2-1; Among them, the area ratio of the mixed adsorption zone, the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone and the cooling zone is 2:1:1:1.4:1.

[0177] This example also provides a gas adsorption separation method for the rotary adsorption separation device, and the steps are as follows: E11. The mixed gas enters the mixed adsorption zone for adsorption, and among them, the adsorption temperature is 25 °C.

[0178] E21. The desorbed gas enters the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone, and performs zoned desorption on the composite adsorbent; Among them, the temperature of the desorbed gas is 360 °C.

[0179] Examples 2-4 Examples 2-4 provide a fixed bed adsorption separation device, and the adsorbent uses the composite adsorbent provided in Example 2-1.

[0180] This example also provides a gas adsorption separation method for the fixed bed adsorption separation device, and the steps are as follows: E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ; Among them, the adsorption pressure is 0.2 mPa.

[0181] E22. Under vacuum conditions, the composite adsorbent is heated to 150 °C at a heating rate of 2 °C / min and then held for 30 min.

[0182] E32. Under vacuum conditions, the composite adsorbent is heated from 150 °C to 250 °C at a heating rate of 2 °C / min and then held for 30 min.

[0183] E42. Under vacuum conditions, the composite adsorbent is heated from 250 °C to 290 °C at a heating rate of 2 °C / min and then held for 30 min.

[0184] Example 3-1 Example 3-1 provides a composite adsorbent, the raw materials of which are Beta zeolite, Ti-MCM-41, and NaX zeolite.

[0185] Among them, the mass ratio of Beta zeolite, Ti-MCM-41, and NaX zeolite is 12:15:10.

[0186] Example 3-2 Example 3-2 provides a preparation method of the composite adsorbent provided in Example 3-1, and the steps are as follows: E10. Preparation of the first slurry: At a constant temperature of 50 °C, Ti-MCM-41, silica sol, and water are stirred and mixed and then ultrasonically dispersed. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the first slurry, and the first slurry is cooled to room temperature using an ice bath; Among them, the dosage of silica sol is 60% of the total mass and the mass concentration is 40%; The dosage of water is 300% of the mass of Ti-MCM-41; The pH value of the first slurry is 10.32 and the viscosity is 73.9 mPa·s; The stirring and mixing time is 12 h and the rotation speed is 300 rpm; The ultrasonic dispersion time is 30 min.

[0187] E20. The first slurry, NaX zeolite, sodium dodecyl sulfate, and water are stirred and mixed and then ultrasonically dispersed. Sodium phosphate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the second slurry, and the second slurry is cooled to room temperature using an ice bath; Among them, based on Beta zeolite, Ti-MCM-41, and NaX zeolite, the dosage of sodium dodecyl sulfate is 0.05% of the total mass; The dosage of water is 300% of the mass of NaX zeolite; The dosage of phosphoric acid is 0.2% of the total mass and the mass concentration is 0.5%; The pH value of the second slurry is 9.61, and the viscosity is 83.0 mPa·s; The stirring and mixing time is 16 h, and the rotation speed is 600 rpm; The ultrasonic dispersion time is 120 min.

[0188] E30. The second slurry, Beta zeolite, polyvinylpyrrolidone and water are stirred and mixed and then ultrasonically dispersed. Phosphoric acid and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the third slurry, and the third slurry is cooled to room temperature by using an ice bath; Among them, based on the total mass of Beta zeolite, Ti-MCM-41 and NaX zeolite being 100%, the dosage of polyvinylpyrrolidone is 0.05% of the total mass; The dosage of water is 300% of the mass of Beta zeolite; The dosage of phosphoric acid is 0.2% of the total mass and the mass concentration is 0.5%; The pH value of the third slurry is 10.11, and the viscosity is 113.6 mPa·s; The stirring and mixing time is 24 h, and the rotation speed is 800 rpm; The ultrasonic dispersion time is 160 min.

[0189] E40. The third slurry and polyoxypropylene are mixed and ball-milled to obtain a mixed coating slurry; Among them, the dosage of polyoxypropylene is 0.2% of the total mass and the mass concentration is 0.1%; The ball-milling time is 1 h, and the ball-milling rotation speed is 600 rpm.

[0190] E50. The glass fiber and the mixed coating slurry are subjected to pulling treatment, purging treatment and drying treatment; Among them, the volume ratio of the mixed coating slurry to the glass fiber is 4:1; In the pulling treatment, the number of pulling times is 5 times, the interval between two adjacent pullings is 10 min, and the infiltration time for a single pulling is 2 min; In the purging treatment, the purging speed is 10 L / min and the purging duration is 20 min; In the drying treatment, vacuum drying is carried out in a vacuum drying oven, the vacuum degree is -0.1 MPa, the drying temperature is 120 °C, and the time is 12 h; The relative position structure schematic diagram of the prepared composite adsorbent is as Figure 9 shown; Figure 9 Among them, 15 is Beta zeolite; 16 is Ti-MCM-41; 17 is NaX zeolite; 10 is silica sol; 11 is glass fiber.

[0191] Example 3-3 Example 3-3 provides a rotary wheel adsorption separation device. The rotary wheel consists of a mixed adsorption zone, a CO2 desorption zone, an H2O desorption zone, a NO x desorption zone, and a cooling zone; The adsorbent in the rotary wheel uses the composite adsorbent provided in Example 3-1; Among them, the area ratio of the mixed adsorption zone, the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone, and the cooling zone is 2:1.2:1.2:1.6:1.

[0192] This example also provides a gas adsorption separation method for the rotary wheel adsorption separation device, and the steps are as follows: E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 30 °C.

[0193] E21. The desorbed gas enters the CO2 desorption zone, the H2O desorption zone, and the NO x desorption zone to perform zoned desorption on the composite adsorbent; Among them, the temperature of the desorbed gas is 380 °C.

[0194] Example 3-4 Example 3-4 provides a fixed bed adsorption separation device, and the adsorbent uses the composite adsorbent provided in Example 3-1.

[0195] This example also provides a gas adsorption separation method for the fixed bed adsorption separation device, and the steps are as follows: E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O, and NO in the gas x ; Among them, the adsorption pressure is 0.3 mPa.

[0196] E22. Under vacuum conditions, the composite adsorbent is heated to 150 °C at a heating rate of 5 k / min and kept warm for 20 min.

[0197] E32. Under vacuum conditions, the composite adsorbent is heated from 150 °C to 250 °C at a heating rate of 5 k / min and kept warm for 20 min.

[0198] E42. Under vacuum conditions, the composite adsorbent is heated from 250 °C to 275 °C at a heating rate of 5 k / min and kept warm for 20 min.

[0199] Example 4-1 Example 4-1 provides a composite adsorbent, and the raw materials are composed of SAPO-34, 3A, and NaY.

[0200] Among them, the mass ratio of SAPO-34, 3A, and NaY zeolites is 11:12:10.

[0201] Example 4-2 Example 4-2 provides the preparation method of the composite adsorbent provided by Example 4-1, and the steps are as follows: E10. Preparation of the first slurry: At a constant temperature of 60 °C, 3A, silica sol and water are stirred and mixed and then ultrasonically dispersed, and sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the first slurry, and the first slurry is cooled to room temperature by using an ice bath; Among them, the dosage of silica sol is 40% of the total mass and the mass concentration is 30%; The dosage of water is 200% of the mass of 3A; The pH value of the first slurry is 8.93 and the viscosity is 38.5 mPa·s; The stirring and mixing time is 8 h and the rotation speed is 400 rpm; The ultrasonic dispersion time is 60 min.

[0202] E20. The first slurry, NaY zeolite, perfluoroundecanoic acid and water are stirred and mixed and then ultrasonically dispersed, and sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the second slurry, and the second slurry is cooled to room temperature by using an ice bath; Among them, based on the total mass of SAPO-34, 3A and NaY zeolite being 100%, the dosage of perfluoroundecanoic acid is 0.1% of the total mass; The dosage of water is 200% of the mass of NaY zeolite; The pH value of the second slurry is 9.42 and the viscosity is 47.9 mPa·s; The stirring and mixing time is 14 h and the rotation speed is 500 rpm; The ultrasonic dispersion time is 80 min.

[0203] E30. The second slurry, SAPO-34, sodium polymethacrylate and water are stirred and mixed and then ultrasonically dispersed, and sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the third slurry, and the third slurry is cooled to room temperature by using an ice bath; Among them, based on the total mass of SAPO-34, 3A and NaY zeolite being 100%, the dosage of sodium polymethacrylate is 0.1% of the total mass; The dosage of water is 200% of the mass of SAPO-34; The pH value of the third slurry is 9.85 and the viscosity is 53.8 mPa·s; The stirring and mixing time is 20 h and the rotation speed is 600 rpm; The ultrasonic dispersion time is 180 min.

[0204] E40. The third slurry and polyoxyethylene are mixed and ball-milled to obtain a mixed coating slurry; Among them, the dosage of polyethylene oxide is 0.2% of the total mass, and the mass concentration is 0.1%. The ball milling time is 1 h, and the ball milling speed is 600 rpm.

[0205] E50. The glass fiber and the mixed coating slurry are subjected to pulling treatment, purging treatment and drying treatment. Among them, the volume ratio of the mixed coating slurry to the glass fiber is 4:1. In the pulling treatment, the number of pulling times is 3, the interval between two adjacent pullings is 5 min, and the infiltration time for a single pulling is 2 min. In the purging treatment, the purging speed is 5 L / min and the purging time is 10 min. In the drying treatment, vacuum drying is carried out using a vacuum drying oven, the vacuum degree is -0.1 MPa, the drying temperature is 100 °C, and the time is 24 h.

[0206] Example 4-3 Example 4-3 provides a rotary wheel adsorption separation device. The rotary wheel is composed of a mixed adsorption zone, a CO2 desorption zone, an H2O desorption zone, a NO x desorption zone and a cooling zone. The adsorbent in the rotary wheel uses the composite adsorbent provided in Example 4-1. Among them, the area ratio of the mixed adsorption zone, the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone and the cooling zone is 2:1:1:1.2:1.

[0207] This example also provides a gas adsorption separation method for the rotary wheel adsorption separation device of this example. The steps are as follows: E11. The mixed gas enters the mixed adsorption zone for adsorption. Among them, the adsorption temperature is 25 °C.

[0208] E21. The desorbed gas enters the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone to perform zoned desorption on the composite adsorbent. Among them, the temperature of the desorbed gas is 350 °C.

[0209] Example 4-4 Example 4-4 provides a fixed bed adsorption separation device, and the adsorbent uses the composite adsorbent provided in Example 4-1.

[0210] This example also provides a gas adsorption separation method for the fixed bed adsorption separation device. The steps are as follows: E12. Adsorption stage: The composite adsorbent simultaneously adsorbs CO2, H2O and NO in the gas x ; Among them, the adsorption pressure is 0.2 mPa.

[0211] E22. Desorption E221. Under vacuum conditions, heat the composite adsorbent at a heating rate of 2 °C / min to 150 °C and then hold for 30 min.

[0212] E222. Under vacuum conditions, heat the composite adsorbent from 150 °C to 220 °C at a heating rate of 2 °C / min and then hold for 30 min.

[0213] E223. Under vacuum conditions, heat the composite adsorbent from 220 °C to 315 °C at a heating rate of 2 °C / min and then hold for 30 min.

[0214] Example 5-1 Example 5-1 provides a composite adsorbent, the raw materials of which are composed of SSZ-13, 3A and NaY zeolites.

[0215] Among them, the mass ratio of SSZ-13, 3A and NaY is 12:12:10.

[0216] Example 5-2 Example 5-2 provides a preparation method of the composite adsorbent provided in Example 5-1, and the steps are as follows: E10. Preparation of the first slurry: At a constant temperature of 55 °C, stir and mix 3A, silica sol and water, and then disperse them ultrasonically. Sodium carbonate and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the first slurry, and cool the first slurry to room temperature by using an ice bath; Among them, the dosage of silica sol is 30% of the total mass and the mass concentration is 30%; The dosage of water is 200% of the mass of 3A; The pH value of the first slurry is 9.17 and the viscosity is 68.3 mPa·s; The stirring and mixing time is 12 h and the rotation speed is 200 rpm; The ultrasonic dispersion time is 40 min.

[0217] E20. Stir and mix the first slurry, NaY zeolite, ethoxylated fatty acid methyl ester and water, and then disperse them ultrasonically. Sodium hydroxide and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the second slurry, and cool the second slurry to room temperature by using an ice bath; Among them, based on the total mass of SSZ-13, 3A and NaY zeolites being 100%, the dosage of ethoxylated fatty acid methyl ester is 0.3% of the total mass; The dosage of water is 200% of the mass of NaY zeolite; The pH value of the second slurry is 9.84 and the viscosity is 81.9 mPa·s; The stirring and mixing time is 16 h and the rotation speed is 600 rpm; The ultrasonic dispersion time is 120 min.

[0218] E30. The second slurry, SSZ-13, ammonium polymethacrylate and water are stirred and mixed, and then ultrasonically dispersed. Sodium hydroxide and sodium carboxymethylcellulose are used to adjust the pH value and viscosity respectively to obtain the third slurry, and the third slurry is cooled to room temperature by using an ice bath; Among them, based on the total mass of SSZ-13, 3A and NaY zeolites being 100%, the dosage of ammonium polymethacrylate is 0.3% of the total mass; The dosage of water is 200% of the mass of SSZ-13; The pH value of the third slurry is 10.37, and the viscosity is 126.4 mPa·s; The stirring and mixing time is 24 h, and the rotation speed is 800 rpm; The ultrasonic dispersion time is 180 min.

[0219] E40. The third slurry and polypropylene oxide are mixed and ball-milled to obtain a mixed coating slurry; Among them, the dosage of polypropylene oxide is 0.2% of the total mass, and the mass concentration is 0.1%; The ball-milling time is 1 h, and the ball-milling rotation speed is 1000 rpm.

[0220] E50. The glass fiber and the mixed coating slurry are subjected to pulling treatment, purging treatment and drying treatment; Among them, the volume ratio of the mixed coating slurry to the glass fiber is 3:1; In the pulling treatment, the number of pulling times is 3 times, the interval between two adjacent pullings is 5 min, and the infiltration duration of a single pulling is 2 min; In the purging treatment, the purging speed is 5 L / min, and the purging duration is 10 min; In the drying treatment, vacuum drying is carried out by using a vacuum drying oven, the vacuum degree is -0.1 MPa, the drying temperature is 100 °C, and the time is 24 h.

[0221] Example 5-3 Example 5-3 provides a rotary adsorption separation device. The rotor consists of a mixed adsorption zone, a CO2 desorption zone, an H2O desorption zone, a NO x desorption zone and a cooling zone; The adsorbent in the rotor adopts the composite adsorbent provided in Example 5-1; Among them, the area ratio of the mixed adsorption zone, the CO2 desorption zone, the H2O desorption zone, the NO x desorption zone and the cooling zone is 2:1.2:1.2:1.4:1.

[0222] This example also provides a gas adsorption and separation method for the rotary adsorption separation device, and the steps are as follows: E11. The mixed gas enters the mixed adsorption zone for adsorption, where the adsorption temperature is 25 °C.

[0223] E21. The desorbed gas enters the CO2 desorption zone, the H2O desorption zone, and the NO x desorption zone to perform zone desorption on the composite adsorbent; Among them, the temperature of the desorbed gas is 350 °C.

[0224] Example 5-4 Example 5-4 provides a fixed-bed adsorption separation device, and the adsorbent uses the composite adsorbent provided in Example 5-1.

[0225] This example also provides a gas adsorption separation method for the fixed-bed adsorption separation device, and the steps are as follows: E12. Adsorption stage: The composite adsorbent simultaneously adsorbs H2O, CO2, and NO in the gas x ; Among them, the adsorption pressure is 0.2 mPa.

[0226] E22. Under vacuum conditions, the composite adsorbent is heated to 150 °C at a heating rate of 2 °C / min and then kept warm for 30 min.

[0227] E32. Under vacuum conditions, the composite adsorbent is heated from 150 °C to 220 °C at a heating rate of 2 °C / min and then kept warm for 30 min.

[0228] E42. Under vacuum conditions, the composite adsorbent is heated from 180 °C to 300 °C at a heating rate of 2 °C / min and then kept warm for 30 min.

[0229] Comparative Example 1 Comparative Example 1 provides a mixed adsorbent, which is composed of NO x honeycomb adsorbent, H2O honeycomb adsorbent, and CO2 honeycomb adsorbent mixed.

[0230] This comparative example provides a preparation method for the mixed adsorbent provided in this comparative example, and the steps are as follows: D10. Preparation of NO x honeycomb adsorbent The ZSM-35 slurry and glass fiber are mixed and coated and then dried; Among them, the ZSM-35 slurry is composed of ZSM-35 and water, and the mass of water is 200% of ZSM-35; The volume ratio of the ZSM-35 slurry to the glass fiber is 3:1.

[0231] D20. Preparation of H2O honeycomb adsorbent The 3A slurry and glass fiber are mixed, coated, and then dried; Among them, the 3A slurry is composed of 3A and water, and the mass of water is 200% of that of 3A; The volume ratio of the 3A slurry to the glass fiber is 3:1.

[0232] Preparation of D30.CO2 honeycomb adsorbent The MOR slurry and glass fiber are mixed, coated, and then dried; Among them, the MOR slurry is composed of MOR and water, and the mass of water is 200% of that of MOR; The volume ratio of the MOR slurry to the glass fiber is 3:1.

[0233] The mass ratio of ZSM-35, 3A, and MOR is 8:12:10.

[0234] Comparative Example 2 Comparative Example 2 provides a gas adsorption and separation method for a fixed-bed adsorption separation device provided in Examples 1-4. The steps are basically the same as those in Examples 1-4, except that: The desorption step in Step E22 is as follows: Under vacuum conditions, the composite adsorbent is heated to 285 °C at a heating rate of 2 k / min and then held for 90 min.

[0235] In order to verify the progressiveness of the composite adsorbent, 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 tests and rotary-wheel adsorption tests under the adsorption and desorption conditions of Examples 2-3 and Examples 2-4, respectively. The rotary-wheel adsorption test is shown in Table 1 below, the fixed-bed test results are shown in Table 2 below, and the concentrations of the NO x enriched gas, CO2 enriched gas, and H2O enriched gas obtained by desorption are shown in Table 3 below.

[0236] Table 1

[0237] Table 2

[0238] Table 3

[0239] As can be seen from the above table: (1) The composite adsorbent provided in the embodiments of the present invention can achieve the co-adsorption of NO x , H2O, and CO2.

[0240] (2) The preparation method of the composite adsorbent provided in the embodiments of the present invention can remove NO xThe adsorption materials, water adsorption materials, and CO2 adsorption materials are reasonably loaded on the carrier, and the obtained composite adsorbent can achieve the co-adsorption of NO x , H2O, and CO2.

[0241] (3) In Table 3, from the gas enrichment concentrations of the examples and comparative examples, it can be seen that for the rotary adsorption separation device provided by the embodiments of the present invention, during desorption, temperature gradient desorption of NO x , H2O, and CO2 can be carried out, and the enrichment of NO x , H2O, and CO2 can be achieved simultaneously.

[0242] (4) For the fixed-bed adsorption separation device provided by the embodiments of the present invention, using the composite adsorbent provided by the embodiments of the present invention, during desorption, temperature gradient desorption of NO x , H2O, and CO2 can be carried out, and the enrichment of NO x , H2O, and CO2 can be achieved simultaneously.

[0243] The above are only the preferred embodiments of the composite adsorbent and its preparation method, gas separation device and method of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A composite adsorbent, characterized in that, The raw materials include a carrier and an active material; The active material includes NO x adsorbents, water adsorbents, and CO2 adsorbents; The NO x The mass ratio of the NO adsorption material, the water adsorption material, and the CO2 adsorption material is 5 to 15:7 to 18:

10.

2. The composite adsorbent according to claim 1, wherein The NO x adsorbent material includes at least one of ZSM-35 zeolite, ZSM-5 zeolite, Beta zeolite, SAPO-34 zeolite, and SSZ-13 zeolite; and / or, the water adsorption material includes at least one of 3A, 4A, and Ti-MCM-41; and / or, the CO2 adsorption material includes at least one of Y zeolite, X zeolite, and MOR zeolite; and / or, the material of the carrier includes at least one of glass fiber and ceramic fiber.

3. A method for preparing a composite adsorbent as described in claim 1 or 2, characterized in that, It includes the following steps: Perform a coating treatment on the mixed coating slurry and the carrier; The mixed coating slurry contains the active material, a first dispersant, a second dispersant, a sol, and an auxiliary agent.

4. The preparation method of the composite adsorbent according to claim 3, wherein The mass of the first dispersant is 0.05% - 2% of the active material; and / or, the first dispersant includes at least one of polyether-modified polydimethylsiloxane, sodium dodecyl sulfate, ethoxylated fatty acid methyl ester, heptafluorobutyric acid, perfluoroundecanoic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonamide; and / or, the mass of the second dispersant is 0.05% - 2% of the active material; and / or, the second dispersant includes at least one of sodium methylene bisnaphthalene sulfonate, polyvinylpyrrolidone, ammonium polymethacrylate, sodium polymethacrylate, and sodium polyacrylate; and / or, the mass of the sol is 20% - 60% of the active material; and / or, the sol includes at least one of silica sol and alumina sol; and / or, the auxiliary agent includes a pH regulator, an antifoaming agent, a viscosity modifier, and a solvent; and / or, the pH value of the mixed coating slurry is 8 - 11; and / or, the viscosity of the mixed coating slurry is 10 mPa·s - 200 mPa·s.

5. The preparation method of the composite adsorbent according to claim 3 or 4, characterized in that, The preparation of the mixed coating slurry includes the following steps: Perform a first mixing treatment on a first slurry, the CO2 adsorption material, the first dispersant, and the auxiliary agent to obtain a second slurry; the first slurry contains the water adsorption material, the sol, and the auxiliary agent; The second slurry and the NO x Adsorbent material, second dispersant and auxiliary agent are subjected to a second mixing treatment to obtain a third slurry; Perform a third mixing treatment on the third slurry to obtain the mixed coating slurry.

6. The preparation method of the composite adsorbent according to claim 3 or 4, characterized in that, The coating treatment includes the following steps: The carrier is subjected to a lifting treatment, a purging treatment, and a drying treatment.

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

8. A separation method of the rotary adsorption separation device according to claim 7, characterized in that It includes the following steps: Use the composite adsorbent as described in claim 1 or 2 to perform rotary adsorption and rotary desorption on the gas.

9. A fixed-bed adsorption separation device, characterized in that, The adsorbent used includes the composite adsorbent as described in claim 1 or 2.

10. A method for adsorption separation of the fixed-bed adsorption separation device according to claim 9, characterized in that, It includes the following steps: Use the composite adsorbent as described in claim 1 or 2 to perform fixed-bed adsorption and fixed-bed desorption on the gas.

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