Magnetic induction heating gas separation adsorbent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of gas separation, and particularly discloses a magnetic induction heating gas separation adsorbent and a preparation method and application thereof.The method comprises the steps that metal or metal oxide nanoparticles are modified, and modified metal or metal oxide nanoparticles are obtained; the modified metal or metal oxide nanoparticles, metal organic framework powder and a binder are put into water to be stirred, and slurry of the magnetic induction heating gas separation adsorbent is obtained; and molding and roasting the slurry to obtain the magnetic induction heating gas separation adsorbent. The prepared magnetic induction heating gas separation adsorbent has the remarkable advantage of low energy consumption in the field of gas separation, in-situ generation of heat is achieved through an alternating magnetic field, the heating rate is high, the heat transfer path is short, the energy utilization rate is high, and compared with a traditional high-temperature gas heating method, the energy consumption is reduced by 23% or above.

Description

Technical Field

[0001] This invention relates to the field of gas separation technology, and more specifically, to a magnetic induction heating gas separation adsorbent, its preparation method, and its application. Background Technology

[0002] Light hydrocarbon separation is a crucial step in chemical production, playing a key role in natural gas purification, VOCs treatment in industrial waste gas, and oil and gas recovery in the petrochemical industry. Selectively capturing light hydrocarbon gases through adsorption separation technology is an important method for achieving light hydrocarbon separation.

[0003] Traditional gas separation adsorbents require high-temperature desorption for regeneration after adsorption saturation, necessitating external heating of the entire adsorption bed. This results in low thermal conductivity and high energy consumption, limiting their industrial applications. Preparing novel gas separation materials and developing efficient thermal desorption technologies based on these materials are key to overcoming these challenges.

[0004] Therefore, it is necessary to design a magnetic induction heating gas separation adsorbent and its preparation method to solve the problems of high desorption heat consumption and low heat transfer efficiency of traditional adsorbents. Summary of the Invention

[0005] In view of this, the present invention proposes a magnetic induction heating gas separation adsorbent and its preparation method to solve the problems of high desorption heat consumption and low heat conduction efficiency of traditional adsorbents.

[0006] On the one hand, the present invention provides a magnetic induction heating gas separation adsorbent and its preparation method, comprising the following preparation steps:

[0007] Metal or metal oxide nanoparticles are mixed with sodium acetate and oleic acid, separated by ultrasonication, washed and dried to obtain modified metal or metal oxide nanoparticles.

[0008] The modified metal or metal oxide nanoparticles, metal-organic framework powder, and binder are placed in water and stirred to obtain a slurry of magnetic induction heating gas separation adsorbent.

[0009] The slurry is shaped and calcined to obtain the magnetic induction heating gas separation adsorbent.

[0010] Furthermore, the metal or metal oxide nanoparticles include: Fe3O4, γ-Fe2O3, CoFe2O4, Mn x Zn 1-x Fe2O4 (0≤x≤1), Ni x Zn 1-x Fe2O4 (0≤x≤1), Zn 1-x Mo xFe2O4 (0≤x≤1), Li 0-5 Fe 2-5 O4, Mg 1-x Ni x One or more of Fe2O4 (0≤x≤1), alloy powder, and stainless steel.

[0011] Furthermore, the mass ratio of the metal or metal oxide nanoparticles, sodium acetate, and oleic acid is 5:(1-3):(1-6).

[0012] Furthermore, the metal-organic framework powder is one or more of the following: two-dimensional layered MOF material, porphyrin-based MOF material, ZIF series MOF material, or MIL series material.

[0013] Furthermore, the adhesive is one or more of the following: kaolin, attapulgite, bentonite, ceramic clay, water glass, calcium carbide sludge, sodium sulfate (Na2SO4), silica sol, alumina sol, aluminum dihydrogen phosphate, magnesium phosphate, epoxy resin, phenolic resin, chloroprene rubber, silicone rubber, silicate cement, aluminate cement, phosphate cement, and clay minerals.

[0014] Furthermore, the mass ratio of the modified metal or metal oxide nanoparticles to the metal-organic framework powder and binder is (1-3):(5-8):(2-4).

[0015] Furthermore, the molding process specifically involves extrusion molding or ball rolling molding.

[0016] On the other hand, the present invention also provides the application of a magnetic induction heating gas separation adsorbent, wherein the magnetic induction heating gas separation adsorbent is filled into an adsorption bed to adsorb hydrocarbon gases. After the adsorption is completed, the adsorption bed is placed in an induction coil, and then an alternating magnetic field is generated by passing an electric current through it. Metal or metal oxide nanoparticles desorb hydrocarbon gases through magnetic induction heating.

[0017] Furthermore, the hydrocarbon gas includes: alkanes, alkenes, or alkynes.

[0018] Furthermore, the frequency of the alternating magnetic field is 50Hz-5MHz, the power is 100-4000W, and the regeneration temperature is 40-160℃.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: the magnetic induction heating gas separation adsorbent prepared by the present invention has significant low energy consumption advantages in the field of gas separation. It achieves in-situ heat generation through alternating magnetic field, with fast heating rate, short heat transfer path and high energy utilization rate, reducing energy consumption by more than 23% compared with traditional high temperature gas heating method. Attached Figure Description

[0020] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0021] Figure 1 A flowchart illustrating the preparation method of the magnetic induction heating gas separation adsorbent provided in this embodiment of the invention. Detailed Implementation

[0022] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0023] In the description of this application, it should be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0024] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, unless otherwise stated, "a plurality of" means two or more.

[0025] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection between two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0026] On the one hand, such as Figure 1 As shown in some embodiments of this application, a magnetic induction heating gas separation adsorbent and its preparation method include the following preparation steps:

[0027] Metal or metal oxide nanoparticles are mixed with sodium acetate and oleic acid, separated by ultrasonication, washed and dried to obtain modified metal or metal oxide nanoparticles.

[0028] The modified metal or metal oxide nanoparticles, metal-organic framework powder, and binder are placed in water and stirred to obtain a slurry of magnetic induction heating gas separation adsorbent.

[0029] The slurry is shaped and calcined to obtain the magnetic induction heating gas separation adsorbent.

[0030] Specifically, the magnetic induction heating gas separation adsorbent is in particulate form.

[0031] Specifically, the ultrasonic separation time is 15 minutes.

[0032] Specifically, when the modified metal or metal oxide nanoparticles, metal-organic framework powder, and binder are placed in water and stirred, the water temperature is 30°C and the stirring time is 2 hours.

[0033] It is understood that the magnetic induction heating gas separation adsorbent prepared by this invention has significant low energy consumption advantages in the field of gas separation. It achieves in-situ heat generation through alternating magnetic field, with fast heating rate, short heat transfer path and high energy utilization rate, reducing energy consumption by more than 23% compared with traditional high temperature gas heating method.

[0034] In some embodiments of this application, the metal or metal oxide nanoparticles include: Fe3O4, γ-Fe2O3, CoFe2O4, Mn x Zn 1-x Fe2O4 (0≤x≤1), Ni x Zn 1-x Fe2O4 (0≤x≤1), Zn 1-x Mo x Fe2O4 (0≤x≤1), Li 0-5 Fe 2-5 O4, Mg 1-x Ni x One or more of Fe2O4 (0≤x≤1), alloy powder, and stainless steel, preferably γ-Fe2O3.

[0035] Specifically, the alloy powder is FeB. 23 Co .05 FeB 16 C 1.0 FeCo 35 FeCo 50 Ni 70 Fe 30 Ni 50 Fe50 Ni 30 Fe 70 FeCr 55 FeMn 78 C 8.0 FeMn 82 C 1.0 FeMo 65 、FeSiAl.

[0036] Specifically, the stainless steel is 316 stainless steel or 304 stainless steel.

[0037] Specifically, the metal or metal oxide nanoparticles have a spherical, cubic, or spindle-shaped morphology and a particle size of 3 nm-500 μm.

[0038] In some embodiments of this application, the mass ratio of the metal or metal oxide nanoparticles, sodium acetate and oleic acid is 5:(1-3):(1-6), preferably 5:2:4.

[0039] In some embodiments of this application, the metal-organic framework powder is one or more of the following: two-dimensional layered MOF material, porphyrin-based MOF material, ZIF series MOF material, or MIL series material.

[0040] Specifically, two-dimensional layered MOF materials include: Fe-MOF-74, Mg-MOF-74, and Co-MOF-74; porphyrin-based MOF materials include: NKMOF-1-Ni and NKMOF-1-Cu; ZIF series MOF materials include: ZIF-8, ZIF-4, ZIF-7, and ZIF-76; and MIL series materials include: MIL-101, MIL-53, MIL-47, and MIL-100.

[0041] In some embodiments of this application, the adhesive is one or more of the following: kaolin, attapulgite, bentonite, ceramic clay, water glass, calcium carbide sludge, sodium sulfate (Na2SO4), silica sol, alumina sol, aluminum dihydrogen phosphate, magnesium phosphate, epoxy resin, phenolic resin, chloroprene rubber, silicone rubber, silicate cement, aluminate cement, phosphate cement, and clay minerals.

[0042] In some embodiments of this application, the mass ratio of the modified metal or metal oxide nanoparticles to the metal-organic framework powder and binder is (1-3):(5-8):(2-4); preferably 3:8:2.

[0043] In some embodiments of this application, the molding process specifically refers to extrusion molding or ball rolling molding.

[0044] Specifically, the particle size after molding is 2-5 mm.

[0045] On the other hand, in some embodiments of this application, the magnetic induction heating gas separation adsorbent is used to fill the adsorption bed to adsorb hydrocarbon gases. After adsorption, the adsorption bed is placed in an induction coil, and then an alternating magnetic field is generated by energizing. Metal or metal oxide nanoparticles desorb hydrocarbon gases through magnetic induction heating.

[0046] In some embodiments of this application, the hydrocarbon gas includes: alkanes, alkenes, or alkynes.

[0047] In some embodiments of this application, the frequency of the alternating magnetic field is 50Hz-5MHz, the power is 100-4000W, and the regeneration temperature is 40-160℃; preferably, the frequency of the alternating magnetic field is 1kHz, the power is 300W, and the regeneration temperature is 140℃.

[0048] Example 1

[0049] S1. Fe3O4 nanoparticles, sodium acetate, and oleic acid are mixed in a mass ratio of 5:2:4, sonicated for 15 min, and finally washed and dried to obtain modified Fe3O4 nanoparticles.

[0050] S2. The modified Fe3O4 nanoparticles are combined with MOF-74 and kaolin in a mass ratio of 1:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0051] S3 The slurry is extruded into strips with a particle size of 2 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0052] Example 2

[0053] S1. Mix CoFe2O4 nanoparticles with sodium acetate and oleic acid in a mass ratio of 5:2:4, sonicate for 15 min, and finally wash and dry to obtain modified CoFe2O4 nanoparticles.

[0054] S2. The modified CoFe2O4 nanoparticles are combined with ZIF-8 and attapulgite in a mass ratio of 1:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0055] S3 The slurry is extruded into strips with a particle size of 3 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0056] Example 3

[0057] S1, FeCo 35Nanoparticles, sodium acetate, and oleic acid were mixed at a mass ratio of 5:2:4, sonicated for 15 minutes, and finally washed and dried to obtain modified FeCo. 35 Nanoparticles;

[0058] S2, the modified FeCo 35 Nanoparticles were combined with MIL-100 and kaolin in a mass ratio of 1:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0059] S3 The slurry is extruded into strips with a particle size of 2 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0060] Example 4

[0061] S1. Fe3O4 nanoparticles, sodium acetate, and oleic acid are mixed in a mass ratio of 5:2:4, sonicated for 15 min, and finally washed and dried to obtain modified Fe3O4 nanoparticles.

[0062] S2. The modified Fe3O4 nanoparticles are combined with ZIF-8 and attapulgite in a mass ratio of 2:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0063] S3 The slurry is extruded into strips with a particle size of 3 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0064] Example 5

[0065] S1. Mix CoFe2O4 nanoparticles with sodium acetate and oleic acid in a mass ratio of 5:2:4, sonicate for 15 min, and finally wash and dry to obtain modified CoFe2O4 nanoparticles.

[0066] S2. The modified CoFe2O4 nanoparticles are combined with MIL-100 and kaolin in a mass ratio of 2:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0067] S3 The slurry is extruded into strips with a particle size of 2 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0068] Example 6

[0069] S1, FeCo 35 Nanoparticles, sodium acetate, and oleic acid were mixed at a mass ratio of 5:2:4, sonicated for 15 minutes, and finally washed and dried to obtain modified FeCo. 35 Nanoparticles;

[0070] S2, the modified FeCo 35 Nanoparticles were combined with MOF-74 and attapulgite in a mass ratio of 2:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0071] S3 The slurry is extruded into strips with a particle size of 3 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0072] Example 7

[0073] S1. Fe3O4 nanoparticles, sodium acetate, and oleic acid are mixed in a mass ratio of 5:2:4, sonicated for 15 min, and finally washed and dried to obtain modified Fe3O4 nanoparticles.

[0074] S2. The modified Fe3O4 nanoparticles are combined with MIL-100 and kaolin in a mass ratio of 3:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0075] S3 The slurry is extruded into strips with a particle size of 2 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0076] Example 8

[0077] S1. Mix CoFe2O4 nanoparticles with sodium acetate and oleic acid in a mass ratio of 5:2:4, sonicate for 15 min, and finally wash and dry to obtain modified CoFe2O4 nanoparticles.

[0078] S2. The modified CoFe2O4 nanoparticles are combined with MOF-74 and attapulgite in a mass ratio of 3:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0079] S3 The slurry is extruded into strips with a particle size of 3 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0080] Example 9

[0081] S1, FeCo 35 Nanoparticles, sodium acetate, and oleic acid were mixed at a mass ratio of 5:2:4, sonicated for 15 minutes, and finally washed and dried to obtain modified FeCo. 35 Nanoparticles;

[0082] S2, the modified FeCo 35Nanoparticles were combined with ZIF-8 and kaolin in a mass ratio of 3:8:2 and stirred in an aqueous solution at 30°C for 2 hours to form a slurry of magnetic induction heating gas separation adsorbent.

[0083] S3 The slurry is extruded into strips with a particle size of 2 mm, and then calcined to obtain granular magnetic induction heating gas separation adsorbent.

[0084] Effect test

[0085] The adsorbents prepared in Examples 1-9 were used for the separation of alkanes and alkenes. 10g of each adsorbent prepared in Examples 1-9 was loaded into an adsorption bed, and desorption was performed using different heating methods. The desorption time was then analyzed by gas chromatography. The results and processing parameters are shown in Tables 1-2.

[0086] Table 1. Results of ethane separation and desorption using the adsorbents from Examples 1-9.

[0087]

[0088]

[0089] Table 2. Results of the separation and desorption of ethylene using the adsorbents from Examples 1-9.

[0090]

[0091] It is evident that the adsorbents prepared in Examples 1-9 of this application are far more effective at desorption by magnetic induction heating than by hot nitrogen heating, with Example 7 exhibiting the shortest desorption time.

[0092] The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention should be covered within the protection scope of the claims of the present invention.

Claims

1. A magnetic induction heating gas separation adsorbent and its preparation method, characterized in that, The preparation steps include the following: Metal or metal oxide nanoparticles are mixed with sodium acetate and oleic acid, separated by ultrasonication, washed and dried to obtain modified metal or metal oxide nanoparticles. The modified metal or metal oxide nanoparticles, metal-organic framework powder, and binder are placed in water and stirred to obtain a slurry of magnetic induction heating gas separation adsorbent. The slurry is shaped and calcined to obtain the magnetic induction heating gas separation adsorbent.

2. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 1, characterized in that, The metal or metal oxide nanoparticles include: Fe3O4, γ-Fe2O3, CoFe2O4, Mn x Zn 1-x Fe2O4 (0≤x≤1), Ni x Zn 1-x Fe2O4 (0≤x≤1), Zn 1-x Mo x Fe2O4 (0≤x≤1), Li 0-5 Fe 2-5 O4, Mg 1-x Ni x One or more of Fe2O4 (0≤x≤1), alloy powder, and stainless steel.

3. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 2, characterized in that, The mass ratio of the metal or metal oxide nanoparticles, sodium acetate and oleic acid is 5:(1-3):(1-6).

4. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 3, characterized in that, The metal-organic framework powder is one or more of the following: two-dimensional layered MOF material, porphyrin-based MOF material, ZIF series MOF material, or MIL series material.

5. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 4, characterized in that, The adhesive is one or more of the following: kaolin, attapulgite, bentonite, ceramic clay, water glass, calcium carbide sludge, sodium sulfate (Na2SO4), silica sol, alumina sol, aluminum dihydrogen phosphate, magnesium phosphate, epoxy resin, phenolic resin, chloroprene rubber, silicone rubber, silicate cement, aluminate cement, phosphate cement, and clay minerals.

6. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 5, characterized in that, The mass ratio of the modified metal or metal oxide nanoparticles to the metal-organic framework powder and binder is (1-3):(5-8):(2-4).

7. The magnetic induction heating gas separation adsorbent and its preparation method according to claim 6, characterized in that, The molding process specifically refers to extrusion molding or ball rolling molding.

8. The application of the magnetic induction heating gas separation adsorbent according to any one of claims 1-7, characterized in that, The magnetic induction heating gas separation adsorbent is loaded into the adsorption bed to adsorb hydrocarbon gases. After adsorption, the adsorption bed is placed in the induction coil, and then an alternating magnetic field is generated by energizing. Metal or metal oxide nanoparticles desorb hydrocarbon gases through magnetic induction heating.

9. The application of the magnetic induction heating gas separation adsorbent according to claim 8, characterized in that, The hydrocarbon gases include: alkanes, alkenes, or alkynes.

10. The application of the magnetic induction heating gas separation adsorbent according to claim 8, characterized in that, The alternating magnetic field has a frequency of 50Hz-5MHz, a power of 100-4000W, and a regeneration temperature of 40-160℃.

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