Hydrogen-bonded organic framework and preparation method therefor, and adsorbent
The hydrogen-bonded organic framework HIAM-103 material, synthesized via a hydrothermal method, solves the structural instability and environmental pollution problems of existing HOF materials in flue gas carbon dioxide capture, achieving low-energy consumption and high-efficiency carbon dioxide capture, and supporting the realization of the "dual carbon" target.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- SHENZHEN POLYTECHNIC
- Filing Date
- 2025-03-21
- Publication Date
- 2026-07-30
AI Technical Summary
Existing HOF materials are structurally unstable when capturing carbon dioxide in flue gas, and the long synthesis process can easily cause environmental pollution. Existing organic amine solution systems have high energy consumption and release toxic substances.
HIAM-103, a hydrogen-bonded organic framework, was synthesized using a hydrothermal method. It was then linked by hydrogen bonds to form a highly stable porous material, which was used to selectively capture carbon dioxide from flue gas using a physical adsorption method.
It achieves efficient, low-energy-consumption, and environmentally friendly carbon dioxide capture, has good structural stability, is suitable for flue gas purification, and supports the achievement of "dual carbon" goals.
Smart Images
Figure CN2025084144_30072026_PF_FP_ABST
Abstract
Description
Hydrogen-bonded organic frameworks and their preparation methods, adsorbents Technical Field
[0001] This invention relates to the field of organic framework technology, and in particular to hydrogen-bonded organic frameworks, their preparation methods, and adsorbents. Background Technology
[0002] To address the increasingly severe global climate change situation, the Paris Agreement proposed limiting the rise in global average temperature to well below 2°C above pre-industrial levels, and striving to limit it to 1.5°C. The International Energy Agency (IEA), in its Energy Technology Outlook 2017, pointed out that to achieve the climate target of limiting warming to 2°C by the end of this century, carbon dioxide capture and storage (CCS) technology needs to contribute 14% of carbon dioxide emission reductions. If a lower warming rate is considered, with the energy sector needing to achieve net-zero emissions by 2060 and a warming rate of 1.75°C by the end of this century, CCS technology would need to contribute 32% of carbon dioxide emission reductions. Among these, carbon dioxide capture and storage (CCS) technology in coal-fired power plants is the most important research direction for greenhouse gas emission reduction by 2050. Currently, carbon dioxide capture processes in flue gas mainly rely on organic amine solvent systems. The principle of this process is that carbon dioxide reacts chemically with an amine solution to form unstable salts, which, upon heating, release carbon dioxide again. This process can effectively remove carbon dioxide, but organic amines have significant limitations in absorbing carbon dioxide, mainly due to high regeneration energy consumption and the potential decomposition of amines during regeneration, leading to the release of toxic substances. Therefore, it is essential to develop a more energy-efficient, effective, and safe method for capturing carbon dioxide from flue gas.
[0003] Compared to carbon dioxide absorption technology using organic amine solution systems, carbon dioxide adsorption and separation technology via physical adsorption offers significant advantages, including low regeneration energy consumption, high selectivity, and low equipment investment. The core challenge of this technology lies in the development of low-cost, high-efficiency porous adsorbents. Hydrogen-bonded organic frameworks (HOFs) are a class of crystalline porous materials formed through self-assembly via complementary intermolecular hydrogen bonding. Currently, HOF materials are developing rapidly. Besides their framework structure characteristics and high specific surface area similar to MOFs and COFs, HOFs possess flexible and reversible hydrogen bonding, endowing them with unique properties such as easy purification, high crystallinity, solution processability, and self-healing properties, making them highly promising for gas adsorption and separation. Although some HOFs have been reported for selectively adsorbing carbon dioxide from flue gas, these HOF materials are structurally unstable due to relying solely on single hydrogen bonds, and most require long-term diffusion synthesis using organic solutions, resulting in high time costs and potential secondary environmental pollution from wastewater treatment. Summary of the Invention
[0004] The technical problem to be solved by this invention is to provide a hydrogen-bonded organic framework (HOF) material with high stability and green, pollution-free properties for capturing carbon dioxide in flue gas.
[0005] To solve the above technical problems, the present invention adopts the following technical solution: A hydrogen-bonded organic framework, the molecular formula of which is C 33 H 24 O 12 Named HIAM-103, it has a crystal structure and its crystal belongs to the triclinic P space group. 31c .
[0006] Preferably, the HIAM-103 is a porous material synthesized by hydrothermal method from 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzeneH6TMBTI.
[0007] Furthermore, in the crystal structure, each H6TMBTI building unit is connected to six adjacent structural units via hydrogen bonds; the bond angles and bond lengths of the OH…O bonds are 167.8° and 175.9°, respectively. Interconnected H6TMBTI units form an ACS topology network; four identical networks interweave to form a methyl-rich one-dimensional channel.
[0008] Furthermore, the three-dimensional crystal structure of HIAM-103 contains triangular one-dimensional channels, and the specific surface area of its pore structure is 578.8 cm². 2 / g, pore size distribution is concentrated in
[0009] The crystallographic parameters of the HIAM-103 are as follows:
[0010] This invention provides a preparation method for preparing the hydrogen-bonded organic framework described in the above embodiments, comprising the following steps: Step S1, preparing a reaction system: ultrasonically dispersing 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)benzene in a solvent to obtain a reaction system mixture; Step S2, performing a hydrothermal synthesis reaction: reacting the reaction system mixture at a predetermined reaction temperature for a predetermined time to obtain a mixture containing HAIM-103; Step S3, filtering and washing to obtain HAIM-103 crystalline powder.
[0011] In some embodiments, the solvent is water or formic acid; the reaction temperature is 120–180°C.
[0012] Furthermore, the preparation method further includes: Step S4, activating HAIM-103 crystals to obtain adsorbent material; Step S is to activate the crystals to activated HAIM-103 crystal material in a dynamic vacuum at an activation temperature of 60-100℃, which is used as an adsorbent.
[0013] This invention provides an adsorbent, which is the hydrogen-bonded organic framework described in the above embodiments, and uses a physical adsorption method to selectively capture carbon dioxide from flue gas, thereby purifying the flue gas.
[0014] In some embodiments, the adsorption temperature of the physical adsorption method is 0–50°C, the adsorption pressure is 0–2 bar, the desorption temperature is 60–120°C, and the desorption pressure is 0.005–1.0 bar; the physical adsorption method employs a fixed bed.
[0015] The beneficial effects of this invention are: This invention synthesizes a highly stable porous HOF material with multiple interpenetrating structures through a simple hydrothermal synthesis technique, and selectively captures carbon dioxide from the binary mixture of flue gas (CO2 / N2) by physical adsorption, thereby purifying the flue gas and contributing to the achievement of the "dual carbon" target. Attached Figure Description
[0016] Figure 1 shows the coordination diagram of different building units of the hydrogen-bonded organic framework (HOF) material HAIM-103 of the present invention, wherein (a) shows the coordination environment of HAIM-103 and (b) shows a schematic diagram of the structure of HAIM-103.
[0017] Figure 2 is an X-ray diffraction pattern of the HAIM-103 material obtained in Example 1 of the present invention. As can be seen from Figure 2, the powder X-ray diffraction of the synthesized sample is consistent with the simulation pattern, which proves that the synthesized HAIM-103 sample has high purity and that activation and testing have no significant impact on the structure of HAIM-103 material.
[0018] Figure 3 shows the N2 adsorption-desorption isotherm of the HAIM-103 material obtained in Embodiment 1 of the present invention at 77 K. As can be seen from Figure 3, the HAIM-103 material is a microporous material.
[0019] Figure 4 shows the adsorption isotherms of HAIM-103 material synthesized in Example 1 of the present invention as an adsorbent for carbon dioxide and nitrogen under room temperature conditions. As can be seen from Figure 4, HAIM-103 material shows that the adsorption capacity of carbon dioxide is much higher than that of nitrogen, proving that HAIM-103 material preferentially adsorbs carbon dioxide.
[0020] Figure 5 shows the selectivity of the HAIM-103 material synthesized in Example 1 of this invention to carbon dioxide and nitrogen. As can be seen from Figure 5, the selectivity of carbon dioxide to nitrogen at 1 bar is close to 50, proving that HIAM-103 has excellent selectivity for carbon dioxide / nitrogen.
[0021] Figure 6 shows the dynamic breakthrough curves of the HAIM-103 material synthesized in Examples 1 and 2 of this invention as an adsorbent. As can be seen from Figure 6, under dry and 50% RH conditions, nitrogen gas passes through the adsorption column before carbon dioxide gas. Carbon dioxide gas is detected only after a period of time, which proves that the HAIM-103 material can selectively adsorb carbon dioxide under dry and humid conditions, thereby purifying flue gas.
[0022] Figure 7 shows the cyclic dynamic breakthrough curve of the HAIM-103 material obtained in Example 2 as an adsorbent. As can be seen from Figure 7, the synthesized HAIM-103 material maintained good carbon dioxide capture performance in multiple cycles at 50% RH, demonstrating the cyclic stability of the HAIM-103 material and its carbon dioxide capture ability under long-term humidity conditions. Detailed Implementation
[0023] Exemplary embodiments of this application will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of this application are shown in the drawings, it should be understood that this application may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of this application and to fully convey the scope of this application to those skilled in the art.
[0024] It should be understood that the terminology used herein is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “described” as used herein may also include the plural forms. The terms “comprising,” “including,” “containing,” and “having” are inclusive and therefore indicate the presence of the stated features, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein are not construed as requiring them to be performed in a particular order described or illustrated unless the order of performance is explicitly indicated. It should also be understood that additional or alternative steps may be used.
[0025] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are commercially available unless otherwise specified.
[0026] The endpoints and any values disclosed in this invention are not limited to the precise range or value, and such ranges or values should be understood to include values close to such ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0027] This invention synthesizes a highly stable hydrogen-bonded porous material HOF using low-cost 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene (H6TMBTI) as a raw material via a simple and rapid hydrothermal method. The molecular formula is: C 33 H 24 O 12 The material was named HIAM-103 (HIAM: Hoffman institution of advanced material). Its reaction principle involves the ultrasonic dispersion of the H6TMBTI organic ligand in solution, followed by molecular self-assembly at high temperatures to form a rod-shaped hydrogen-bonded organic framework material (HIAM-103) with one-dimensional channels. The crystal structure of HIAM-103 was determined by X-ray single-crystal diffraction, and its space group is triclinic P. 31c In the crystal structure, each H6TMBTI building unit is connected to six adjacent building units by 12 hydrogen bonds. The bond angles and bond lengths of the OH…O hydrogen bonds are 167.8° and 175.9°, respectively. Interconnected H6TMBTI units form an ACS topology network. Four identical networks interweave to form methyl-rich one-dimensional channels, with a channel diameter of approximately [missing information].
[0028] The hydrogen-bonded organic framework (HOF) material HAIM-103 of this invention has different building units, as shown in Figure 1. The coordination environment is shown in Figure (a), and the structural schematic is shown in Figure (b). The crystal structure of HAIM-103 was obtained by X-ray single-crystal diffraction. Figure (a) shows the specific coordination mode between different atoms; each H6TMBTI building unit is connected to its neighboring building units through hydrogen bonds. Figure (b) shows the three-dimensional crystal structure of HAIM-103, which exhibits distinct triangular one-dimensional channels. Nitrogen adsorption tests at 77 K showed that its specific surface area is 578.8 cm². 2 / g, pore size distribution is mainly concentrated in
[0029] Table 1 below shows the crystallographic parameters of the hydrogen-bonded organic framework (HOF) material of this invention: Table 1 Crystallographic Parameters
[0030] The hydrogen-bonded porous material HOF (HIAM-103) compound of this invention provides a suitable pore size and pore chemical environment for carbon dioxide molecule adsorption, enabling it to generate strong interactions with carbon dioxide. The abundant -CH3 functional groups in the pores resist the erosion of the structure by water molecules, thereby achieving complete capture of carbon dioxide from the binary mixture of flue gas and realizing one-step purification of flue gas. This invention synthesizes a highly stable porous HOF material with a multi-interpenetrating structure through a simple hydrothermal synthesis technique. It is suitable for selectively capturing carbon dioxide from the binary mixture of flue gas (CO2 / N2) through physical adsorption, achieving flue gas purification and contributing to the realization of the "dual carbon" target.
[0031] In a first aspect, the present invention provides a hydrogen-bonded porous material HOF (HIAM-103), with the molecular formula: C 33 H 24 O 12 This compound is a hydrogen-bonded organic framework material generated by the hydrothermal reaction of 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene (H6TMBTI).
[0032] Secondly, the method for preparing the hydrogen-bonded porous material HOF (HIAM-103) of the present invention comprises the following specific reaction steps: Step S1, preparing the reaction system: 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)benzene is ultrasonically dispersed in a certain amount of solvent, and then the mixture of the reaction system is transferred to a reaction vessel (e.g., a stainless steel reaction vessel lined with Teflon); Step S2, performing a hydrothermal synthesis reaction: the reaction vessel is placed in an oven and reacted at a predetermined reaction temperature for a predetermined time to obtain a mixture containing HOF; Step S3, filtration and washing: the mixture containing HOF is filtered to obtain HOF yellow powder, and washed with water three times (not limited to three times) to obtain HOF crystal powder; Step S4, activating the HOF crystals to obtain an adsorbent material: the crystals are activated in a dynamic vacuum at a predetermined activation temperature for 2 hours (not limited to 2 hours) to obtain activated HOF crystal material that can be used as an adsorbent.
[0033] Among them, the only reactant material mentioned above is 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene.
[0034] Ultrasonic dispersion can be performed at room temperature for about ten minutes. Conventional ultrasonic dispersion can be used to ensure that the raw material reactants are uniformly dispersed in the solvent.
[0035] Preferably, the solvent is water or formic acid; more preferably, the solvent is water.
[0036] Preferably, the ratio of reactant 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene to solvent is 3 to 8 mL of solvent for every 1 mmol of 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene; more preferably, the amount of solvent added is 5 mL for every 1 mmol of H6TMBTI.
[0037] Preferably, the reaction temperature is 120–180°C; more preferably, the reaction temperature is 150°C.
[0038] Preferably, the activation temperature of the above-mentioned crystal powder is 60-100°C, and more preferably, the activation temperature is 80°C.
[0039] Thirdly, the present invention also provides a method for selectively adsorbing carbon dioxide in flue gas using the above-mentioned HOF as an adsorbent, thereby achieving one-step purification of flue gas.
[0040] As one embodiment, flue gas (e.g., a binary mixture of simulated carbon dioxide and nitrogen) is passed through a synthesized HIAM-103 adsorbent, which selectively adsorbs carbon dioxide from the mixture, thus achieving carbon dioxide capture in the flue gas.
[0041] The gas can be adsorbed using one or more of the following methods: pressure swing adsorption (PSA), temperature swing adsorption (TSA), or low-pressure adsorption-desorption with a fixed bed. At a set adsorption temperature and pressure, the mixed gas is introduced into a fixed bed packed with HIAM-103 adsorbent at a set flow rate. Nitrogen preferentially permeates the bed, while carbon dioxide is enriched within the adsorption bed. After carbon dioxide permeates, the bed is regenerated through desorption, and the next cycle begins.
[0042] Preferably, the adsorption temperature is 0–50°C and the adsorption pressure is 0–2 bar; the desorption temperature is 60–120°C and the desorption pressure is 0.005–1.0 bar.
[0043] Example 1: In this example, 0.1 mmol of 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)benzene was ultrasonically dispersed in 5 mL of H2O. The mixture was then transferred to a Teflon-lined reactor and placed in an oven at 150°C for 2 days. The product HIAM-103 was obtained by filtration; then washed five times with water, and the resulting HIAM-103 crystalline powder was vacuum dried at 60°C for 2 hours to obtain the activated adsorbent.
[0044] Figure 2 shows the X-ray diffraction pattern of the HIAM-103 material obtained in Example 1. As can be seen from Figure 2, the X-ray diffraction pattern of the synthesized HIAM-103 powder is consistent with the simulation pattern, which proves that the synthesized HIAM-103 has high purity and no significant impact on the material structure after activation and testing.
[0045] Figure 3 shows the N2 adsorption-desorption isotherm of the HIAM-103 material obtained in Example 1 at 77 K. As can be seen from Figure 3, the HIAM-103 material is a microporous material.
[0046] Figure 4 shows the adsorption isotherms of carbon dioxide and nitrogen gas of the HIAM-103 material synthesized in Example 1 at room temperature. As can be seen from Figure 4, the HIAM-103 material exhibits a much higher adsorption capacity for carbon dioxide than for nitrogen gas, proving that the material preferentially adsorbs carbon dioxide.
[0047] Figure 5 shows the selectivity of the HIAM-103 material synthesized in Example 1 for carbon dioxide and nitrogen. As can be seen from Figure 5, the selectivity of carbon dioxide to nitrogen at 1 bar is close to 50, proving that the HIAM-103 material has excellent selectivity for carbon dioxide / nitrogen.
[0048] Figure 6 shows the dynamic penetration curves of the HIAM-103 material obtained in Example 1 and Example 2 below. As can be seen from Figure 6, under dry and 50% RH conditions, nitrogen gas passes through the adsorption column before carbon dioxide gas. Carbon dioxide gas is detected only after a period of time, which proves that the HIAM-103 material can selectively adsorb carbon dioxide under dry and humid conditions, thereby purifying flue gas.
[0049] Example 2: In this example, 0.1 mmol of 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)benzene was ultrasonically dispersed in 5 mL of formic acid. The mixture was then transferred to a Teflon-lined reactor and placed in an oven at 150°C for 2 days. The product HIAM-103 was obtained by filtration; then washed five times with formic acid. The resulting HIAM-103 crystalline powder was vacuum dried at 60°C for 2 hours to obtain the activated adsorbent.
[0050] Figure 7 shows the cyclic dynamic breakthrough curve of the HIAM-103 material obtained in Example 2 as an adsorbent. As can be seen from the figure, the synthesized HIAM-103 material maintains good carbon dioxide capture performance in multiple cycles at 50% RH, demonstrating the cyclic stability of the HIAM-103 material and its excellent carbon dioxide capture ability under long-term humidity conditions.
[0051] Example 3: In this example, 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzene (1 mmol) was ultrasonically dispersed in formic acid (10 mL). The mixture was then transferred to a Teflon-lined reactor and placed in an oven at 180°C for 2 days. The product HIAM-103 was obtained by filtration. The product was then washed five times with formic acid. The resulting HIAM-103 crystal powder was vacuum dried at 60°C for 2 hours to obtain the activated adsorbent.
[0052] Application Example 1
[0053] In this embodiment, the HIAM-103 material obtained in Example 3 was used as an adsorbent and loaded into a fixed-bed adsorption column (5 mm inner diameter, 2 ml volume). At 25°C and a back pressure of 1 bar, a two-component gas mixture of carbon dioxide and nitrogen (molar ratio 15 / 85) was passed through the adsorption column at a flow rate of 4.0 mL / min. High-purity nitrogen (>99%) was detected at the end of the adsorption column. Adsorption was stopped after complete carbon dioxide penetration. The adsorption column was then purged with helium at 120°C to achieve cyclic regeneration. Alternatively, desorption regeneration could be performed at room temperature using a vacuum pump with a vacuum level of 0.05 bar.
[0054] Application Example 2
[0055] In this embodiment, the HIAM-103 material obtained in Example 3 was used as an adsorbent and loaded into a fixed-bed adsorption column (5 mm inner diameter, 2 ml volume). At 25°C and a back pressure of 1 bar, a two-component gas mixture of carbon dioxide and nitrogen (molar ratio 15 / 85) was passed through a steam generator at a flow rate of 4.0 mL / min, ensuring a gas humidity of 50% RH. The gas then flowed through the adsorption column, and high-purity nitrogen (>99%) was detected at the end of the column. Adsorption stopped after complete carbon dioxide penetration. The adsorption column was then purged with helium at 120°C to achieve cyclic regeneration. Alternatively, desorption regeneration could be performed at room temperature using a vacuum pump with a vacuum level of 0.05 bar.
[0056] This invention synthesizes a novel compound, HIAM-103, and utilizes this compound to preferentially adsorb carbon dioxide from a binary mixture of flue gas, thereby achieving flue gas purification capabilities. It is expected to replace the current energy-intensive organic amine-solution carbon dioxide absorption process used in industry and has great application potential in the field of carbon capture in industrial flue gas.
[0057] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A hydrogen-bonded organic framework having a molecular formula of C 33 H 24 O 12 , designated as HIAM-103, having a crystal structure with a crystal in a space group of P 31c .
2. The hydrogen-bonding organic framework of claim 1, wherein: The HIAM-103 is a porous material synthesized by hydrothermal method from 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)]benzeneH6TMBTI.
3. The hydrogen-bonding organic framework of claim 2, wherein: In the crystal structure, each H6TMBTI building unit is connected to six neighboring units through one hydrogen bond; the O-H…O bond angle and bond length in the hydrogen bond are 167.8 / 175.9° and The interconnected H6TMBTI units form acs topological networks; four identical networks interpenetrate to form one-dimensional channels rich in methyl groups.
4. The hydrogen-bonding organic framework of claim 3, wherein: The H IAM- 103 has a one-dimensional channel with a triangular shape in the three-dimensional crystal structure, and the specific surface area of the pore structure is 578.8 cm 2 / g, and the pore size distribution is concentrated in The crystallographic parameters of the H IAM-103 are as follows:
5. The hydrogen-bonding organic framework of claim 1, wherein: The coordination environment of the crystal structure of HAIM-103 is: The crystal structure of HAIM-103 is:
6. A preparation method for preparing the hydrogen-bonded organic framework according to any one of claims 1 to 5, comprising the following steps: Step S1, Preparation of the reaction system: 1,3,5-trimethyl-2,4,6-tris(3',5'-dicarboxyphenyl)benzene is ultrasonically dispersed in a solvent to obtain a mixture of reaction systems; Step S2, hydrothermal synthesis reaction: The reaction system mixture is reacted at a predetermined reaction temperature for a predetermined time to obtain a mixture containing HAIM-103; Step S3: Filter and wash to obtain HAIM-103 crystal powder.
7. The production method according to claim 6, characterized by: The solvent is water or formic acid; the reaction temperature is 120–180°C.
8. The production method according to claim 6, characterized by: The preparation method further includes: Step S4: Activate HAIM-103 crystals to obtain adsorbent material; Step S involves activating the crystal in a dynamic vacuum at an activation temperature of 60–100°C to obtain activated HAIM-103 crystal material, which is then used as an adsorbent.
9. An adsorbent, which is a hydrogen-bonded organic framework as described in any one of claims 1 to 5, selectively captures carbon dioxide from flue gas using a physical adsorption method to purify the flue gas.
10. The adsorbent of claim 9, wherein: The adsorption temperature of the physical adsorption method is 0–50℃, and the adsorption pressure is 0–2 bar; the desorption temperature is 60–120℃, and the desorption pressure is 0.005–1.0 bar; the physical adsorption method uses a fixed bed.