CN115975139A - For CO 2 Preparation method and application of desorbed covalent organic framework material - Google Patents
For CO 2 Preparation method and application of desorbed covalent organic framework material Download PDFInfo
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- CN115975139A CN115975139A CN202211548694.3A CN202211548694A CN115975139A CN 115975139 A CN115975139 A CN 115975139A CN 202211548694 A CN202211548694 A CN 202211548694A CN 115975139 A CN115975139 A CN 115975139A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention discloses a method for preparing CO 2 A method for preparing a desorbed covalent organic framework material comprising the steps of: (1) Mixing 1,3,5-tris (4-aminophenyl) benzene and terephthalaldehyde into dimethyl sulfoxide to obtain homogeneous liquid A serving as a reactant precursor solution; (2) Immersing the nickel ferrite nanocrystals into the homogeneous solution A and uniformly dispersing to obtain a turbid solution B; (3) Slowly dropwise adding glacial acetic acid with the purity of 99% into the turbid liquid B to obtain a suspension C; (4) Continuously placing the suspension C at room temperature for reacting for 0.5-1.5 hours to obtain a brown colloidal suspension after full reaction; (5) Adding an organic solvent into the suspension C, washing for 4-8 times in a centrifugal mode, and removing residual impurities in the brown colloid to obtain a brown colloid product D; (6) Placing the brown colloid product D in vacuum for dryingDrying in a box for 12-24 hours to obtain deep yellow CO desorption catalyst with nickel and iron double metal ion modified covalent organic framework 2 I.e. Ni/Fe-COF.
Description
The technical field is as follows:
the invention belongs to the field of organic amine solution CO desorption 2 In particular to a material for CO 2 A preparation method and application of the desorbed covalent organic framework material.
Background art:
the organic amine absorption method is currently recognized as a relatively mature post-combustion carbon dioxide (CO) 2 ) The trapping method has the advantages that the corresponding trapping engineering is applied to large-scale power plants at home and abroad, has higher decarburization efficiency and absorption selectivity, and can capture 75-95% of CO in the flue gas of the power plants 2 Amount (v). China CO 2 The unit carbon capture cost in the capture demonstration project is about 300 yuan/ton, however, the total capture energy consumption of the capture demonstration project accounts for about 30 percent of the energy consumption of a power plant, except for a small part for capturing CO 2 In addition to the increased energy consumption of impurity removal, separation, concentration, waste disposal and the like in the process, most of the energy is consumed by the regeneration link of the organic amine absorbent, because the CO absorbed by the organic amine solution is generally absorbed by the organic amine absorbent in a heating mode during regeneration of the organic amine absorbent 2 Desorbing, controlling the regeneration temperature at 120-170 deg.c, and consuming great amount of heat energy for the evaporation of water in the solution. Therefore, the method for reducing regeneration energy consumption is widely applied to the organic amine solution absorption method and needs to be understood urgentlySolving the key difficult problem.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
The invention content is as follows:
the invention aims to provide a method for preparing CO 2 A method for preparing a desorbed covalent organic framework material and its use, thereby overcoming the above-mentioned deficiencies of the prior art.
In order to achieve the above object, the present invention provides a method for CO 2 A method for preparing a desorbed covalent organic framework material, comprising the steps of:
(1) Mixing 1,3,5-tris (4-aminophenyl) benzene and terephthalaldehyde into dimethyl sulfoxide to obtain homogeneous liquid A serving as a reactant precursor solution;
(2) Immersing the nickel ferrite nanocrystals into the homogeneous solution A and uniformly dispersing to obtain a turbid solution B;
(3) Slowly dropwise adding glacial acetic acid with the purity of 99% into the turbid liquid B to obtain a suspension C;
(4) Continuously placing the suspension C at room temperature for reacting for 0.5-1.5 hours to obtain a brown colloidal suspension after full reaction;
(5) Adding an organic solvent into the suspension C, washing for 4-8 times in a centrifugal mode, and removing residual impurities in the brown colloid to obtain a brown colloid product D;
(6) Placing the brown colloid product D in a vacuum drying oven for drying for 12-24 hours to obtain deep yellow CO which is catalyzed and desorbed by a nickel and iron double-metal ion modified covalent organic framework 2 I.e., ni/Fe-COF.
Further, preferably, the ratio of the amounts of 1,3,5-tris (4-aminophenyl) benzene to terephthalaldehyde in the step (1) is n1: n2 is 1:1-1:2.
Further, preferably, the particle size of the nickel ferrite nanocrystals in the step (2) is 3 to 30nm.
Further, preferably, the nickel ferrite nanocrystals obtained in step (2) are immersed in the homogeneous solution a and then vibrated by an ultrasonic oscillator until being uniformly dispersed.
Further, preferably, the glacial acetic acid added in the step (3) accounts for 5-10% of the volume of the dimethyl sulfoxide added in the step (1).
Further, in the step (5), preferably, tetrahydrofuran with a purity of 99% and methanol with a purity of 99% are used as the organic solvent, and tetrahydrofuran and methanol are alternately used in washing.
Further, preferably, the drying temperature in the step (6) is 60 to 80 ℃.
Use according to any one of claims 1-7 for CO 2 Desorption of CO from desorbed covalent organic framework materials in organic amine solutions 2 Application in the field of application.
Compared with the prior art, one aspect of the invention has the following beneficial effects:
the invention is used as a catalyst for desorbing CO in an organic amine solution 2 The desorption temperature can be reduced to about 95 ℃ in the application, and the requirement of desorbing CO can be met 2 The requirement of (3) can also reduce the evaporation of water, can reduce the heat consumption in the regeneration link as a whole, and plays a role in energy conservation and environmental protection.
The specific implementation mode is as follows:
the following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
The following presents a simplified summary of one or more aspects in order to provide a basic understanding of such aspects. This summary is not an extensive overview of all contemplated aspects, and is intended to neither identify key or critical elements of all aspects nor delineate the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that is presented later.
Example 1:
for CO 2 A method for preparing a desorbed covalent organic framework material, comprising the steps of:
(1) Taking a certain amount of 1,3,5-tri (4-aminophenyl) benzene and terephthalaldehyde, wherein the mass ratio of the 1,3,5-tri (4-aminophenyl) benzene to the terephthalaldehyde is 1:1.5, adding the two into 200ml of dimethyl sulfoxide, and uniformly mixing to obtain a homogeneous solution A, wherein the homogeneous solution is used as a reactant precursor solution;
(2) Taking a certain amount of nickel ferrite (NiFe) with crystal grain diameter of 10-20nm 2 O 4 ) Adding the nano crystal into the homogeneous solution A, and performing ultrasonic dispersion to obtain a turbid solution B, wherein nickel ferrite (NiFe) 2 O 4 ) The ratio of the amount of material of nanocrystals to 1,3,5-tris (4-aminophenyl) benzene was 2:1;
(3) Slowly dripping 15ml of glacial acetic acid with the purity of 99% into the turbid liquid B under the shaking condition, and continuing shaking for 5min after dripping is finished to obtain a suspension C;
(4) Placing the suspension C at room temperature of 25 ℃ for reacting for 1h to obtain brown colloidal suspension;
(5) Washing the suspension C by using tetrahydrofuran with the purity of 99% and methanol with the purity of 99% in sequence, removing impurities in the suspension C to obtain a brown colloid product D, washing by adopting a centrifugal mode of a centrifugal machine during washing, and washing the tetrahydrofuran and the methanol for 4 times respectively;
(6) Drying the brown colloid product D in a vacuum drying oven for 12-24 hours to obtain dark yellow CO desorption catalyst with a nickel and iron double metal ion modified covalent organic framework 2 I.e. Ni/Fe-COF.
The prepared Ni/Fe-COF is applied to an organic amine solution to desorb CO 2 The specific application mode in the field of (1) is as follows:
s1: under normal pressure, CO 2 Continuously introducing the mixture into a reactor filled with 30wt% ethanolamine (MEA) solution at a certain flow rate in a bubbling manner to enable the mixture to reach an absorption saturation state, and obtaining CO 2 Absorbing the saturated MEA solution (also called pregnant solution);
s2: ni/Fe-COF as a catalyst was charged into a reactor, and residual CO in the reactor was replaced using nitrogen as a replacement gas and a carrier gas 2 A gas;
s3: by using infrared CO 2 Analyzer (measuring CO) 2 Of gasesInstrument) for gradually raising the temperature of the reactor to 90 ℃ and keeping the temperature stable, adopting electric heating for raising the temperature, measuring the power consumption by an electric meter, and recording the CO in the gas flow at the outlet of the reactor once every 1 minute 2 Calculating the desorption rate by combining the concentration with the curve of the outlet CO2 concentration changing along with time, see the formulas (1) and (2);
in the formula:
-reactor Outlet CO 2 Amount of substance (molar amount), mmol;
r-desorption rate, mmol/min;
t-time, min;
x-, CO at the outlet of the reactor 2 Volume percent,%;
V M ——22.4(L/mol)；
s4: CO per unit volume generated during regeneration of ethanolamine (MEA) solutions 2 The required energy is represented by the desorption heat load and its relative desorption heat load, calculated in conjunction with the kilowatt-hour meter record, see equations (3) and (4);
in the formula: h i Desorption Heat load (when using regenerated catalyst), kJ/mol
H o Desorption Heat load without regenerated catalyst, kJ/mol
wt-electric energy consumed for desorbing CO2, J.
Example 2:
unlike example 1, in S3, the reactor temperature was gradually increased to 95 ℃ and kept stable, the temperature was increased by electric heating, and the power consumption was measured by an electric meter.
Comparative example:
CO desorption of organic amine solution without Ni/Fe-COF catalyst in accordance with example 1 2 。
Example 1, example 2 and comparative example desorption of CO from a 30wt% saturated Ethanolamine (MEA) solution 2 The details of (A) are shown in the following table:
from the above test results, it can be seen that the saturated MEA rich solution releases CO at 90 deg.C desorption temperature 2 The relative desorption heat load is reduced by about 54 percent, and the energy consumption is greatly saved; at the desorption temperature of 95 ℃, CO is released from the saturated MEA rich solution 2 The relative desorption heat load is reduced by about 32 percent, the energy consumption is saved to a certain extent, and the desorption rate is obviously improved.
Experiments prove that the catalyst of the invention is used for desorbing CO in an organic amine solution 2 The desorption temperature can be reduced to about 95 ℃ in the traditional Chinese medicine application, and the desorption temperature can be reducedMeet the requirement of desorbing CO 2 The requirement of (3) can also reduce the evaporation of water, can reduce the heat consumption in the regeneration link as a whole, and plays a role in energy conservation and environmental protection.
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. For CO 2 A method for preparing a desorbed covalent organic framework material, comprising the steps of:
(1) Mixing 1,3,5-tris (4-aminophenyl) benzene and terephthalaldehyde into dimethyl sulfoxide to obtain homogeneous liquid A serving as a reactant precursor solution;
(2) Immersing the nickel ferrite nanocrystals into the homogeneous solution A and uniformly dispersing to obtain a turbid solution B;
(3) Slowly dropwise adding glacial acetic acid with the purity of 99% into the turbid liquid B to obtain a suspension C;
(4) Continuously placing the suspension C at room temperature for reacting for 0.5-1.5 hours to obtain a brown colloidal suspension after full reaction;
(5) Adding an organic solvent into the suspension C, washing for 4-8 times in a centrifugal mode, and removing residual impurities in the brown colloid to obtain a brown colloid product D;
(6) Drying the brown colloid product D in a vacuum drying oven for 12-24 hours to obtain dark yellow CO desorption catalyst with a nickel and iron double metal ion modified covalent organic framework 2 I.e., ni/Fe-COF.
2. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that the mass ratio of 1,3,5-tri (4-aminophenyl) benzene to terephthalaldehyde n1: n2 is 1:1-1:2.
3. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that the particle size of the nickel ferrite nano-crystal in the step (2) is 3-30nm.
4. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that the nickel ferrite nanocrystals obtained in the step (2) are immersed in the homogeneous solution A and then vibrated by an ultrasonic vibrator until being uniformly dispersed.
5. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that the volume of the glacial acetic acid added in the step (3) accounts for 5-10% of the volume of the dimethyl sulfoxide in the step (1).
6. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that in the step (5), tetrahydrofuran with the purity of 99% and methanol with the purity of 99% are adopted as organic solvents, and the tetrahydrofuran and the methanol are alternately used during washing.
7. A process for CO according to claim 1 2 The preparation method of the desorbed covalent organic framework material is characterized in that the drying temperature in the step (6) is 60-80 ℃.
8. Use according to any one of claims 1-7 for CO 2 Desorption of CO from desorbed covalent organic framework materials in organic amine solutions 2 Application in the field of application.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211548694.3A CN115975139A (en) | 2022-12-05 | 2022-12-05 | For CO 2 Preparation method and application of desorbed covalent organic framework material |
| PCT/CN2023/090321 WO2024119699A1 (en) | 2022-12-05 | 2023-04-24 | Preparation method for and use of covalent organic framework material for co2 desorption |
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| CN202211548694.3A CN115975139A (en) | 2022-12-05 | 2022-12-05 | For CO 2 Preparation method and application of desorbed covalent organic framework material |
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| CN115975139A true CN115975139A (en) | 2023-04-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024119699A1 (en) * | 2022-12-05 | 2024-06-13 | 苏州西热节能环保技术有限公司 | Preparation method for and use of covalent organic framework material for co2 desorption |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3077103B1 (en) * | 2013-12-02 | 2021-03-10 | University of Southern California | Regenerative adsorbents of modified amines on nano-structured supports |
| US20160030880A1 (en) * | 2014-07-30 | 2016-02-04 | William Marsh Rice University | Co2 capture with amines and acidic materials |
| EP3964279A1 (en) * | 2020-09-07 | 2022-03-09 | Indian Oil Corporation Limited | Solvent composition for co2 capture and a process mediated thereof |
| KR20220067591A (en) * | 2020-11-16 | 2022-05-25 | 한국에너지기술연구원 | Ion-exchanged regenerative catalyst for carbon dioxide capture |
| CN115975139A (en) * | 2022-12-05 | 2023-04-18 | 苏州西热节能环保技术有限公司 | For CO 2 Preparation method and application of desorbed covalent organic framework material |
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- 2022-12-05 CN CN202211548694.3A patent/CN115975139A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024119699A1 (en) * | 2022-12-05 | 2024-06-13 | 苏州西热节能环保技术有限公司 | Preparation method for and use of covalent organic framework material for co2 desorption |
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