WO2024119699A1 - Preparation method for and use of covalent organic framework material for co2 desorption - Google Patents
Preparation method for and use of covalent organic framework material for co2 desorption Download PDFInfo
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- WO2024119699A1 WO2024119699A1 PCT/CN2023/090321 CN2023090321W WO2024119699A1 WO 2024119699 A1 WO2024119699 A1 WO 2024119699A1 CN 2023090321 W CN2023090321 W CN 2023090321W WO 2024119699 A1 WO2024119699 A1 WO 2024119699A1
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- desorption
- framework material
- organic framework
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- 238000003795 desorption Methods 0.000 title claims abstract description 44
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002159 nanocrystal Substances 0.000 claims abstract description 9
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 6
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052742 iron Chemical group 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- the present application belongs to the technical field of material preparation for desorption of CO2 by organic amine solution, and in particular to a preparation method and application of a covalent organic framework material for desorption of CO2 .
- Organic amine absorption is currently recognized as a relatively mature post-combustion carbon dioxide (CO 2 ) capture method.
- the corresponding capture project has been applied to large power plants at home and abroad. It has high decarbonization efficiency and absorption selectivity, and can capture 75% to 95% of the CO 2 in the flue gas of power plants.
- the unit carbon capture cost in China's CO 2 capture demonstration project is about 300 yuan/ton, but its total capture energy consumption accounts for about 30% of the power plant's energy consumption. In addition to a small part of the energy consumption for impurity removal, separation, concentration, waste disposal, etc. in the process of capturing CO 2 , most of it is consumed by the regeneration of the organic amine absorbent.
- the organic amine absorbent generally uses a temperature-raising method to desorb the CO 2 absorbed by the organic amine solution during regeneration.
- the regeneration temperature is generally controlled at 120°C-170°C.
- the gasification and evaporation of water in the solution will also consume a lot of heat energy. Therefore, reducing the regeneration energy consumption is a key problem that needs to be solved for the widespread application of the organic amine solution absorption method.
- the purpose of the present application is to provide a preparation method and application of a covalent organic framework material for CO2 desorption, thereby overcoming the above-mentioned defects in the prior art.
- the present application provides a method for preparing a covalent organic framework material for CO2 desorption, comprising the following steps:
- the brown colloidal product D is placed in a vacuum drying oven and dried for 12-24 hours to obtain a dark yellow nickel and iron bimetallic ion modified covalent organic framework material for catalytic desorption of CO2 , namely Ni/Fe-COF.
- step (1) the molar ratio n1:n2 of 1,3,5-tri(4-aminophenyl)benzene to terephthalaldehyde is 1:1-1:2.
- the particle size of the nickel ferrite nanocrystals in step (2) is 3-30 nm.
- step (2) the nickel ferrite nanocrystals are immersed in the homogenous liquid A and then oscillated by an ultrasonic oscillator until they are evenly dispersed.
- the volume of glacial acetic acid added in step (3) accounts for 5%-10% of the volume of dimethyl sulfoxide in step (1).
- the organic solvents used are tetrahydrofuran with a purity of 99% and methanol with a purity of 99%, and tetrahydrofuran and methanol are used alternately during washing.
- the drying temperature in step (6) is 60-80°C.
- one aspect of the present application has the following beneficial effects:
- the application of the present invention as a catalyst in the desorption of CO2 from an amine solution can reduce the desorption temperature to about 95°C, which can not only meet the requirements for desorption of CO2 , but also reduce the evaporation of water. Overall, it can reduce the heat consumption in the regeneration process and play a role in energy conservation and environmental protection.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- a method for preparing a covalent organic framework material for CO2 desorption comprises the following steps:
- NiFe 2 O 4 nickel ferrite
- a turbid liquid B wherein the molar ratio of nickel ferrite (NiFe 2 O 4 ) nanocrystals to 1,3,5-tris(4-aminophenyl)benzene is 2:1;
- the brown colloidal product D is placed in a vacuum drying oven and dried for 12-24 hours to obtain a dark yellow nickel and iron bimetallic ion modified covalent organic framework material for catalytic desorption of CO2 , namely Ni/Fe-COF.
- the prepared Ni/Fe-COF is applied to the field of CO2 desorption by organic amine solution.
- the specific application methods are as follows:
- Ni/Fe-COF is put into the reactor as a catalyst, and nitrogen is used as a replacement gas and carrier gas to replace the residual CO2 gas in the reactor;
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- the temperature of the reactor is gradually increased to 95° C. and kept stable, the temperature is increased by electric heating, and the power consumption is measured by an electric meter.
- the CO 2 in the organic amine solution was desorbed according to the method of Example 1 without using the Ni/Fe-COF catalyst.
- Example 1 The specific conditions of desorption of CO 2 in 30 wt % saturated ethanolamine (MEA) solution in Example 1, Example 2 and Comparative Example are shown in the following table:
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- Polymers & Plastics (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Disclosed in the present application is a preparation method for a covalent organic framework material for CO2 desorption. The preparation method comprises the following steps: (1) mixing 1,3,5-tri(4-aminophenyl)benzene and terephthalaldehyde into dimethyl sulfoxide to obtain a homogeneous solution A as a reactant precursor solution; (2) immersing nickel ferrite nanocrystals in the homogeneous solution A, and uniformly dispersing same to obtain a turbid solution B; (3) slowly adding glacial acetic acid with a purity of 99% dropwise into the turbid solution B to obtain a suspension C; (4) continuously placing the suspension C at room temperature to react same for 0.5-1.5 hours, so as to obtain a brown colloidal suspension after full reaction; (5) adding an organic solvent to the suspension C, and washing same 4-8 times by using a centrifugal approach to remove residual impurities from the brown colloid, so as to obtain a brown colloid product D; and (6) placing the brown colloid product D in a vacuum drying oven and drying same for 12-24 hours, so as to obtain a deep yellow covalent organic framework material, which is modified with nickel and iron bimetal ions, for catalyzing CO2 desorption, namely Ni/Fe-COF.
Description
相关申请的交叉引用CROSS-REFERENCE TO RELATED APPLICATIONS
本申请要求在2022年12月5日提交中国专利局、申请号为202211548694.3、申请名称为“一种用于CO2解吸的共价有机框架材料的制备方法及应用”的中国专利申请的优先权，其全部内容通过引用的方式并入本文中。This application claims priority to a Chinese patent application filed with the Chinese Patent Office on December 5, 2022, with application number 202211548694.3 and application name “A preparation method and application of covalent organic framework materials for CO2 desorption”, the entire contents of which are incorporated herein by reference.
本申请属于有机胺溶液解吸CO2的材料制备技术领域，特别涉及一种用于CO2解吸的共价有机框架材料的制备方法及应用。The present application belongs to the technical field of material preparation for desorption of CO2 by organic amine solution, and in particular to a preparation method and application of a covalent organic framework material for desorption of CO2 .
有机胺吸收法是目前公认的相对成熟的燃烧后二氧化碳(CO2)捕集方法，相应捕集工程已应用于国内外的大型电厂，其具有较高的脱碳效率和吸收选择性，可以捕获电厂烟气中75％～95％的CO2量。我国CO2捕获示范项目中单位碳捕获成本约为300元/吨，然而其总捕集能耗约占电厂能耗30％左右，除了小部分用于实现捕获CO2过程中的杂质去除、分离、浓缩、废物处置等增加的耗能外，大部分被有机胺吸收剂再生环节所消耗，这是因为一般有机胺吸收剂再生时采用升温的方式将有机胺溶液吸收的CO2解吸出来，再生温度一般控制在120℃-170℃，除了有机胺自身的挥发，溶液中水的气化蒸发也会消耗大量的热能。因此，降低再生能耗，是有机胺溶液吸收法广泛应用亟需解决的关键难题。Organic amine absorption is currently recognized as a relatively mature post-combustion carbon dioxide (CO 2 ) capture method. The corresponding capture project has been applied to large power plants at home and abroad. It has high decarbonization efficiency and absorption selectivity, and can capture 75% to 95% of the CO 2 in the flue gas of power plants. The unit carbon capture cost in China's CO 2 capture demonstration project is about 300 yuan/ton, but its total capture energy consumption accounts for about 30% of the power plant's energy consumption. In addition to a small part of the energy consumption for impurity removal, separation, concentration, waste disposal, etc. in the process of capturing CO 2 , most of it is consumed by the regeneration of the organic amine absorbent. This is because the organic amine absorbent generally uses a temperature-raising method to desorb the CO 2 absorbed by the organic amine solution during regeneration. The regeneration temperature is generally controlled at 120℃-170℃. In addition to the volatilization of the organic amine itself, the gasification and evaporation of water in the solution will also consume a lot of heat energy. Therefore, reducing the regeneration energy consumption is a key problem that needs to be solved for the widespread application of the organic amine solution absorption method.
公开于该背景技术部分的信息仅仅旨在增加对本申请的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。The information disclosed in this background technology section is only intended to increase the understanding of the overall background of the application and should not be regarded as acknowledging or suggesting in any form that the information constitutes the prior art already known to a person skilled in the art.
发明内容Summary of the invention
本申请的目的在于提供一种用于CO2解吸的共价有机框架材料的制备方法及应用，从而克服上述现有技术中的缺陷。
The purpose of the present application is to provide a preparation method and application of a covalent organic framework material for CO2 desorption, thereby overcoming the above-mentioned defects in the prior art.
为了实现上述目的，本申请提供了一种用于CO2解吸的共价有机框架材料的制备方法，包括以下步骤：In order to achieve the above object, the present application provides a method for preparing a covalent organic framework material for CO2 desorption, comprising the following steps:
(1)将1,3,5-三(4-氨基苯基)苯与对苯二甲醛混合到二甲基亚砜中，得到均质液A，作为反应物前驱体溶液；(1) mixing 1,3,5-tri(4-aminophenyl)benzene and terephthalaldehyde in dimethyl sulfoxide to obtain a homogeneous solution A as a reactant precursor solution;
(2)将铁酸镍纳米晶体浸入到均质液A中并分散均匀，得到浑浊液B；(2) immersing nickel ferrite nanocrystals into homogeneous liquid A and dispersing them evenly to obtain turbid liquid B;
(3)将纯度为99％的冰乙酸缓慢滴加到浑浊液B中，得到悬浮液C；(3) slowly adding 99% pure glacial acetic acid dropwise to the turbid liquid B to obtain a suspension C;
(4)将悬浮液C继续置于室温条件下反应0.5-1.5小时，得到充分反应后的棕色胶体悬浮液；(4) the suspension C is allowed to react for 0.5-1.5 hours at room temperature to obtain a fully reacted brown colloidal suspension;
(5)往悬浮液C中加入有机溶剂后采用离心的方式洗涤4-8次，去除棕色胶体中残留的杂质，得到棕色胶体产物D；(5) adding an organic solvent to the suspension C and washing the suspension C by centrifugation for 4-8 times to remove impurities remaining in the brown colloid to obtain a brown colloid product D;
(6)将棕色胶体产物D置于真空干燥箱中干燥12-24小时，得到深黄色的镍与铁双金属离子修饰共价有机框架催化解吸CO2的材料，即Ni/Fe-COF。(6) The brown colloidal product D is placed in a vacuum drying oven and dried for 12-24 hours to obtain a dark yellow nickel and iron bimetallic ion modified covalent organic framework material for catalytic desorption of CO2 , namely Ni/Fe-COF.
可选地，所述步骤(1)中1,3,5-三(4-氨基苯基)苯与对苯二甲醛的物质的量之比n1：n2为1:1-1:2。Optionally, in step (1), the molar ratio n1:n2 of 1,3,5-tri(4-aminophenyl)benzene to terephthalaldehyde is 1:1-1:2.
可选地，所述步骤(2)中铁酸镍纳米晶体的粒径为3-30nm。Optionally, the particle size of the nickel ferrite nanocrystals in step (2) is 3-30 nm.
可选地，所述步骤(2)铁酸镍纳米晶体浸入到均质液A中后采用超声波震荡器震荡至分散均匀。Optionally, in step (2), the nickel ferrite nanocrystals are immersed in the homogenous liquid A and then oscillated by an ultrasonic oscillator until they are evenly dispersed.
可选地，所述步骤(3)中冰乙酸加入的体积量占步骤(1)中二甲基亚砜体积的5％-10％。Optionally, the volume of glacial acetic acid added in step (3) accounts for 5%-10% of the volume of dimethyl sulfoxide in step (1).
可选地，所述步骤(5)中有机溶剂采用纯度为99％的四氢呋喃和纯度为99％的甲醇，洗涤时四氢呋喃和甲醇交替使用。Optionally, in step (5), the organic solvents used are tetrahydrofuran with a purity of 99% and methanol with a purity of 99%, and tetrahydrofuran and methanol are used alternately during washing.
可选地，所述步骤(6)中干燥温度为60-80℃。Optionally, the drying temperature in step (6) is 60-80°C.
一种根据权利要求1-7中任一项所述的用于CO2解吸的共价有机框架材料在有机胺溶液解吸CO2领域的应用。A use of the covalent organic framework material for CO2 desorption according to any one of claims 1 to 7 in the field of CO2 desorption from organic amine solutions.
与现有技术相比，本申请的一个方面具有如下有益效果：Compared with the prior art, one aspect of the present application has the following beneficial effects:
本申请作为催化剂在机胺溶液解吸CO2中应用可将解吸温度降低到95℃左右，既能满足解吸CO2的要求，又能降低水分的蒸发，整体上可降低再生环节中热量的消耗，起到节能环保的作用。The application of the present invention as a catalyst in the desorption of CO2 from an amine solution can reduce the desorption temperature to about 95°C, which can not only meet the requirements for desorption of CO2 , but also reduce the evaporation of water. Overall, it can reduce the heat consumption in the regeneration process and play a role in energy conservation and environmental protection.
下面对本申请的具体实施方式进行详细描述，但应当理解本申请的保护范围并不受具体实施方式的限制。The specific implementation methods of the present application are described in detail below, but it should be understood that the protection scope of the present application is not limited by the specific implementation methods.
以下给出一个或多个方面的简要概述以提供对这些方面的基本理解。此概述不是所有构想到的方面的详尽综览，并且既非旨在指认出所有方面的关键性或决定性要素亦非试图界定任何或所有方面的范围。其唯一的目的是要以简化形式给出一个或多个方面的一些概念以为稍后给出的更加详细的描述之序。A brief summary of one or more aspects is given below to provide a basic understanding of these aspects. This summary is not an exhaustive overview of all conceived aspects, and is neither intended to identify the key or critical elements of all aspects nor to define the scope of any or all aspects. Its only purpose is to give some concepts of one or more aspects in a simplified form as a prelude to a more detailed description that will be given later.
实施例1：Embodiment 1:
一种用于CO2解吸的共价有机框架材料的制备方法，包括以下步骤：A method for preparing a covalent organic framework material for CO2 desorption comprises the following steps:
(1)取一定量的1,3,5-三(4-氨基苯基)苯与和对苯二甲醛，两者的物质的量之比为1：1.5，将两者加入到200ml的二甲亚砜中混合均匀，得到均质液A，该均质液作为反应物前驱体溶液；(1) taking a certain amount of 1,3,5-tri(4-aminophenyl)benzene and terephthalaldehyde, the molar ratio of the two being 1:1.5, adding the two into 200 ml of dimethyl sulfoxide and mixing them evenly to obtain a homogeneous solution A, which is used as a reactant precursor solution;
(2)取一定量的晶体粒径为10-20nm的铁酸镍(NiFe2O4)纳米晶体加入到均质液A中超声分散均匀，得到浑浊液B，其中铁酸镍(NiFe2O4)纳米晶体与1,3,5-三(4-氨基苯基)苯的物质的量之比为2：1；(2) taking a certain amount of nickel ferrite (NiFe 2 O 4 ) nanocrystals with a crystal particle size of 10-20 nm and adding them to the homogeneous liquid A for uniform ultrasonic dispersion to obtain a turbid liquid B, wherein the molar ratio of nickel ferrite (NiFe 2 O 4 ) nanocrystals to 1,3,5-tris(4-aminophenyl)benzene is 2:1;
(3)在震荡条件下取15ml纯度为99％的冰乙酸缓慢滴加到浑浊液B中，滴加完毕后，继续震荡5min，得到悬浮液C；(3) Slowly drop 15 ml of 99% pure glacial acetic acid into the turbid liquid B under shaking conditions. After the addition is complete, continue shaking for 5 min to obtain a suspension C.
(4)将悬浮液C置于25℃的室温条件下反应1h，得到棕色胶体悬浮液；(4) The suspension C was placed at room temperature of 25°C for 1 h to obtain a brown colloidal suspension;
(5)使用纯度为99％的四氢呋喃和纯度为99％的甲醇依次洗涤悬浮液C，去除悬浮液C中的杂质，得到棕色胶体产物D，洗涤时采用离心机离心的方式洗涤，四氢呋喃和甲醇各洗涤4次；(5) washing the suspension C with 99% purity tetrahydrofuran and 99% purity methanol in sequence to remove impurities in the suspension C and obtain a brown colloidal product D. The suspension C is washed by centrifugation, and the tetrahydrofuran and methanol are washed 4 times each.
(6)将棕色胶体产物D置于真空干燥箱中干燥12-24小时，得到深黄色的镍与铁双金属离子修饰共价有机框架催化解吸CO2的材料，即Ni/Fe-COF。(6) The brown colloidal product D is placed in a vacuum drying oven and dried for 12-24 hours to obtain a dark yellow nickel and iron bimetallic ion modified covalent organic framework material for catalytic desorption of CO2 , namely Ni/Fe-COF.
将制得的Ni/Fe-COF的应用到有机胺溶液解吸CO2的领域中，具体应用方式如下：The prepared Ni/Fe-COF is applied to the field of CO2 desorption by organic amine solution. The specific application methods are as follows:
S1：在常压条件下，CO2以一定流速持续通过鼓泡方式通入装有30wt％的乙醇胺(MEA)溶液的反应器中，使其达到吸收饱和状态，得到CO2吸收达到饱和的MEA溶液(也称富液)；S1: Under normal pressure, CO2 is continuously bubbled into a reactor containing 30 wt% ethanolamine (MEA) solution at a certain flow rate to achieve saturated absorption, thereby obtaining a MEA solution (also called rich solution) in which CO2 absorption is saturated;
S2：将Ni/Fe-COF作为催化剂投入到反应器中，并使用氮气作为置换气和载气，置换反应器中的残余CO2气体；S2: Ni/Fe-COF is put into the reactor as a catalyst, and nitrogen is used as a replacement gas and carrier gas to replace the residual CO2 gas in the reactor;
S3：采用红外CO2分析仪(测量CO2气体的仪器)，逐渐升高反应器温度至
90℃并保持稳定，升温采用电热，电耗由电度表计量，每1分钟记录一次反应器出口气流中的CO2浓度，结合出口CO2浓度随时间变化曲线，进行解吸速率计算，见式(1)和(2)；
S3: Using an infrared CO 2 analyzer (an instrument for measuring CO 2 gas), gradually increase the reactor temperature to 90℃ and keep it stable. The temperature is raised by electric heating. The power consumption is measured by the electric meter. The CO2 concentration in the reactor outlet gas flow is recorded every 1 minute. Combined with the outlet CO2 concentration change curve over time, the desorption rate is calculated, see equations (1) and (2);
S3: Using an infrared CO 2 analyzer (an instrument for measuring CO 2 gas), gradually increase the reactor temperature to 90℃ and keep it stable. The temperature is raised by electric heating. The power consumption is measured by the electric meter. The CO2 concentration in the reactor outlet gas flow is recorded every 1 minute. Combined with the outlet CO2 concentration change curve over time, the desorption rate is calculated, see equations (1) and (2);
式中——反应器出口CO2物质的量(摩尔量)，mmol；In the formula ——The amount of CO2 substance at the reactor outlet (molar amount), mmol;
r——解吸速率，mmol/min；r——desorption rate, mmol/min;
t——时间，min；t——time, min;
——N2载气的流量，mL/min； ——N2 carrier gas flow rate, mL/min;
x——，反应器出口CO2体积百分含量，％；x——, volume percentage of CO 2 at the reactor outlet, %;
VM——22.4(L/mol)；V M ——22.4 (L/mol);
S4：乙醇胺(MEA)溶液再生过程中产生的每单位体积CO2所需的能量由解吸热负荷及其相对解吸热负荷来表示，结合电度表记录来计算，见式(3)和(4)；
S4: The energy required per unit volume of CO 2 produced during the regeneration of ethanolamine (MEA) solution is represented by the desorption heat load and its relative desorption heat load, which is calculated in combination with the watt-hour meter records, see equations (3) and (4);
S4: The energy required per unit volume of CO 2 produced during the regeneration of ethanolamine (MEA) solution is represented by the desorption heat load and its relative desorption heat load, which is calculated in combination with the watt-hour meter records, see equations (3) and (4);
式中：Hi——解吸热负荷(使用再生催化剂时)，kJ/molWhere: Hi - desorption heat load (when using regenerated catalyst), kJ/mol
Ho——无再生催化剂时解吸热负荷，kJ/molH o ——Desorption heat load without regenerated catalyst, kJ/mol
——相对解吸热负荷， ——relative desorption heat load,
——反应器出口CO2物质的量，mmol； ——the amount of CO2 at the reactor outlet, mmol;
Wt——解吸CO2消耗的电能，J。Wt——Electric energy consumed in desorption of CO 2 , J.
实施例2：Embodiment 2:
与实施例1不同的是，S3中逐渐升高反应器温度至95℃并保持稳定，升温采用电热，电耗由电度表计量。Different from Example 1, in S3, the temperature of the reactor is gradually increased to 95° C. and kept stable, the temperature is increased by electric heating, and the power consumption is measured by an electric meter.
对比实施例：Comparative Example:
不使用Ni/Fe-COF催化剂，按照实施例1的方法解吸有机胺溶液中的CO2。
The CO 2 in the organic amine solution was desorbed according to the method of Example 1 without using the Ni/Fe-COF catalyst.
实施例1、实施例2和对比实施例解吸30wt％的饱和乙醇胺(MEA)溶液中CO2的具体情况如下表所示：
The specific conditions of desorption of CO 2 in 30 wt % saturated ethanolamine (MEA) solution in Example 1, Example 2 and Comparative Example are shown in the following table:
The specific conditions of desorption of CO 2 in 30 wt % saturated ethanolamine (MEA) solution in Example 1, Example 2 and Comparative Example are shown in the following table:
从上述测试结果可知，在90℃解吸温度条件下，饱和MEA富液释放CO2的相对解吸热负荷下降了约54％，能耗得到了大幅度节约；在95℃解吸温度条件下，饱和MEA富液释放CO2的相对解吸热负荷下降了约32％，能耗也得到了一定幅度的节约，且解吸速率均有显著的提高。From the above test results, it can be seen that under the desorption temperature condition of 90℃, the relative desorption heat load of CO2 released by saturated MEA rich liquid decreased by about 54%, and the energy consumption was greatly saved; under the desorption temperature condition of 95℃, the relative desorption heat load of CO2 released by saturated MEA rich liquid decreased by about 32%, and the energy consumption was also saved to a certain extent, and the desorption rate was significantly improved.
实验证明本申请作为催化剂在机胺溶液解吸CO2中应用可将解吸温度降低到95℃左右，既能满足解吸CO2的要求，又能降低水分的蒸发，整体上可降低再生环节中热量的消耗，起到节能环保的作用。Experiments have shown that the application of this application as a catalyst in the desorption of CO2 from an amine solution can reduce the desorption temperature to about 95°C, which can not only meet the requirements for desorption of CO2 , but also reduce the evaporation of water. Overall, it can reduce the heat consumption in the regeneration process and play a role in energy saving and environmental protection.
前述对本申请的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本申请限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本申请的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本申请的各种不同的示例性实施方案以及各种不同的选择和改变。本申请的范围意在由权利要求书及其等同形式所限定。
The foregoing description of the specific exemplary embodiments of the present application is for the purpose of illustration and illustration. These descriptions are not intended to limit the present application to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present application and its practical application, so that those skilled in the art can realize and utilize the various exemplary embodiments of the present application and various selections and changes. The scope of the present application is intended to be limited by the claims and their equivalents.
Claims (8)
- 一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，包括以下步骤：A method for preparing a covalent organic framework material for CO2 desorption, characterized in that it comprises the following steps:(1)将1,3,5-三(4-氨基苯基)苯与对苯二甲醛混合到二甲基亚砜中，得到均质液A，作为反应物前驱体溶液；(1) mixing 1,3,5-tri(4-aminophenyl)benzene and terephthalaldehyde in dimethyl sulfoxide to obtain a homogeneous solution A as a reactant precursor solution;(2)将铁酸镍纳米晶体浸入到均质液A中并分散均匀，得到浑浊液B；(2) immersing nickel ferrite nanocrystals into homogeneous liquid A and dispersing them evenly to obtain turbid liquid B;(3)将纯度为99％的冰乙酸缓慢滴加到浑浊液B中，得到悬浮液C；(3) slowly adding 99% pure glacial acetic acid dropwise to the turbid liquid B to obtain a suspension C;(4)将悬浮液C继续置于室温条件下反应0.5-1.5小时，得到充分反应后的棕色胶体悬浮液；(4) the suspension C is allowed to react for 0.5-1.5 hours at room temperature to obtain a fully reacted brown colloidal suspension;(5)往悬浮液C中加入有机溶剂后采用离心的方式洗涤4-8次，去除棕色胶体中残留的杂质，得到棕色胶体产物D；(5) adding an organic solvent to the suspension C and washing the suspension C by centrifugation for 4-8 times to remove impurities remaining in the brown colloid to obtain a brown colloid product D;(6)将棕色胶体产物D置于真空干燥箱中干燥12-24小时，得到深黄色的镍与铁双金属离子修饰共价有机框架催化解吸CO2的材料，即Ni/Fe-COF。(6) The brown colloidal product D is placed in a vacuum drying oven and dried for 12-24 hours to obtain a dark yellow nickel and iron bimetallic ion modified covalent organic framework material for catalytic desorption of CO2 , namely Ni/Fe-COF.
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(1)中1,3,5-三(4-氨基苯基)苯与对苯二甲醛的物质的量之比n1：n2为1:1-1:2。The method for preparing a covalent organic framework material for CO2 desorption according to claim 1 is characterized in that in step (1), the molar ratio n1:n2 of 1,3,5-tris(4-aminophenyl)benzene to terephthalaldehyde is 1:1-1:2.
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(2)中铁酸镍纳米晶体的粒径为3-30nm。The method for preparing a covalent organic framework material for CO2 desorption according to claim 1, characterized in that the particle size of the nickel ferrite nanocrystals in step (2) is 3-30 nm.
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(2)铁酸镍纳米晶体浸入到均质液A中后采用超声波震荡器震荡至分散均匀。The method for preparing a covalent organic framework material for CO2 desorption according to claim 1 is characterized in that, in step (2), the nickel ferrite nanocrystals are immersed in the homogenous liquid A and then vibrated by an ultrasonic oscillator until they are evenly dispersed.
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(3)中冰乙酸加入的体积量占步骤(1)中二甲基亚砜体积的5％-10％。 The method for preparing a covalent organic framework material for CO2 desorption according to claim 1 is characterized in that the volume of glacial acetic acid added in step (3) accounts for 5%-10% of the volume of dimethyl sulfoxide in step (1).
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(5)中有机溶剂采用纯度为99％的四氢呋喃和纯度为99％的甲醇，洗涤时四氢呋喃和甲醇交替使用。The method for preparing a covalent organic framework material for CO2 desorption according to claim 1 is characterized in that the organic solvent in step (5) is tetrahydrofuran with a purity of 99% and methanol with a purity of 99%, and tetrahydrofuran and methanol are used alternately during washing.
- 根据权利要求1所述的一种用于CO2解吸的共价有机框架材料的制备方法，其特征在于，所述步骤(6)中干燥温度为60-80℃。The method for preparing a covalent organic framework material for CO2 desorption according to claim 1 is characterized in that the drying temperature in step (6) is 60-80°C.
- 一种根据权利要求1-7中任一项所述的用于CO2解吸的共价有机框架材料在有机胺溶液解吸CO2领域的应用。 A use of the covalent organic framework material for CO2 desorption according to any one of claims 1 to 7 in the field of CO2 desorption from organic amine solutions.
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| US20170304764A1 (en) * | 2013-12-02 | 2017-10-26 | University Of Southern California | Regenerative adsorbents of modified amines on nano-structured supports |
| US20220072472A1 (en) * | 2020-09-07 | 2022-03-10 | 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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| US20170304764A1 (en) * | 2013-12-02 | 2017-10-26 | 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 |
| US20220072472A1 (en) * | 2020-09-07 | 2022-03-10 | 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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