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CN118403656B - A graphene-based solid acid catalyst, preparation method and application thereof, and method for treating flue gas containing CO2 - Google Patents

A graphene-based solid acid catalyst, preparation method and application thereof, and method for treating flue gas containing CO2 Download PDF

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CN118403656B
CN118403656B CN202410519162.XA CN202410519162A CN118403656B CN 118403656 B CN118403656 B CN 118403656B CN 202410519162 A CN202410519162 A CN 202410519162A CN 118403656 B CN118403656 B CN 118403656B
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graphene
acid catalyst
solid acid
based solid
flue gas
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CN118403656A (en
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王研
杨涛
于勇勇
杨明亮
赵玉
李洋
王垚
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Xiamen Siyan New Material Technology Co ltd
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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/1493—Selection of liquid materials for use as absorbents
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/18—Absorbing units; Liquid distributors therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J35/615—100-500 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
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Abstract

本发明属于CO2捕集技术领域，具体涉及一种石墨烯基固体酸催化剂及其制备方法和应用以及CO2烟气的处理方法。所述石墨烯基固体酸催化剂以分子筛作为载体，以氧化石墨烯、WO3和TiO2作为活性组分。本发明的关键在于将氧化石墨烯、WO3和TiO2同时作为活性组分负载于分子筛载体上，由此不仅可以显著提升CO2的解吸效率，而且还可以降低解吸能耗。此外，本发明提供的石墨烯基固体酸催化剂的催化能力强，循环使用次数多。

The present invention belongs to the technical field of CO2 capture, and specifically relates to a graphene-based solid acid catalyst, a preparation method and application thereof, and a method for treating CO2 flue gas. The graphene-based solid acid catalyst uses a molecular sieve as a carrier, and graphene oxide, WO3 and TiO2 as active components. The key to the present invention is that graphene oxide, WO3 and TiO2 are simultaneously loaded on the molecular sieve carrier as active components, thereby not only significantly improving the desorption efficiency of CO2 , but also reducing the desorption energy consumption. In addition, the graphene-based solid acid catalyst provided by the present invention has a strong catalytic ability and a large number of recycling times.

Description

Graphene-based solid acid catalyst, preparation method and application thereof, and treatment method of CO 2 -containing flue gas
Technical Field
The invention belongs to the technical field of CO 2 trapping, and particularly relates to a graphene-based solid acid catalyst, a preparation method and application thereof, and a treatment method of CO 2 -containing flue gas.
Background
Currently, the chemical absorption method is the most mature application in the CO 2 capturing technology. The technology for absorbing and desorbing CO 2 by using organic amine has the characteristics of higher absorption efficiency, stable operation and the like, adopts the principles of low-temperature absorption and high-temperature desorption, and has the absorption temperature of about 40 ℃ and the desorption temperature of about 100-120 ℃, and the desorption energy consumption is the maximum limit for limiting the wide use of the technology. In order to reduce desorption energy consumption, the total desorption load can be reduced by means of reducing the flow of the rich liquid entering the desorption tower, arranging an MVR system for desorbing lean liquid, shunting a part of the rich liquid entering the desorption tower to be heated by the desorption gas at the bottom of the tower and the like, so that the desorption energy consumption is reduced.
CN106039936A, CN108079746A, CN219043227U, CN205549971U discloses a method for capturing CO 2 based on phase-change absorbent, which adopts a series of organic amine and water to compound, so as to obtain homogeneous aqueous solution, the solution after absorbing CO 2 is automatically layered, the upper light phase is free from CO 2 and directly returns to the absorption tower, the lower heavy phase contains a large amount of CO 2 reactant to desorb in the desorption tower, and the total amount of the solution entering the desorption tower is reduced, so that the desorption energy consumption is reduced, which is a relatively hot method for current research. The ethanol amine (MEA) has very fast CO 2 absorption capacity, but the desorption energy consumption is as high as 3.7-4.0 GJ/tCO 2, the corrosion is very strong, the desorption rate of the N-Methyldiethanolamine (MDEA) is fast, but the absorption efficiency is limited, a large amount of circulating liquid is needed for absorption, and the equipment investment and the occupied area are very large.
CN114452779a discloses a heat pump assisted phase change carbon dioxide capturing system, which adopts a combination of an evaporator, a condenser and a compressor on the basis of capturing carbon dioxide by a phase change method, and is called a heat pump system, and adopts post-desorption lean solution (high temperature 100-120 ℃), pre-absorption lean solution (low temperature 40 ℃) and post-absorption rich solution (low temperature 40 ℃) to perform heat exchange, wherein heat transfer is performed by adopting a heat medium (heat conducting oil and water), and an external heat source is hardly used. Although the phase change absorber is used as a trapping premise in the patent application, the phase change absorber can only reduce the desorption flow rate and cannot reduce the desorption temperature, and the heat pump uses the phase change heat of the heat medium, so that the temperature of the heated amine liquid needs to be lower than the boiling point of the heat medium, and therefore, the heat pump system generally needs to be lower than the boiling point (lower than 90 ℃) of the heat medium to be capable of stably operating.
Disclosure of Invention
The first object of the present invention is to provide a graphene-based solid acid catalyst having an excellent desorption effect for catalyzing desorption of CO 2.
The second object of the present invention is to provide a method for preparing the graphene-based solid acid catalyst.
The third object of the invention is to provide the application of the graphene-based solid acid catalyst as a CO 2 rich amine liquid desorbent.
The fourth object of the invention is to provide a method for treating flue gas containing CO 2.
The graphene-based solid acid catalyst provided by the invention takes a molecular sieve as a carrier and graphene oxide, WO 3 and TiO 2 as active components.
The preparation method of the graphene-based solid acid catalyst comprises the steps of carrying out hydrothermal reaction on graphene oxide, a WO 3 precursor and a TiO 2 precursor in a solution, mixing a hydrothermal reaction product with a molecular sieve carrier, and drying to obtain the graphene-based solid acid catalyst.
The treatment method of the CO 2 -containing flue gas provided by the invention comprises the following steps:
s1, introducing flue gas containing CO 2 into an absorption tower from the lower part, spraying a CO 2 absorbent into the absorption tower from top to bottom, reacting CO 2 in the flue gas with the CO 2 absorbent to generate organic salt so as to remove CO 2 in the flue gas, obtaining rich amine liquid at the bottom of the absorption tower and obtaining flue gas with CO 2 removed at the top of the absorption tower;
S2, introducing the rich amine liquid into a desorption tower for CO 2 desorption, wherein the desorption tower uses the graphene-based solid acid catalyst as a filler, and the generated CO 2 gas is discharged from the top of the desorption tower.
The inventor of the invention has found after intensive and extensive research that molecular sieve has excellent adsorption and catalytic desorption capability, and can be used as a carrier to improve the catalytic capability, graphene is a novel two-dimensional carbon atom crystal formed by monoatomic layers with carbon atoms connected in an sp2 hybridized manner, graphene Oxide (GO) has a large number of oxygen-containing functional groups besides a plurality of reactive carbon-carbon double bonds, so that the surface chemical modification is easy to carry out to change the properties of the Graphene Oxide, WO 3 and TiO 2 are simultaneously used as active components to be loaded on the molecular sieve carrier, and an adsorption micro-region with highly compatible acidic sites and reaction substrates can be simultaneously constructed, so that the desorption efficiency of CO 2 can be remarkably improved. In addition, when the graphene-based solid acid catalyst is used for CO 2 desorption, the high-temperature desorption process can be catalyzed, the CO 2 desorption rate is accelerated, meanwhile, the desorption temperature is reduced to 60-90 ℃, CO 2 desorption can be realized at the lower temperature, the desorption energy consumption can be reduced by more than 30%, and corrosion and pressure are reduced because a large amount of water vapor is not generated during desorption, so that the material and cost of a desorption tower can be reduced. And if the carbon dioxide desorption technology is combined with the heat pump technology, the desorption requirement can be met, the cost of the carbon dioxide desorption technology is reduced by about 60% -80%, and the important promotion effect is achieved for achieving the double-carbon target in China. In addition, the graphene-based solid acid catalyst provided by the invention has strong catalytic capability and is used for a plurality of times.
Drawings
FIG. 1 is an XRD pattern of graphene-based solid acid catalysts doped with different graphene contents;
FIG. 2 is a FTIR spectrum of graphene-based solid acid catalysts doped with different graphene content;
FIG. 3 is an SEM image of an graphene-based solid acid catalyst doped with different graphene contents;
FIG. 4 is an XRD pattern of an graphene-based solid acid catalyst doped with different TiO 2 levels;
FIG. 5 is a FTIR spectrum of graphene-based solid acid catalysts doped with different levels of TiO 2;
FIG. 6 is an SEM image of an ink-based solid acid catalyst doped with different TiO 2 levels;
FIG. 7 is a graph of desorption effectiveness of an alkenyl solid acid catalyst;
fig. 8 is a process flow diagram for CO 2 capture and desorption.
Detailed Description
The graphene-based solid acid catalyst provided by the invention takes a molecular sieve as a carrier and graphene oxide, WO 3 and TiO 2 as active components.
In the invention, the graphene oxide is a hydrophobic nano-sheet, and an acidic group and other polar and nonpolar groups are bonded on the hydrophobic nano-sheet to simulate the catalysis characteristics of biological enzymes, so that an adsorption micro-region with highly affinity of an acidic site and a reaction substrate can be possibly constructed. In addition, the graphene oxide has a larger specific surface area, can provide a large number of adsorption and reaction active sites, has a planar structure, does not contain micropores which can prevent a reaction substrate from entering, is beneficial to reducing mass transfer resistance in a catalytic reaction and improves the mass transfer rate.
In the invention, the content of the carrier is preferably 30-80 wt% and the content of the active component is preferably 20-70 wt% based on the total weight of the graphene-based solid acid catalyst. Specifically, the carrier may be present in an amount of 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or any value therebetween. The active component may be present in an amount of 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% or any value therebetween.
In the invention, the mass ratio of graphene oxide, tiO 2 and WO 3 in the active components is (1-4): (7-21): 7, and at the moment, the active components can better play a synergistic effect, and the CO 2 desorption catalysis effect is better. Specifically, the content of the graphene oxide is preferably 1 to 4 parts by weight, such as 1,2, 3, 4 parts by weight or any value therebetween, and the content of the TiO 2 is preferably 7 to 21 parts by weight, such as 7,8, 9,10, 12, 15, 18, 20, 21 parts by weight or any value therebetween, based on the content of WO 3 being 7 parts by weight.
In the present invention, the molecular sieve may be a ZSM-series molecular sieve, a Y-type molecular sieve, an A-type molecular sieve, a T-type molecular sieve, etc., preferably a ZSM-series molecular sieve, more preferably H-ZSM-5. The H-ZSM-5 carrier has the capabilities of adsorption and catalytic desorption, and the catalytic desorption capability can be further improved after load synthesis.
The preparation method of the graphene-based solid acid catalyst comprises the steps of carrying out hydrothermal reaction on graphene oxide, a WO 3 precursor and a TiO 2 precursor in a solution, mixing a hydrothermal reaction product with a molecular sieve carrier, and drying to obtain the graphene-based solid acid catalyst.
In a preferred embodiment, the hydrothermal reaction is carried out by ultrasonically dispersing graphene oxide in water, mixing the obtained dispersion with an organic solvent I to obtain a solution A, mixing a TiO 2 precursor with an organic solvent II to obtain a solution B, mixing a WO 3 precursor with an organic solvent III to obtain a solution C, mixing the solution A, the solution B and the solution C, and then carrying out the reaction under the hydrothermal reaction condition. The dispersing time is preferably 2-20 h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or any value therebetween. The hydrothermal reaction condition preferably comprises a temperature of 120-250 ℃, such as 120-140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 250 ℃ or any value between the two, and a time of 1-3 d, such as 1d, 1.5d, 2d, 2.5d, 3d or any value between the two.
In the specific process of the hydrothermal reaction, the dosage ratio of the WO 3 precursor, the TiO 2 precursor, the graphene oxide, the molecular sieve, the organic solvent I, the organic solvent II and the organic solvent III is preferably (1-5) g (1-10) mL (10-150) mL (3-5) g (5-50) mL (5-10) mL (3-8) mL. Specifically, the dosage ratio of the TiO 2 precursor to the WO 3 precursor may be (1-10) mL (1-5) g, such as 1mL:1g、2mL:1g、4mL:1g、6mL:1g、8mL:1g、10mL:1g、1mL:3g、2mL:3g、4mL:3g、6mL:3g、8mL:3g、10mL:3g、1mL:5g、2mL:5g、4mL:5g、6mL:5g、8mL:5g、10mL:5g or any value therebetween. The dosage ratio of the graphene oxide to the WO 3 precursor can be (10-150) mL (1-5) g, such as 10mL:1g、10mL:3g、10mL:5g、30mL:1g、30mL:3g、30mL:5g、50mL:1g、50mL:3g、50mL:5g、80mL:1g、80mL:3g、80mL:5g、100mL:1g、100mL:3g、100mL:5g、120mL:1g、120mL:3g、120mL:5g、140mL:1g、140mL:3g、140mL:5g、150mL:1g、150mL:3g、150mL:5g or any value between the graphene oxide and the WO 3 precursor. The dosage ratio of the molecular sieve to the WO 3 precursor may be (3-5) g, such as 3g:1g, 3g:3g, 3g:5g, 4g:1g, 4g:3g, 4g:5g, 5g:1g, 5g:3g, 5g:5g, or any value therebetween. The ratio of the amount of the organic solvent I to the WO 3 precursor can be (5-50 mL): (1-5 g), such as 5mL:1g、5mL:3g、5mL:5g、10mL:1g、10mL:3g、10mL:5g、15mL:1g、15mL:3g、15mL:5g、20mL:1g、20mL:3g、20mL:5g、25mL:1g、25mL:3g、25mL:5g、30mL:1g、30mL:3g、30mL:5g、35mL:1g、35mL:3g、35mL:5g、40mL:1g、40mL:3g、40mL:5g、45mL:1g、45mL:3g、45mL:5g、50mL:1g、50mL:3g、50mL:5g or any value between the organic solvent I and the WO 3 precursor. The dosage ratio of the organic solvent II to the WO 3 precursor may be (5-10) mL (1-5) g, such as 5mL:1g, 5mL:3g, 5mL:4g, 8mL:1g, 8mL:3g, 8mL:4g, 10mL:1g, 10mL:3g, 10mL:4g, or any value therebetween. The ratio of the amount of the organic solvent III to the WO 3 precursor may be (3-8) mL (1-5) g, such as 3mL:1g, 3mL:3g, 3mL:5g, 5mL:1g, 5mL:3g, 5mL:5g, 8mL:1g, 8mL:3g, 8mL:5g, or any value therebetween.
In the present invention, the WO 3 precursor may be an existing compound which can be converted into WO 3 after hydrothermal reaction, mixing and drying, preferably a tungstate. The tungstate may specifically be at least one of sodium tungstate (Na 2WO4·2H2 O), potassium tungstate (K 2WO4·2H2 O), ammonium tungstate [ (NH 4)6W7O24·6H2 O ], calcium tungstate (CaWO 4), cobalt tungstate (CoWO 4), cadmium tungstate (CdWO 4), ferrous tungstate (FeWO 4), and zinc tungstate (5zno·12wo 3).
In the present invention, the TiO 2 precursor may be an existing compound which can be converted into TiO 2 after hydrothermal reaction, mixing and drying, preferably titanate, and specific examples of the titanate include, but are not limited to, at least one of tetrabutyl titanate, isopropyl titanate, titanyl sulfate, titanium trichloride and titanium tetrachloride.
In the present invention, the organic solvent I is preferably a glacial acetic acid solution. The organic solvent II is preferably DMF and/or absolute ethanol. The organic solvent III is preferably a hydrochloric acid solution. The terms "I", "II" and "III" are used to distinguish between different organic solvents for ease of description and have no other special meaning.
In the present invention, the conditions for drying preferably include a temperature of 50 to 120 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or any value therebetween.
The invention also provides application of the graphene-based solid acid catalyst as a CO 2 rich amine liquid desorbent.
As shown in fig. 8, the treatment method of the flue gas containing CO 2 provided by the invention comprises the following steps:
s1, introducing flue gas containing CO 2 into an absorption tower from the lower part, spraying a CO 2 absorbent into the absorption tower from top to bottom, reacting CO 2 in the flue gas with the CO 2 absorbent to generate organic salt so as to remove CO 2 in the flue gas, obtaining rich amine liquid at the bottom of the absorption tower and obtaining flue gas with CO 2 removed at the top of the absorption tower;
S2, introducing the rich amine liquid into a desorption tower for CO 2 desorption, wherein the desorption tower uses the graphene-based solid acid catalyst as a filler, and the generated CO 2 gas is discharged from the top of the desorption tower.
In the present invention, the CO 2 absorbent may be at least one of organic amine such as ethanolamine (MEA), N-Methyldiethanolamine (MDEA), and the like.
In the present invention, the temperature of the desorption of CO 2 is preferably 80 to 85 ℃, such as 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃ or any value therebetween. In order to control the temperature of the desorption of CO 2 to the desired range, it is generally necessary to heat exchange the rich amine solution with a heat exchanger prior to introducing it into the desorber.
In the present invention, the absorber is generally also packed with a packing in order to further facilitate the removal of CO 2. The filler material can be at least one of TiO 2、WO3、TiO2/WO3, tiO 2/WO3/GO and the like.
In a specific embodiment, the treatment method of the flue gas containing CO 2 provided by the invention further comprises the steps of standing and layering the rich amine solution before the rich amine solution is introduced into the desorption tower to desorb CO 2, wherein the bottom layer is rich in CO 2 solution, the top layer is lean in CO 2 solution, the rich CO 2 solution is introduced into the desorption tower to desorb CO 2, and the lean in CO 2 solution is returned to the absorption tower as a CO 2 absorbent.
In a specific embodiment, the treatment method of the flue gas containing CO 2 further comprises the step of returning the lean amine liquid obtained from the bottom of the desorption tower to the absorption tower as the CO 2 absorbent.
The present invention will be described in detail by examples.
Example 1
Diluting the high-concentration graphene oxide solution to 1% (10 mg/mL) by deionized water, performing ultrasonic dispersion for 6h to obtain GO dispersion liquid, stirring and mixing 37mL of GO dispersion liquid and 12mL of glacial acetic acid for 30min to obtain solution A, stirring and mixing 3.7g of tetrabutyl titanate and 6mL of absolute ethyl alcohol uniformly to obtain solution B, stirring and mixing 3.7g of sodium tungstate and 7mL of dilute hydrochloric acid (15%) uniformly to obtain solution C, stirring and mixing the solution A, the solution B and the solution C uniformly, then placing the solution C into an oven, gradually heating to 160 ℃ and maintaining for 1d to complete hydrothermal reaction, and cooling to room temperature after the reaction is finished to obtain a hydrothermal reaction product. Mixing the hydrothermal reaction product with 4.44g of spherical H-ZSM-5 molecular sieve, performing ultrasonic treatment, repeatedly cleaning and filtering the obtained ultrasonic treatment product with deionized water, and drying the obtained solid product at the temperature of 80 ℃ to obtain the graphene-based solid acid catalyst, which is marked as W 1T1-G1.
The graphene-based solid acid catalyst W 1T1-G1 takes an H-ZSM-5 molecular sieve as a carrier and takes graphene oxide, WO 3 and TiO 2 as active components, wherein the content of the carrier in the catalyst is 53.9wt%, the content of the active components is 46.1wt%, and the mass ratio of the graphene oxide, WO 3 and TiO 2 in the active components is 1:7:7.
Example 2
A graphene-based solid acid catalyst was prepared according to the method of example 1, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 2:7:7, to obtain a graphene-based solid acid catalyst, which was denoted as W 1T1-G2.
Example 3
A graphene-based solid acid catalyst was prepared in the same manner as in example 1, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 4:7:7, to give a graphene-based solid acid catalyst, which was denoted as W 1T1-G3.
Example 4
A graphene-based solid acid catalyst was prepared in the same manner as in example 1 except that the amount of titanium salt added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 1:7:14, to give a graphene-based solid acid catalyst, which was denoted as W 1T2-G1.
Example 5
A graphene-based solid acid catalyst was prepared in the same manner as in example 4, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 2:7:14, to give a graphene-based solid acid catalyst, which was denoted as W 1T2-G2.
Example 6
A graphene-based solid acid catalyst was prepared in the same manner as in example 4, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 4:7:14, to give a graphene-based solid acid catalyst, which was denoted as W 1T2-G3.
Example 7
A graphene-based solid acid catalyst was prepared in the same manner as in example 1 except that the amount of titanium salt added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 1:7:21, to give a graphene-based solid acid catalyst, which was denoted as W 1T3-G1.
Example 8
A graphene-based solid acid catalyst was prepared in the same manner as in example 7, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 2:7:21, to give a graphene-based solid acid catalyst, which was denoted as W 1T3-G2.
Example 9
A graphene-based solid acid catalyst was prepared in the same manner as in example 7, except that the amount of graphene oxide added was changed during the catalyst preparation so that the mass ratio of graphene oxide, WO 3 and TiO 2 was 4:7:21, to give a graphene-based solid acid catalyst, which was denoted as W 1T3-G3.
Test example 1
And respectively performing X-ray diffraction, infrared and field emission Scanning Electron Microscope (SEM) detection on W 1T1-G1、W1T1-G2 and W 1T1-G3, wherein the obtained X-ray diffraction spectrogram, infrared spectrogram and SEM are respectively shown in figures 1, 2 and 3.
As can be seen from fig. 1, the characteristic diffraction peaks of WO 3/TiO2/GO correspond to tungsten oxide in the standard pattern (JCPDS cards 33-1387) and titanium dioxide in the standard pattern (JCPDS cards 21-1272), respectively, at which time the peak of graphene has disappeared, which means that graphene has been completely dispersed into a single layer, no longer in a regularly arranged layer, but rather is spatially disordered stacked, whereby it can be demonstrated that WO 3/TiO2/GO solid acid catalyst has been successfully prepared.
The main characteristic peaks in the infrared spectrum chart shown in FIG. 2 are 785cm -1 which is the vibration band of WO 3 tetrahedron, 1401cm -1 which is the vibration band of Ti-O-Ti, 1601cm -1 which is the absorption peak of Ti-O-W bond, 1040cm -1 which is the vibration absorption peak of C-O-C, and 2398cm -1 which is the weak peak of-OH bending vibration, which is mainly related to the surface hydroxyl groups of TiO 2-WO3 and the surface adsorbed water.
The characterization results of FIGS. 1 and 2 show that the molecular sieve H-ZSM-5 supported WO 3/TiO2/GO solid acid catalyst has been successfully prepared.
As can be seen from fig. 3, WO 3/TiO2/GO is a steric bulk structure formed by the stacking of nanoparticles, which provides more active sites for the redox reaction and can shorten the transport path of the reaction particles, thus exhibiting better catalytic performance.
Test example 2
And respectively carrying out X-ray diffraction, infrared and SEM detection on the W 1T1-G2、W1T2-G2 and the W 1T3-G2, wherein the obtained X-ray diffraction spectrogram, infrared spectrogram and SEM image are respectively shown in fig. 4, 5 and 6.
It can be seen from fig. 4 that the characteristic diffraction peaks of W 1T1-G2、W1T2-G2 and W 1T3-G2 also correspond to tungsten oxide in the standard pattern (JCPDS cards 33-1387) and titanium dioxide in the standard pattern (JCPDS cards 21-1272), indicating that WO 3/TiO2/GO solid acid catalyst can also be successfully prepared by changing the mass ratio of tungsten salt to titanium salt.
The main characteristic peaks in the infrared spectrum chart shown in FIG. 5 are 1480cm -1 as the vibration band of Ti-O-Ti, 1603cm -1 as the vibration absorption peak of Ti-O-W bond, 1041cm -1 as the vibration absorption peak of C-O-C, and 2398cm -1 as the content of TiO 2 increases, which shows that the absorption of hydroxyl groups on the surface of TiO 2-WO3 and water on the surface increases.
The characterization results of fig. 4 and 5 show that the molecular sieve H-ZSM-5 supported WO 3/TiO2/GO solid acid catalyst has been successfully prepared.
It can be seen from fig. 6 that WO 3/TiO2/GO is also a three-dimensional block structure formed by stacking nanoparticles, and different mass ratios of tungsten salt and titanium salt occupy different sites, so that the size and stacking degree of the formed catalyst particles are partially different.
Test example 3 test example for the description of the catalytic desorption of a CO 2 -rich amine solvent
The batch-type desorption device body adopted in the test example is a three-neck flask with 2L volume, a condensing reflux device is arranged at the middle bottleneck to prevent evaporation of the amine solution, a thermometer is arranged at one bottleneck at two sides to measure the desorption temperature of the solution, the other is used for sampling, and the three-neck flask adopts magnetic stirring to ensure that the amine solution and the catalyst are contacted uniformly.
The carbon-rich amine solution to be desorbed, having a volume of 300mL, was added to a three-necked flask, 3g of the above-mentioned catalyst W1T1-G1、W1T1-G2、W1T1-G3、W1T2-G1、W1T2-G2、W1T2-G3、W1T3-G1、W1T3-G2 and W 1T3-G3 were added thereto, respectively, and a blank control was not added with the catalyst, and the three-necked flask was placed in an oil bath and heated to a desired desorption temperature (specifically 80 ℃) and sampled and analyzed for its desorption process. The amounts of CO 2 desorbed by the catalysts in different ratios are shown in FIG. 7. As can be seen from fig. 7, the use of the WO 3/TiO2/GO solid acid catalyst provided by the present invention is beneficial to increase the desorption content and desorption rate of CO 2 relative to the blank rich amine solution.
Comparative example 1
(1) The desorption effects of the best desorption effect catalyst W 1T3-G3, the worst desorption effect catalyst W 1T2-G2 and the commercial catalyst prepared in the above examples were selected for comparison, and the results are shown in table 1 below.
TABLE 1
From the above table, it can be seen that the desorption effect of the W 1T3-G3 catalyst is superior to that of the commonly used commercial catalyst.
(2) BET specific surface area measurements were made on the best desorbing effect catalyst W 1T3-G3, the worst desorbing effect catalyst W 1T2-G2, and the commercial catalyst, and the measurement results are shown in Table 2 below.
TABLE 2
Project Specific surface area (m 2/g) Pore volume (cm 3/g) Aperture (nm)
Commercial catalyst 128.30 0.219 5.999
W1T3-G3 157.75 0.465 4.956
W1T2-G2 129.81 0.221 6.003
BET measurement results show that the W 1T3-G3 catalyst has the largest specific surface area and pore volume, larger pore volume and specific surface area possibly provide richer active sites, smaller nanometer particle size can reduce the transmission path and diffusion effect of CO 2 and products, and the added graphene material can improve the mass transfer rate, accelerate the desorption reaction rate and improve the utilization rate of the catalyst. Therefore, the WO 3/TiO2/GO solid acid catalyst prepared by the invention has better application effect on desorption of CO 2.
Application example
The experiment builds a method for recovering CO 2 by utilizing a graphene solid acid catalyst to catalyze and desorb carbon capture aiming at CO 2 -enriched flue gas generated by a certain heating power station in China, wherein a specific process flow chart is shown in figure 8, and specifically:
S1, introducing CO 2 flue gas into an absorption tower from the lower part, spraying a CO 2 absorbent (organic amine) into the absorption tower from top to bottom, and reacting CO 2 in the flue gas with the CO 2 absorbent to generate organic salt so as to trap CO 2 in the flue gas, thereby obtaining a CO 2 -rich solution and a CO 2 -lean flue gas;
S2, fixing a catalyst W 1T1-G2 in a desorption tower through a fine metal wire, heating the CO 2 -rich solution to 85 ℃, introducing the solution into the desorption tower, performing high-temperature desorption by flowing through the catalyst from top to bottom, and discharging generated CO 2 gas from the top of the desorption tower. Wherein the operational data of each process section is shown in table 3 below.
TABLE 3 Table 3
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.

Claims (30)

1.一种石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述石墨烯基固体酸催化剂以分子筛作为载体，以氧化石墨烯、WO3和TiO2作为活性组分。1. Application of a graphene-based solid acid catalyst as a desorbent for CO2- rich amine liquid, characterized in that the graphene-based solid acid catalyst uses a molecular sieve as a carrier and graphene oxide, WO3 and TiO2 as active components. 2.根据权利要求1所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，以所述石墨烯基固体酸催化剂的总重量为基准，所述载体的含量为30~80wt%，所述活性组分的含量为20~70wt%。2. The use of the graphene-based solid acid catalyst as a desorbent for CO2- rich amine liquid according to claim 1, characterized in that, based on the total weight of the graphene-based solid acid catalyst, the content of the carrier is 30-80wt%, and the content of the active component is 20-70wt%. 3.根据权利要求1所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述活性组分中氧化石墨烯、TiO2和WO3的质量比为(1~4):(7~21):7。3. The use of the graphene-based solid acid catalyst according to claim 1 as a desorbent for CO2- rich amine liquid, characterized in that the mass ratio of graphene oxide, TiO2 and WO3 in the active components is (1~4):(7~21):7. 4.根据权利要求1所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述分子筛为H-ZSM-5。4. Use of the graphene-based solid acid catalyst according to claim 1 as a desorbent for CO2 - rich amine liquid, characterized in that the molecular sieve is H-ZSM-5. 5.权利要求1~4中任意一项所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述石墨烯基固体酸催化剂按照以下方法制备得到：将氧化石墨烯、WO3前驱体和TiO2前驱体于溶液中进行水热反应，再将水热反应产物和分子筛载体进行混合后烘干，即得石墨烯基固体酸催化剂。5. Use of the graphene-based solid acid catalyst according to any one of claims 1 to 4 as a desorbent for CO2- rich amine liquid, characterized in that the graphene-based solid acid catalyst is prepared according to the following method: graphene oxide, WO3 precursor and TiO2 precursor are subjected to hydrothermal reaction in a solution, and then the hydrothermal reaction product and a molecular sieve carrier are mixed and dried to obtain the graphene-based solid acid catalyst. 6.根据权利要求5所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述水热反应的方式为将氧化石墨烯超声分散于水中，之后将所得分散液与有机溶剂I混合得到溶液A；将TiO2前驱体与有机溶剂II混合得到溶液B；将WO3前驱体与有机溶剂III混合得到溶液C；将溶液A、溶液B和溶液C混合后置于水热反应条件下进行反应。6. The use of the graphene-based solid acid catalyst as a desorbent for a CO2- rich amine liquid according to claim 5, characterized in that the hydrothermal reaction is carried out by ultrasonically dispersing graphene oxide in water, then mixing the obtained dispersion with an organic solvent I to obtain a solution A; mixing a TiO2 precursor with an organic solvent II to obtain a solution B; mixing a WO3 precursor with an organic solvent III to obtain a solution C; and mixing solution A, solution B and solution C and reacting them under hydrothermal reaction conditions. 7.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述分散的时间为2~20h。7. Use of the graphene-based solid acid catalyst according to claim 6 as a desorbent for CO2- rich amine liquid, characterized in that the dispersion time is 2 to 20 hours. 8.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述水热反应条件包括温度为120~250℃，时间为1~3d。8. The use of the graphene-based solid acid catalyst as a desorbent for CO2- rich amine liquid according to claim 6, characterized in that the hydrothermal reaction conditions include a temperature of 120-250°C and a time of 1-3 days. 9.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述WO3前驱体为钨酸盐。9. Use of the graphene-based solid acid catalyst as a desorbent for CO2 - rich amine liquid according to claim 6, characterized in that the WO3 precursor is tungstate. 10.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述TiO2前驱体为钛酸盐。10. Use of the graphene-based solid acid catalyst as a desorbent for CO2- rich amine liquid according to claim 6, characterized in that the TiO2 precursor is titanate. 11.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述有机溶剂I为冰醋酸溶液。11. Use of the graphene-based solid acid catalyst according to claim 6 as a desorbent for CO2 - rich amine liquid, characterized in that the organic solvent I is a glacial acetic acid solution. 12.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述有机溶剂II为DMF和/或无水乙醇。12. Use of the graphene-based solid acid catalyst as a desorbent for CO2 - rich amine liquid according to claim 6, characterized in that the organic solvent II is DMF and/or anhydrous ethanol. 13.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述有机溶剂III为盐酸溶液。13. Use of the graphene-based solid acid catalyst as a desorbent for CO2 - rich amine liquid according to claim 6, characterized in that the organic solvent III is a hydrochloric acid solution. 14.根据权利要求6所述的石墨烯基固体酸催化剂作为CO2富胺液解吸剂的应用，其特征在于，所述烘干的条件包括温度为50~120℃。14. The use of the graphene-based solid acid catalyst as a desorbent for CO2 - rich amine liquid according to claim 6, characterized in that the drying condition includes a temperature of 50-120°C. 15.一种含CO2烟气的处理方法，其特征在于，该方法包括以下步骤：15. A method for treating flue gas containing CO2 , characterized in that the method comprises the following steps: S1、将含CO2烟气自下部引入吸收塔中，同时将CO2吸收剂自上而下喷淋至吸收塔中，烟气中的CO2与CO2吸收剂反应生成有机盐以将烟气中的CO2脱除，吸收塔的塔底得到富胺液且塔顶得到脱除CO2的烟气；S1. Introduce the flue gas containing CO2 into the absorption tower from the bottom, and spray the CO2 absorbent into the absorption tower from top to bottom. The CO2 in the flue gas reacts with the CO2 absorbent to generate organic salt to remove the CO2 in the flue gas. The bottom of the absorption tower obtains rich amine liquid and the top of the tower obtains the flue gas with CO2 removed; S2、将富胺液引入解吸塔中进行CO2解吸，所述解吸塔以石墨烯基固体酸催化剂作为填料，产生的CO2气体自解吸塔顶排出；S2, introducing the rich amine solution into a desorption tower for CO2 desorption, wherein the desorption tower uses a graphene-based solid acid catalyst as a filler, and the generated CO2 gas is discharged from the top of the desorption tower; 所述石墨烯基固体酸催化剂以分子筛作为载体，以氧化石墨烯、WO3和TiO2作为活性组分。The graphene-based solid acid catalyst uses molecular sieve as a carrier and graphene oxide, WO 3 and TiO 2 as active components. 16.根据权利要求15所述的CO2烟气的处理方法，其特征在于，所述CO2吸收剂为有机胺。16. The method for treating CO2 flue gas according to claim 15, characterized in that the CO2 absorbent is an organic amine. 17.根据权利要求15所述的CO2烟气的处理方法，其特征在于，所述CO2解吸的温度为80~85℃。17. The method for treating CO2 flue gas according to claim 15, characterized in that the temperature of CO2 desorption is 80-85°C. 18.根据权利要求15所述的CO2烟气的处理方法，其特征在于，以所述石墨烯基固体酸催化剂的总重量为基准，所述载体的含量为30~80wt%，所述活性组分的含量为20~70wt%。18. The method for treating CO2 flue gas according to claim 15, characterized in that, based on the total weight of the graphene-based solid acid catalyst, the content of the carrier is 30-80wt%, and the content of the active component is 20-70wt%. 19.根据权利要求15所述的CO2烟气的处理方法，其特征在于，所述活性组分中氧化石墨烯、TiO2和WO3的质量比为(1~4):(7~21):7。19. The method for treating CO2 flue gas according to claim 15, characterized in that the mass ratio of graphene oxide, TiO2 and WO3 in the active components is (1~4):(7~21):7. 20.根据权利要求15所述的CO2烟气的处理方法，其特征在于，所述分子筛为H-ZSM-5。20. The method for treating CO2 flue gas according to claim 15, characterized in that the molecular sieve is H-ZSM-5. 21.权利要求15~20中任意一项所述的CO2烟气的处理方法，其特征在于，所述石墨烯基固体酸催化剂按照以下方法制备得到：将氧化石墨烯、WO3前驱体和TiO2前驱体于溶液中进行水热反应，再将水热反应产物和分子筛载体进行混合后烘干，即得石墨烯基固体酸催化剂。21. The method for treating CO2 flue gas according to any one of claims 15 to 20, characterized in that the graphene-based solid acid catalyst is prepared according to the following method: graphene oxide, WO3 precursor and TiO2 precursor are subjected to hydrothermal reaction in a solution, and then the hydrothermal reaction product and the molecular sieve carrier are mixed and dried to obtain the graphene-based solid acid catalyst. 22.根据权利要求21所述的CO2烟气的处理方法，其特征在于，所述水热反应的方式为将氧化石墨烯超声分散于水中，之后将所得分散液与有机溶剂I混合得到溶液A；将TiO2前驱体与有机溶剂II混合得到溶液B；将WO3前驱体与有机溶剂III混合得到溶液C；将溶液A、溶液B和溶液C混合后置于水热反应条件下进行反应。22. The method for treating CO2 flue gas according to claim 21, characterized in that the hydrothermal reaction is carried out by ultrasonically dispersing graphene oxide in water, then mixing the obtained dispersion with organic solvent I to obtain solution A; mixing TiO2 precursor with organic solvent II to obtain solution B; mixing WO3 precursor with organic solvent III to obtain solution C; and mixing solution A, solution B and solution C and reacting them under hydrothermal reaction conditions. 23.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述分散的时间为2~20h。23. The method for treating CO2 flue gas according to claim 22, characterized in that the dispersion time is 2 to 20 hours. 24.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述水热反应条件包括温度为120~250℃，时间为1~3d。24. The method for treating CO2 flue gas according to claim 22, characterized in that the hydrothermal reaction conditions include a temperature of 120-250°C and a time of 1-3 days. 25.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述WO3前驱体为钨酸盐。25. The method for treating CO2 flue gas according to claim 22, characterized in that the WO3 precursor is tungstate. 26.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述TiO2前驱体为钛酸盐。26. The method for treating CO2 flue gas according to claim 22, characterized in that the TiO2 precursor is titanate. 27.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述有机溶剂I为冰醋酸溶液。27. The method for treating CO2 flue gas according to claim 22, characterized in that the organic solvent I is a glacial acetic acid solution. 28.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述有机溶剂II为DMF和/或无水乙醇。28. The method for treating CO2 flue gas according to claim 22, characterized in that the organic solvent II is DMF and/or anhydrous ethanol. 29.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述有机溶剂III为盐酸溶液。29. The method for treating CO2 flue gas according to claim 22, characterized in that the organic solvent III is a hydrochloric acid solution. 30.根据权利要求22所述的CO2烟气的处理方法，其特征在于，所述烘干的条件包括温度为50~120℃。30. The method for treating CO2 flue gas according to claim 22, characterized in that the drying condition includes a temperature of 50-120°C.
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