CN113210021A - Transition metal-based composite catalyst for promoting carbon dioxide pregnant solution desorption, and preparation method and application thereof - Google Patents
Transition metal-based composite catalyst for promoting carbon dioxide pregnant solution desorption, and preparation method and application thereof Download PDFInfo
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- 238000003795 desorption Methods 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 23
- 239000001569 carbon dioxide Substances 0.000 title description 11
- 239000000243 solution Substances 0.000 claims description 58
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011156 metal matrix composite Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 239000002841 Lewis acid Substances 0.000 abstract description 9
- 150000007517 lewis acids Chemical class 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000011973 solid acid Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000005265 energy consumption Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- -1 alcohol amine Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- 241000931197 Themeda Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910000175 cerite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a method for promoting CO2A transition metal-based composite catalyst desorbed by rich solution, a preparation method and application thereof relate to the technical field of catalyst processing. The invention takes MOFs as a base material to synthesize a composite material simultaneously having
And CO at the Lewis acid site2Desorption of solid acid catalysisAgent-phosphotungstic acid modified cerium-based MOF derived material (CeO)2MOF _ HPW), i.e., a transition metal-based composite catalyst. The invention is provided with
And Lewis acid is controlled in two positions and is CeO2MOF HPW catalyst as proton donor for CO promotion2Proton transfer in regeneration reactions to achieve CO2And (4) high-efficiency desorption.
Description
Technical Field
The invention belongs to the technical field of catalyst processing, and particularly relates to a method for promoting CO2Transition metal-based composite catalyst desorbed by rich solution, and preparation method and application thereof.
Background
The absorption method of alcohol amine solution represented by ethanolamine (MEA) is the CO which is currently internationally commercialized2The process has the advantages of large absorption capacity, high capture efficiency and the like, and is suitable for large-smoke-volume CO of a coal-fired power plant2And (4) trapping. The trapping process includes two mutually reversible reaction processes of absorption and desorption, and the alcohol amine and CO react2The bonding effect is very strong, and the absorption product needs to be desorbed under the temperature condition of 110-130 ℃, so that the technology has the problem of excessive energy consumption, wherein CO2The desorption energy consumption accounts for more than half of the whole process of the trapping process, so that the existing cost is obviously increased, and the large-scale popularization and application are difficult.
In addition, during the desorption of the absorption product at high temperature, the MEA is easy to volatilize to cause great loss of the absorbent, and secondary pollution and equipment corrosion are easy to cause. Therefore, due to CO2The absorption product is over-high in total energy consumption due to difficult desorption, namely CO in the flue gas2The bottleneck problem of the capture-alcohol amine absorption method is faced at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for promoting CO2The transition metal-based composite catalyst for rich solution desorption is synthesized by taking MOFs as a base material
And CO at the Lewis acid site2Desorption solid acid catalyst-phosphotungstic acid modified cerium-based MOF (CeO)2MOF _ HPW). By passing
And Lewis acid is controlled in two positions and is CeO2MOF HPW catalyst as proton donor for CO promotion2Proton transfer in regeneration reactions to achieve CO2And (4) high-efficiency desorption.
The method for promoting CO2The preparation method of the transition metal-based composite catalyst desorbed by rich solution comprises the following steps:
1) adding 4.2g of 1,3, 5-benzene tricarboxylic acid into an ethanol water solution to prepare a solution A:
2) 8.68g of Ce (NO)3)3·6H2Adding O into water to prepare a solution B:
3) heating the solution A to 60 ℃, pouring the solution B into the solution A, and rapidly stirring for 1 h;
4) filtering and collecting the precipitate, and washing and drying the precipitate;
5) placing the dried product in a muffle furnace for calcining for 2h at the calcining temperature of 350 ℃ to obtain a calcined product;
6) adding a proper amount of water into the calcined product for dispersion treatment, then adding a phosphotungstic acid aqueous solution, wherein the mass ratio of the phosphotungstic acid to the calcined product is 15:100, stirring and mixing for 20min, filtering, and drying to obtain the transition metal matrix composite catalyst.
Preferably, the methanol aqueous solution in the step 1) is prepared from 20mL of H2O and 20mL of ethanol.
Preferably, the B solution in step 2) is at 8.68g Ce (NO)3)3·6H2O to which 90mL of H was added2And O.
Preferably, the detergent used for washing the precipitate in step 4) is ethanol.
Preferably, step 4) dries the washed precipitate at a temperature of 70 ℃ for 8 h.
Preferably, the temperature rise rate of the muffle furnace in the step 5) is 5 ℃/min.
Preferably, the drying temperature in the step 6) is 100 ℃, and the drying time is 8 h.
The invention also aims to provide an application method of the transition metal-based composite catalyst, namely, smoke (main gases are carbon dioxide and nitrogen) is blown into an ethanolamine solution for absorption, and an ethanolamine rich solution is obtained after saturation; and adding the transition metal-based composite catalyst, and desorbing at the temperature of 80-90 ℃ to realize the desorption of the ethanolamine rich solution.
Preferably, the mass concentration of the transition metal-based composite catalyst in the ethanolamine rich solution is 1%.
The action mechanism of the invention is as follows:
alcohol amine method for capturing CO2They can be classified into primary amines (e.g., MEA-ethanolamine), secondary amines (e.g., DEA) and tertiary amines (e.g., MDEA) according to the number of active hydrogen atoms on the nitrogen atom. Primary amine (MEA) and CO2The reaction rate is fastest, and carbamate with relatively stable property can be formed, so that the MEA solution is used for absorbing CO2The resulting rich solution has the worst regeneration performance. MEA and CO2The reaction first produces a zwitterionic intermediate which is subsequently deprotonated by the action of a base to form a stable carbamate salt. Secondary amine with CO2The reaction principle is about the same, but the reaction rate is slower than that of primary amine, and the reaction equation is as follows:
RNH2+RNH2 +COO－→RNHCOO－+RNH3 +
tertiary amines having no active hydrogen atoms on the nitrogen atom and therefore not directly reacting with CO2And (4) reacting. CO 22Must be dissolved in water to activate hydrogen atoms before reacting with the MEDA. Absorption of CO by tertiary amines2In three alcoholsThe reaction speed in the amine absorption liquid is the slowest, so that a better effect can be achieved in the desorption aspect.
In addition, alcohol amine is mixed with CO2There is a cross-interaction of chemical reactions during the reaction, tertiary amines can also react with primary amines and CO2The generated protons react:
RNH2 +COO－+R3N→RNHCOO－+R3NH+
CO2+H2O+R2CH3N→R2CH3NH++HCO3 -
2RNH2+RNH2 +COO－+CO2→RNHCOO－+RNH3 ++RNH2 +COO－
the invention relates to an alcamines absorption liquid CO2The desorption mechanism is the reverse of the above absorption process. The project takes MOFs as a base material, synthesizes the MOFs with the MOFs
And CO at the Lewis acid site2Desorption solid acid catalyst-phosphotungstic acid modified cerium-based MOF (CeO)2MOF _ HPW). Respectively introducing phosphotungstic acid and cerium dioxide into the catalyst to obtain
Acid and Lewis acid, and based on dual acidity site regulation and control, CeO is prepared2MOF HPW catalyst as CO2Regenerating the proton donor of the reaction by promoting CO2The proton transfer in the regeneration reaction realizes the CO in the MEA rich solution2And (4) low-temperature high-efficiency desorption.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes transition metal cerium and organic ligand to bridge and form organic metal framework MOFs, has a three-dimensional pore structure, takes metal ions as connecting points, and supports the organic ligand to form space 3D extension, is another important novel porous material besides zeolite and carbon nano tubes, and has wide application in catalysis, energy storage and separation.
The transition metal-based composite catalyst has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structures and the like. In addition, the invention utilizes HPW (phosphotungstic acid) to modify the cerium-based MOF material so as to introduce Lewis acid sites and improve the catalytic activity of the Lewis acid sites;
the transition metal-based composite catalyst is used for desorbing the ethanolamine rich solution containing carbon dioxide, so that the desorption temperature can be reduced, the desorption rate is greatly increased, and the desorption energy consumption is reduced.
Drawings
FIG. 1 shows CeO prepared in example 1 of the present invention2A microstructure diagram of _ MOF _ HPW;
FIG. 2 shows CeO prepared in example 1 of the present invention2X-ray diffraction pattern of _ MOF _ HPW;
FIG. 3 shows CO used in example 1 of the present invention2A desorption device diagram;
FIG. 4 is a CO of the present invention2A plot of desorption rate change;
FIG. 5 shows a CO according to the present invention2Maximum desorption rate comparison plot;
FIG. 6 shows CO according to the present invention2The amount of desorption varied with time;
FIG. 7 shows CO in the MEA rich solution2Concentration and initial CO2The concentration ratio was varied.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The catalyst for desorbing ethanolamine rich liquid containing carbon dioxide is a transition metal-based composite catalyst (CeO)2MOF _ HPW) prepared as follows:
1) 4.2g of 1,3, 5-benzenetricarboxylic acid was added to an aqueous ethanol solution (from 20mL of H2O and 20mL ethanol) to prepare a solution a:
2) 8.68g of Ce (NO)3)3·6H2O into 90mL of waterPreparing a solution B:
3) heating the solution A to 60 ℃, pouring the solution B into the solution A, and rapidly stirring for 1 h;
4) filtering and collecting precipitate, washing the precipitate with ethanol, and drying at 70 deg.C for 8 hr;
5) placing the dried product in a muffle furnace for calcining at the heating rate of 5 ℃/min and the calcining temperature of 350 ℃ for 2h to obtain a calcined product;
6) adding a proper amount of water into the calcined product for dispersion treatment, then adding a phosphotungstic acid aqueous solution, wherein the mass ratio of the phosphotungstic acid to the calcined product is 15:100, stirring and mixing for 20min, filtering, and drying at the temperature of 100 ℃ for 8h to obtain CeO2MOF HPW catalyst.
Through detection, the CeO prepared by the invention2The specific surface area of the MOF HPW catalyst was 80.45m2In terms of a/g, the mean pore diameter is 1.35 nm. The pore diameter is far larger than that of MEA and CO2Molecular diameter is convenient for shuttling reactants and products in catalyst pore channels, and is CO2The desorption reaction provides a large number of active sites.
FIG. 1 is a view showing CeO observed by a transmission electron microscope2Microstructure of MOF HPW, from which CeO can be observed2The MOF-HPW catalyst has a strip structure, wherein the black particles are CeO2. And further amplified to obtain a lattice spacing of 0.3nm, which is classified as CeO2The result is consistent with the XRD characterization result, further illustrating the CeO crystal face2And is CO2The desorption reaction provides Lewis acid sites to promote CO2And (4) desorbing.
FIG. 2 shows CeO2-X-ray diffraction pattern of MOF-HPW. As can be seen from the figure, 8 diffraction peaks were observed at diffraction angles of 28 °, 33 °, 46 °, 57 °, 69 °, 77 °, 79 °, and 88 °. By comparing the MDI Jade 6 analysis results with the PDF card library, the diffraction peaks are all attributed to CeO2The structure of cerite of (A) illustrates CeO2The active component in the MOF-HPW catalyst is CeO2。
Comparative example 1
A pairThe catalyst for desorbing the ethanolamine rich solution containing carbon dioxide is CeO2。
Comparative example 2
Catalyst (CeO) for desorbing ethanolamine rich solution containing carbon dioxide2MOF) was prepared as follows:
1) 4.2g of 1,3, 5-benzenetricarboxylic acid was added to an aqueous ethanol solution (from 20mL of H2O and 20mL ethanol) to prepare a solution a:
2) 8.68g of Ce (NO)3)3·6H2O was added to 90mL of water to make solution B:
3) heating the solution A to 60 ℃, pouring the solution B into the solution A, and rapidly stirring for 1 h;
4) filtering and collecting precipitate, washing the precipitate with ethanol, and drying at 70 deg.C for 8 hr;
5) calcining the dried product in a muffle furnace at a heating rate of 5 ℃/min and a calcining temperature of 350 ℃ for 2h to obtain a calcined product, namely CeO2_MOF。
The ethanolamine rich solution was desorbed by using the catalysts of example 1 and comparative examples 1 to 2. CO constructed first2The desorption device is shown in figure 3, and the simulated flue gas is composed of N2And CO2Gas is prepared, the flow rate is controlled by a mass flowmeter, and the gas is introduced into a constant temperature reaction device to ensure that the MEA absorbs CO2When the catalyst is added, CO2Desorbing, introducing the gas into a drying bottle after the gas passes through a cold water bath, and finally introducing the gas into a gas phase analyzer to obtain CO2The real-time concentration of the gas. The specific operation is as follows:
firstly, mixing the following components in a volume ratio of 1: 1 is N2And CO2The mixture of (1) (simulated flue gas) at 400 mL. min-1Was bubbled into 200mL of a 30 wt% MEA solution, MEA vs CO2The absorption of (A) is the saturation (CO) achieved at room temperature at 25 ℃ and atmospheric pressure2The loading was 0.53mol CO2Per mol amine, 30 wt% MEA); then adding a catalyst, wherein the mass concentration of the catalyst in the reaction system is 1.00 wt%, and the carbon dioxide desorption reaction temperature is 88 ℃. While adding a blankControl group (i.e. desorption without any catalyst)
As can be seen from fig. 4 to 5, the catalyst of comparative example 1 can increase the carbon dioxide desorption efficiency to 3.72mmol/min relative to the blank control during the carbon dioxide desorption process; the catalyst of comparative example 2 gave a catalytic efficiency of 4.57 mmol/min; the catalyst of the embodiment 1 of the invention has the catalytic efficiency reaching 4.87mmol/min, which is close to twice of the blank catalytic efficiency, and shows the excellent catalytic capability.
Meanwhile, the operation temperature of the experiment is 88 ℃, the catalyst belongs to the catalysis under the condition of low temperature, and the conventional thermal desorption temperature is 110 ℃, and certain heating is needed, so that the addition of the catalyst greatly reduces the desorption temperature of MEA (membrane electrode assembly), and CeO (CeO)2The MOF-HPW can significantly reduce the energy consumption required for the reaction.
According to the following formula, it can be seen that CO is not catalytically present at a desorption temperature of 88 deg.C2Desorption amount was 151mmol, CeO2CO under MOF-HPW catalysis2The desorption amount was 178 mmol. Calculated as CO under non-catalytic conditions2The energy consumption of desorption reaction is taken as reference, CeO is adopted2MOF-HPW catalysis of CO2During desorption reaction, the required relative desorption energy consumption is 85 percent, which is reduced by 15 percent compared with the non-catalytic condition.
Wherein, nCO2Representing CO at t min2Desorption amount (mmol); VN2(t) is a carrier gas N2Flow rate of (mL/min); x: CO 22Percent (V/V,%); vm: molar volume of gas (L/mol); dr: CO of MEA solution2Desorption rate (mmol/s); alpha CO2Representing the CO at time t during desorption2Concentration (mol CO)2Trame); h: MEA regeneration energy consumption (kJ/mol); Hi/Hbenchmark; catalytic/non-catalytic regeneration of CO2Desorption (kJ/mol); RH: MEA regeneration relative energy consumption (%). Therefore, the catalyst prepared in the embodiment 1 of the invention improves the desorption rate, reduces the production energy consumption of the MEA carbon dioxide desorption method, and is more energy-saving and environment-friendly.
As can be seen from FIGS. 6 to 7, CO2The desorption was faster before 60 minutes, then the desorption rate slowed and the amount of desorption increased slowly. In addition, for non-catalytic, CeO2、CeO2MOF and CeO2CO by MOF-HPW2Desorption reaction of CO thereof2Desorption amount was in the order of CeO2-MOF-HPW＞CeO2-MOF＞CeO2＞Blank，CeO2The catalytic action of the-MOF-HPW catalyst is most remarkable, and CO is generated under the catalytic action2The desorption amount can reach 178 mmol. In addition, the running temperature of the experiment is 88 ℃, which is far lower than the conventional thermal desorption temperature by 110 ℃, so that the CeO of the invention2The MOF-HPW can significantly reduce the energy consumption required for the reaction.
It should be noted that the above-mentioned embodiments are merely examples of the present invention, and it is obvious that the present invention is not limited to the above-mentioned embodiments, and other modifications are possible. All modifications directly or indirectly derivable by a person skilled in the art from the present disclosure are to be considered within the scope of the present invention.
Claims (10)
1. Promoting CO2The preparation method of the transition metal-based composite catalyst desorbed by rich solution is characterized by comprising the following preparation steps：
1) Adding 4.2g of 1,3, 5-benzene tricarboxylic acid into an ethanol water solution to prepare a solution A:
2) 8.68g of Ce (NO)3)3·6H2Adding O into water to prepare a solution B:
3) heating the solution A to 60 ℃, pouring the solution B into the solution A, and rapidly stirring for 1 h;
4) filtering and collecting the precipitate, and washing and drying the precipitate;
5) placing the dried product in a muffle furnace for calcining for 2h at the calcining temperature of 350 ℃ to obtain a calcined product;
6) adding a proper amount of water into the calcined product for dispersion treatment, then adding a phosphotungstic acid aqueous solution, wherein the mass ratio of the phosphotungstic acid to the calcined product is 15:100, stirring and mixing for 20min, filtering, and drying to obtain the transition metal matrix composite catalyst.
2. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst desorbed by rich solution is characterized in that the methanol aqueous solution in the step 1) is prepared from 20mL of H2O and 20mL of ethanol.
3. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst with rich solution desorption is characterized in that the solution B in the step 2) is 8.68g of Ce (NO)3)3·6H2O to which 90mL of H was added2And O.
4. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst desorbed by the rich solution is characterized in that the detergent adopted for washing the precipitate in the step 4) is ethanol.
5. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst desorbed by rich solution is characterized in that the step 4) is carried out on the washed precipitate at the temperature of 70 DEG CDrying for 8 h.
6. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst desorbed by the pregnant solution is characterized in that the temperature rise rate of the muffle furnace in the step 5) is 5 ℃/min.
7. CO promotion according to claim 12The preparation method of the transition metal-based composite catalyst desorbed by the rich solution is characterized in that the drying temperature in the step 6) is 100 ℃, and the drying time is 8 hours.
8. Promoting CO2The transition metal-based composite catalyst desorbed in rich solution is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. CO promotion according to claim 82The application of the transition metal-based composite catalyst for rich solution desorption is characterized in that flue gas is blown into an ethanolamine solution for absorption, and an ethanolamine rich solution is obtained after saturation; and adding the transition metal-based composite catalyst, and desorbing at the temperature of 80-90 ℃ to realize the desorption of the ethanolamine rich solution.
10. The use according to claim 9, wherein the mass concentration of the transition metal-based composite catalyst in the ethanolamine rich solution is 1%.
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