CN113210021B - Transition metal-based composite catalyst for promoting desorption of carbon dioxide rich solution, and preparation method and application thereof - Google Patents
Transition metal-based composite catalyst for promoting desorption of carbon dioxide rich solution, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000003795 desorption Methods 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 11
- 239000001569 carbon dioxide Substances 0.000 title description 11
- 239000007788 liquid Substances 0.000 claims abstract description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 238000001354 calcination Methods 0.000 claims description 7
- 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
- 238000005406 washing Methods 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000012621 metal-organic framework Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 13
- 239000002841 Lewis acid Substances 0.000 abstract description 8
- 150000007517 lewis acids Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 8
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 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 10
- -1 Alcohol amine Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 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 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 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
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 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
- 230000007812 deficiency 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
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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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- 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 CO 2 A transition metal-based composite catalyst desorbed by rich liquid, a preparation method and application thereof relate to the technical field of catalyst processing. The invention synthesizes a composite material with MOFs as a base material and simultaneously comprises
And CO at Lewis acid sites 2 Desorbing solid acid catalyst-phosphotungstic acid modified cerium-based MOF derivative material (CeO) 2 MOF HPW), i.e., transition metal based composite catalyst. The invention is realized by
And Lewis acid double-position regulation and control, which is CeO 2 MOF HPW catalyst as proton donor to promote CO 2 Proton transfer in regeneration reaction, thereby realizing CO 2 High-efficiency desorption.
Description
Technical Field
The invention belongs to the technical field of catalyst processing, and in particular relates to a catalyst for promoting CO 2 A transition metal-based composite catalyst desorbed by rich liquid, a preparation method and application thereof.
Background
Alcohol amine solution absorption method represented by ethanolamine (MEA) is currently internationally commercialized CO 2 The trapping technology has the advantages of large absorption capacity, high trapping efficiency and the like, and is suitable for large smoke CO of coal-fired power plants 2 And (5) capturing. The trapping process comprises two processes of absorption and desorption which are reversible reactions, because of alcohol amine and CO 2 The bonding effect of the catalyst is extremely strong, and the absorption product needs to be desorbed under the temperature condition of 110-130 ℃, so that the technology has the difficult problem of overlarge energy consumption, wherein CO 2 The desorption energy consumption accounts for more than half of the whole process of the trapping technology, so that the existing cost is obviously increased, and the large-scale popularization and application are difficult.
In addition, during the high-temperature desorption process of the absorption product, MEA is easy to volatilize to cause a great deal of loss of the absorbent, and secondary pollution and equipment corrosion are easy to cause. Thus due to CO 2 The total energy consumption caused by difficult desorption of the absorption products is too high, and is the CO in the flue gas 2 The capture-alcohol amine absorption process is currently faced with a bottleneck problem.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a method for promoting CO 2 The transition metal-based composite catalyst is synthesized by taking MOFs as a base material and simultaneously comprises the following components
And CO at Lewis acid sites 2 Desorbing solid acid catalyst-phosphotungstic acid modified cerium-based MOF derivative material (CeO) 2 MOF HPW). By passing through
And Lewis acid double-position regulation and control, which is CeO 2 MOF HPW catalyst as proton donor to promote CO 2 Proton transfer in regeneration reaction, thereby realizing CO 2 High-efficiency desorption.
The invention is used for promoting CO 2 The preparation method of the transition metal-based composite catalyst desorbed from the rich liquid comprises the following steps:
1) 4.2g of 1,3, 5-trimellitic acid was added to an aqueous ethanol solution to prepare a solution A:
2) 8.68g Ce (NO) 3 ) 3 ·6H 2 Adding O into water to prepare solution B:
3) Heating the solution A to 60 ℃, pouring the solution B, and rapidly stirring for 1h;
4) Filtering and collecting precipitate, and washing and drying the precipitate;
5) Calcining the dried product in a muffle furnace at 350 ℃ for 2 hours to obtain a calcined product;
6) Adding a proper amount of water into the calcined product for dispersion treatment, and 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, and then filtering and drying to obtain the transition metal-based composite catalyst.
Preferably, the aqueous methanol solution of step 1) consists of 20mL H 2 O and 20mL of ethanol.
Preferably, the B solution of step 2) is a solution of 8.68g Ce (NO) 3 ) 3 ·6H 2 Adding 90mL of H to O 2 O is prepared.
Preferably, the washing agent used in step 4) to wash the precipitate is ethanol.
Preferably, step 4) is carried out on the washed precipitate for 8 hours at a temperature of 70 ℃.
Preferably, the temperature rise rate of the muffle furnace in step 5) is 5 ℃/min.
Preferably, the drying temperature in step 6) is 100 ℃ and the drying time is 8 hours.
The invention also aims to provide an application method of the transition metal-based composite catalyst, namely, the flue gas (the main gases are carbon dioxide and nitrogen) is blown into an ethanolamine solution for absorption, and the ethanolamine rich solution is obtained after saturation; and then 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 CO 2 Depending on the number of active hydrogen atoms on the nitrogen atom, it can be classified into primary amines (e.g., MEA ethanolamine), secondary amines (e.g., DEA) and tertiary amines (e.g., MDEA). Primary amines (exemplified by MEA) with CO 2 The reaction rate is the fastest, and a carbamate with relatively stable properties can be formed, so that CO is absorbed by the MEA solution 2 The resulting rich liquor had the worst regeneration performance. MEA and CO 2 The reaction first produces a zwitterionic intermediate which is then reacted with a base to deprotonate to form the stable carbamate. Secondary amine and CO 2 The reaction principle is about the same, but the reaction rate is slower than that of primary amine, and the reaction equation is as follows:
RNH 2 +RNH 2 + COO － →RNHCOO － +RNH 3 +
tertiary amines have no active hydrogen atoms on the nitrogen atom and therefore cannot be directly reacted with CO 2 And (3) reacting. CO 2 It must be dissolved in water to activate the hydrogen atom before it reacts with the MEDA. Tertiary amine absorption of CO 2 The reaction speed is slowest in the three alcohol amine absorption liquids, so that better effect can be achieved in the aspect of desorption.
In addition, alcohol amine and CO are mixed 2 The reaction has chemical reaction cross interaction, and tertiary amine can also react with primary amine and CO 2 The resulting proton reaction:
RNH 2 + COO － +R 3 N→RNHCOO － +R 3 NH +
CO 2 +H 2 O+R 2 CH 3 N→R 2 CH 3 NH + +HCO 3 -
2RNH 2 +RNH 2 + COO － +CO 2 →RNHCOO － +RNH 3 + +RNH 2 + COO －
alcohol amine absorption liquid CO of the invention 2 The desorption mechanism is the reverse process of the absorption process. The project synthesizes a composite material with MOFs as a base material and simultaneously has the following functions
And CO at Lewis acid sites 2 Desorbing solid acid catalyst-phosphotungstic acid modified cerium-based MOF derivative material (CeO) 2 MOF HPW). Respectively introducing phosphotungstic acid and cerium oxide into the catalyst as
Acid and Lewis acid, and based on double acid site regulation, ceO is prepared 2 MOF HPW catalyst as CO 2 Regeneration of reacted proton donors by promoting CO 2 Proton transfer in regeneration reaction, and CO in MEA rich solution is realized 2 And (5) 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 frame structure MOFs, has a three-dimensional pore structure, takes metal ions as connection points, supports organic ligands to form space 3D extension, is another important novel porous material except 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 canal, adjustable pore diameter, various 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 cerium-based MOF material;
the transition metal-based composite catalyst is utilized to desorb the ethanolamine rich liquid containing carbon dioxide, so that the desorption temperature can be reduced, the desorption rate is greatly improved, and the energy absorption and absorption consumption can be reduced.
Drawings
FIG. 1 shows CeO prepared in example 1 of the present invention 2 Microstructure of_mof_hpw;
FIG. 2 shows CeO prepared in example 1 of the present invention 2 X-ray diffraction pattern of MOF HPW;
FIG. 3 is a graph of CO employed in example 1 of the present invention 2 A desorption apparatus diagram;
FIG. 4 is a schematic diagram of CO according to the present invention 2 A desorption rate variation map;
FIG. 5 is a schematic diagram of CO according to the present invention 2 A maximum desorption rate comparison plot;
FIG. 6 is a graph of the CO of the present invention 2 The desorption amount varies with time;
FIG. 7 is a graph of CO in MEA rich solution 2 Concentration and initial CO 2 The concentration ratio varies.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
A catalyst for desorbing the enriched ethanolamine solution containing carbon dioxide is a transition metal-base composite catalyst (CeO) 2 MOF HPW), the preparation method is as follows:
1) 4.2g of 1,3, 5-benzenetricarboxylic acid was added to the aqueous ethanol solution (from 20mL of H 2 O and 20mL ethanol) to prepare a solution a:
2) 8.68g Ce (NO) 3 ) 3 ·6H 2 O was added to 90mL of water to make solution B:
3) Heating the solution A to 60 ℃, pouring the solution B, and rapidly stirring for 1h;
4) The precipitate was collected by filtration, washed with ethanol and then dried at 70 ℃ for 8 hours;
5) Calcining the dried product in a muffle furnace at a heating rate of 5 ℃/min and a calcining temperature of 350 ℃ for 2 hours to obtain a calcined product;
6) In the calcination processAdding a proper amount of water into the 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 100 ℃ for 8h to obtain CeO 2 Mof_hpw catalyst.
Through detection, the CeO prepared by the invention 2 Specific surface area of the_MOF_HPW catalyst was 80.45m 2 And/g, average pore diameter of 1.35nm. The pore size is far greater than MEA and CO 2 The molecular diameter is convenient for the reactants and the products to shuttle in the pore canal of the catalyst and is CO 2 The desorption reaction provides a large number of active sites.
FIG. 1 shows the observation of CeO by a transmission electron microscope 2 Microstructure of_MOF_HPW, ceO can be observed from the figure 2 the_MOF_HPW catalyst presents a strip structure, wherein black particles are CeO 2 . And further amplified to obtain a lattice spacing of 0.3nm, which is attributed to CeO 2 The (111) crystal face of (2) is consistent with XRD characterization result, further explaining CeO 2 Is successfully introduced into and is CO 2 The desorption reaction provides Lewis acid sites to promote CO 2 And (5) desorption.
FIG. 2 is CeO 2 -MOF-HPW X-ray diffraction pattern. As can be seen from the figure, 8 diffraction peaks were observed at diffraction angles 28 °, 33 °, 46 °, 57 °, 69 °, 77 °, 79 °, 88 °. The diffraction peaks are attributed to CeO by using MDI Jade 6 analysis results and comparing PDF card library 2 Is a cerium oxide structure, and illustrates CeO 2 The active component in the_MOF_HPW catalyst is CeO 2 。
Comparative example 1
A catalyst for desorbing the rich ethanolamine solution containing carbon dioxide is CeO 2 。
Comparative example 2
Catalyst (CeO) for desorbing ethanolamine rich liquid containing carbon dioxide 2 MOF), the preparation steps are as follows:
1) 4.2g of 1,3, 5-benzenetricarboxylic acid was added to the aqueous ethanol solution (from 20mL of H 2 O and 20mL ethanol) to prepare a solution a:
2) Will be 8.68g Ce(NO 3 ) 3 ·6H 2 O was added to 90mL of water to make solution B:
3) Heating the solution A to 60 ℃, pouring the solution B, and rapidly stirring for 1h;
4) The precipitate was collected by filtration, washed with ethanol and then dried at 70 ℃ for 8 hours;
5) Calcining the dried product in a muffle furnace at a heating rate of 5 ℃/min and a calcining temperature of 350 ℃ for 2 hours to obtain a calcined product, namely CeO 2 _MOF。
The ethanolamine rich solution was desorbed using the catalysts of example 1 and comparative examples 1 to 2. First-built CO 2 The desorption device is shown in figure 3, and simulates the flue gas to be formed by N 2 And CO 2 The gas is prepared, the flow rate is controlled by a mass flowmeter, and the gas is introduced into a constant temperature reaction device to enable the MEA to absorb CO 2 CO when catalyst is added 2 The desorption starts, the gas is introduced into a drying bottle after cold water bath and finally enters a gas phase analysis instrument to obtain CO 2 Real-time concentration of gas. The specific operation is as follows:
firstly, the volume ratio is 1: n of 1 2 And CO 2 Is 400 mL/min -1 Is bubbled into 200mL of 30wt% MEA solution, MEA versus CO 2 Is the saturation (CO) reached at room temperature 25℃and atmospheric pressure 2 Load of 0.53mol CO 2 /mol amine,30wt% MEA); then adding a catalyst, wherein the mass concentration of the catalyst in the reaction system is 1.00wt%, and the carbon dioxide desorption reaction temperature is 88 ℃. At the same time, a blank group is added (i.e. no catalyst is added for desorption)
As can be seen from fig. 4 to 5, the catalyst of comparative example 1 can increase the desorption efficiency of carbon dioxide to 3.72mmol/min during the desorption of carbon dioxide relative to the blank group; the catalyst of comparative example 2 gave a catalytic efficiency of 4.57mmol/min; the catalyst of the embodiment 1 of the invention has the catalytic efficiency reaching 4.87mmol/min and approaching twice of the blank catalytic efficiency, and shows the excellent catalytic capability.
Meanwhile, the operation temperature of the experiment is 88 ℃, belongs to catalysis under the condition of low temperature, and the conventional thermal desorption temperature is 110 ℃, and a certain amount of heating is needed, so that the addition of the catalyst greatly reduces the desorption temperature of the MEA, and therefore, the CeO 2 The MOF-HPW can significantly reduce the energy consumption required for the reaction.
According to the following formula, it can be seen that at 88℃desorption temperature, non-catalytic condition CO 2 The desorption amount was 151mmol, ceO 2 CO under the catalysis of MOF-HPW 2 The desorption amount was 178mmol. Calculated as CO under non-catalytic conditions 2 The energy consumption of desorption reaction is used as a reference, ceO is adopted 2 -MOF-HPW catalysis of CO 2 During the desorption reaction, the required relative desorption energy consumption is 85%, and is reduced by 15% compared with the non-catalytic condition.
Wherein nCO 2 Represents CO at t minutes 2 Desorption amount (mmol); VN (virtual machine) 2 (t) is a carrier gas N 2 Flow rate (mL/min); x: CO 2 Percentage (V/V,%); vm: molar volume of gas (L/mol); dr: CO of MEA solution 2 Desorption rate (mmol/s); alpha CO 2 Representing CO at time t during desorption 2 Concentration of(mol CO 2 /amime); h: MEA regeneration energy consumption (kJ/mol); hi/Hbenchmark; catalytic/non-catalytic regeneration of CO 2 Desorption (kJ/mol); RH: MEA regeneration relative energy consumption (%). Therefore, the catalyst prepared in the embodiment 1 of the invention can improve the desorption rate, reduce the production energy consumption of an MEA carbon dioxide desorption method, and is more energy-saving and environment-friendly.
As can be seen from FIGS. 6 to 7, CO 2 The desorption was faster before 60 minutes, and then the desorption rate was retarded and the desorption amount was slowly increased. In addition, for non-catalytic CeO 2 、CeO 2 MOF and CeO 2 CO under the action of-MOF-HPW 2 Desorption reaction of CO 2 The arrangement sequence of the desorption amount is CeO 2 -MOF-HPW＞CeO 2 -MOF＞CeO 2 ＞Blank，CeO 2 The catalytic action of the-MOF-HPW catalyst is most remarkable, and the catalyst is used for catalyzing CO 2 The desorption amount may be as high as 178mmol. In addition, the experimental operating temperature is 88 ℃ which is far lower than the conventional thermal desorption temperature of 110 ℃, so the CeO of the invention 2 The MOF-HPW can significantly reduce the energy consumption required for the reaction.
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (10)
1. Promoting CO 2 The preparation method of the transition metal-based composite catalyst desorbed from the rich liquid is characterized by comprising the following preparation steps:
1) 4.2g of 1,3, 5-trimellitic acid was added to an aqueous ethanol solution to prepare a solution A:
2) 8.68g Ce (NO) 3 ) 3 ·6H 2 Adding O into water to prepare solution B:
3) Heating the solution A to 60 ℃, pouring the solution B, and rapidly stirring for 1h;
4) Filtering and collecting precipitate, and washing and drying the precipitate;
5) Calcining the dried product in a muffle furnace at 350 ℃ for 2 hours to obtain a calcined product;
6) Adding a proper amount of water into the calcined product for dispersion treatment, and 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, and then filtering and drying to obtain the transition metal-based composite catalyst.
2. The promotion of CO of claim 1 2 The preparation method of the transition metal-based composite catalyst by rich liquid desorption is characterized in that the ethanol aqueous solution in the step 1) is prepared from 20mL of H 2 O and 20mL of ethanol.
3. The promotion of CO of claim 1 2 A process for preparing a transition metal-based composite catalyst by desorption of rich liquid, characterized in that in step 2) the solution B is prepared by dissolving 8.68g Ce (NO) 3 ) 3 ·6H 2 Adding 90mL of H to O 2 O is prepared.
4. The promotion of CO of claim 1 2 The preparation method of the transition metal-based composite catalyst desorbed from the rich liquid is characterized in that the washing agent adopted in the step 4) for washing the precipitate is ethanol.
5. The promotion of CO of claim 1 2 The preparation method of the transition metal-based composite catalyst desorbed from the rich liquid is characterized in that the step 4) is to dry the washed precipitate for 8 hours at the temperature of 70 ℃.
6. The promotion of CO of claim 1 2 The preparation method of the transition metal-based composite catalyst for rich liquid desorption is characterized in that the temperature rising rate of the muffle furnace in the step 5) is 5 ℃/min.
7. The promotion of CO of claim 1 2 A preparation method of a transition metal-based composite catalyst desorbed from rich liquid is characterized in thatThe drying temperature in the step 6) is 100 ℃, and the drying time is 8 hours.
8. Promoting CO 2 A transition metal-based composite catalyst desorbed from a rich liquid, characterized by being prepared by the preparation method according to any one of claims 1 to 7.
9. The promotion of CO of claim 8 2 The application of the transition metal-based composite catalyst for desorbing the rich liquid is characterized in that the flue gas is blown into an ethanolamine solution for absorption, and the ethanolamine rich liquid is obtained after saturation; and then 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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