CN115069068A - Rapid low-energy-consumption CO capture by catalyzing tertiary amine solvent with hydrotalcite catalyst 2 Method (2) - Google Patents
Rapid low-energy-consumption CO capture by catalyzing tertiary amine solvent with hydrotalcite catalyst 2 Method (2) Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 35
- 239000002904 solvent Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005265 energy consumption Methods 0.000 title claims abstract description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 11
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- QUDBKQDNUJKSAM-UHFFFAOYSA-N 4-(diethylamino)butan-2-ol Chemical compound CCN(CC)CCC(C)O QUDBKQDNUJKSAM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- BHUXAQIVYLDUQV-UHFFFAOYSA-N 1-(diethylamino)propan-2-ol Chemical compound CCN(CC)CC(C)O BHUXAQIVYLDUQV-UHFFFAOYSA-N 0.000 claims description 4
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 claims description 4
- ALOCUZOKRULSAA-UHFFFAOYSA-N 1-methylpiperidin-4-amine Chemical compound CN1CCC(N)CC1 ALOCUZOKRULSAA-UHFFFAOYSA-N 0.000 claims description 4
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- NGWSAUQBWVWFCU-UHFFFAOYSA-N n-ethyl-2,3-dimethylbutan-2-amine Chemical compound CCNC(C)(C)C(C)C NGWSAUQBWVWFCU-UHFFFAOYSA-N 0.000 claims description 4
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 claims description 2
- IVDAATCYGBHDGS-UHFFFAOYSA-N 2,3,3-trimethyl-n-propylbutan-2-amine Chemical compound CCCNC(C)(C)C(C)(C)C IVDAATCYGBHDGS-UHFFFAOYSA-N 0.000 claims description 2
- MMMLPDNJYOPBDC-UHFFFAOYSA-N 2-aminoheptan-3-ol Chemical compound CCCCC(O)C(C)N MMMLPDNJYOPBDC-UHFFFAOYSA-N 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- PEFWXSRIUUGCOT-UHFFFAOYSA-N N-butyl-2,3,3-trimethylpentan-2-amine Chemical compound CC(C(NCCCC)(C)C)(CC)C PEFWXSRIUUGCOT-UHFFFAOYSA-N 0.000 claims description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- XBRDBODLCHKXHI-UHFFFAOYSA-N epolamine Chemical compound OCCN1CCCC1 XBRDBODLCHKXHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 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 claims 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims 2
- 102000003846 Carbonic anhydrases Human genes 0.000 abstract description 11
- 108090000209 Carbonic anhydrases Proteins 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 114
- 229910002092 carbon dioxide Inorganic materials 0.000 description 57
- 239000001569 carbon dioxide Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 19
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 13
- 150000003141 primary amines Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- -1 carbamate ions Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
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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
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20431—Tertiary amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a method for capturing CO rapidly with low energy consumption 2 The method specifically adopts a hydrotalcite catalyst to catalyze a tertiary amine solvent to capture CO 2 . Compared with the conventional tertiary amine solvent CO 2 The absorption process, the method provided by the invention can greatly improve CO 2 Absorption rate and thus low energy consumption of CO 2 And (5) a capturing process. Compared with the prior art, the catalyst is cheap and easy to obtain; catalytic tertiary amine solvent CO 2 The absorption performance is excellent, and the cycle stability is excellent; the reaction condition is mild, and the operation is simple and convenient; hydrotalcite like catalysisThe agent has the advantages of large surface area, porosity, high hydrothermal stability, good indication of alkaline sites and the like, can replace expensive and volatile carbonic anhydrase and other catalysts, and has good social and economic benefits.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to hydrotalcite catalysisFast low-energy-consumption CO capture by catalyst tertiary amine solvent 2 The method of (1).
Background
The large combustion of fossil energy sources discharges excess carbon dioxide (CO) into the atmosphere 2 ) This is an important cause of the greenhouse effect. At present, the organic amine solution chemical absorption method has the advantages of large absorption capacity, small equipment investment, low price, high maturity and the like, and is considered to be CO most likely to be applied to a coal-fired power plant in a short period 2 A trapping technique. However, the existing organic amine absorption process has the defects of high energy consumption, solvent degradation, equipment corrosion and the like. Wherein, the regeneration energy consumption of the primary amine absorbent accounts for 60 percent of the total capture cost, thereby reducing CO 2 The key to the capture cost to promote further industrial application of the organic amine solvent is to reduce the energy consumption for regeneration of the organic amine solvent.
Organic amines are classified into primary amines, secondary amines and tertiary amines according to the number of hydrogen atoms bonded to nitrogen atoms in the molecule. Typical primary amines are Monoethanolamine (MEA), CO 2 Chemically reacts with the MEA to form carbamate ions. Primary amine solvent CO 2 The absorption rate is high, but because carbamate is difficult to break, the desorption energy consumption is overlarge, and the problem is the bottleneck problem of the wide application of the two types of absorbents in industry at present. In addition, primary amine solvents have disadvantages such as low absorption capacity and easy degradation of the solvent. The secondary amine solvent can absorb CO at higher temperature although having difficult degradation and higher boiling point 2 But has the disadvantages of low absorption rate, low removal efficiency, high price, etc. Tertiary amine solvents such as N-Methyldiethanolamine (MDEA), on the other hand, are not directly bound to CO 2 The reaction proceeds but promotes CO by a base-catalyzed mechanism 2 Hydration reactions ultimately produce carbonic acid, bicarbonate, and protonated amines. Since carbonate and bicarbonate are unstable, they are easily decomposed to produce CO 2 Therefore, the energy consumption for the regeneration of the tertiary amine solvent is low, and the tertiary amine solvent also has CO 2 Large absorption capacity, excellent degradation resistance and the like. Thus, tertiary amine solvents are a very promising class of low energy CO 2 An absorbent. However, due to absorption of CO by the tertiary amine solvent 2 Too slow, limiting its large-scale practical application.
For tertiary amine solvent CO 2 The problem of too low absorption rate, researchers have suggested that Carbonic Anhydrase (CA) catalysts can effectively accelerate CO 2 Hydration rate, reduction of CO 2 The enthalpy of absorption. CA catalyzed CO 2 The ability of hydration to form HCO 3-has been demonstrated by a number of studies, and CA is known to catalyze CO 2 The enzyme with the fastest hydration rate (Wu et al, Chinese J. chem. Eng.,2020,28(11), 2817-2831.). For example, Shen et al propose that the CA enzyme is embedded in the nanoparticles of ZIF-L to form a novel CA/ZIF-L-1 composite material and used for CO 2 Absorption process, the composite material is to CO 2 Shows better catalytic activity (Shen et al, appl. energy 2018,230, 726-733). Power et al developed a core-shell magnetic ZIF-8@ Fe3O 4-carbonic anhydrase composite material to promote absorption of CO by tertiary amine 2 Performance, the catalytic performance of CA @ ZIF8@ Fe3O4 was investigated for three particle sizes. The results show that the relative catalytic activity of CA @ ZIF-8@ Fe3O4 can be as high as 95.2% (Power et al, environ. Sci. technol.2016,50 (5); 2610-2618). However, the low thermal stability, poor cycle performance and high price of CA itself have limited its industrial application (Luis et al, j.co) 2 Util.,2021,47,101475；Rasouli et al.,Sep.Purif.Technol.2022,296,121299)。
Therefore, the development of a catalyst that is inexpensive, efficient and excellent in stability for promoting the tertiary amine solvent CO 2 Absorption performance, high absorption rate and low energy consumption of CO 2 The capture method has very important theoretical significance and application value.
Disclosure of Invention
Aiming at overcoming the defects of the prior art, the invention aims to provide a method for capturing CO quickly with low energy consumption 2 The method specifically adopts a hydrotalcite catalyst to catalyze a tertiary amine solvent to capture CO 2 . Compared with the conventional tertiary amine solvent CO 2 The absorption process, the method provided by the invention can greatly improve CO 2 Absorption rate and thus low energy consumption of CO 2 And (5) a capturing process. The main reason for this is that the addition of an alkaline hydrotalcite-like catalyst, based on the base catalysis mechanism, can provide CO 2 Basic sites required for hydration reactionsPromoting CO 2 The hydration reaction is promoted by the tertiary amine solvent CO 2 The rate of absorption.
CO used in the invention 2 The absorption system comprises catalyst and tertiary amine aqueous solution, and the absorption system contains CO 2 Introducing the gas of (A) into an absorption system, CO 2 Is firstly dissolved and then is absorbed by catalytic hydration, and finally the CO is captured 2 The purpose of (1).
The catalyst adopted by the invention can be one or more of magnesium aluminum hydrotalcite (Mg/Al-LDH) and corresponding composite oxide (Mg/Al-LDO), calcium aluminum hydrotalcite (Ca/Al-LDH) and corresponding composite oxide (Ca/Al-LDO), but the Mg/Al-LDH is preferably used.
The amount of the catalyst used in the present invention is in the range of 0 to 5% by weight, preferably 1 to 2% by weight, and more preferably 1.25% by weight, based on the mass ratio of the tertiary amine aqueous solution.
The reaction temperature adopted by the invention is 25-50 ℃.
The tertiary amine solvent used in the present invention may be MDEA, Dimethylaminoethanol (DMEA), 4-diethyl-2-butanol (DEAB), 1-diethylamino-2-propanol (1DEA2P), 1- (2-hydroxyethyl) pyrrolidine (1- (2-HE) PRLD), 1- (2-hydroxyethyl) piperidine (1- (2-HE) PP), 4-ethyl-methyl-amino-2-butanol (EMAB), Triethanolamine (TREA), Triethylamine (TEA), 4-diethylamino-2-butanol (DEAB), 3-dimethylamino-1-propanol (3DMA1P), 1-dimethylamino-2-propanol (1DMA2P), N-methyl-4-piperidine (MPDL), One or more kinds of mixed solvents of amines such as Tetramethyldiethylamine (TMEDA), Tetramethyldipropylamine (TMPDA), Tetramethyldibutylamine (TMBDA), 4-amino-1-methylpiperidine (4-A1MPD), and N, N-Diethylethanolamine (DEEA), but it is preferable to use MDEA solvent.
The mass ratio of the tertiary amine solvent contained in the tertiary amine aqueous solution adopted by the invention is 10-40 wt%.
The gas containing CO2 is flue gas discharged by a coal-fired power plant, the content of CO2 is 10-20 vol%, and the content of N2 is 85-90 vol%.
The technology mainly has the following advantages:
(1) the catalyst is cheap and easy to obtain.
(2) Catalytic tertiary amine solvent CO 2 The absorption performance is excellent, and the cycling stability is excellent.
(3) The reaction condition is mild, and the operation is simple and convenient.
(4) The hydrotalcite catalyst has the advantages of large surface area, porosity, high hydrothermal stability, good indication of alkaline sites and the like, can replace expensive and volatile carbonic anhydrase and other catalysts, and has good social and economic benefits.
Drawings
FIG. 1 shows the catalysis of tertiary amine solution CO by the catalyst in the example 2 Absorption rate profile.
FIG. 2 shows the catalysis of tertiary amine solution CO by the catalyst in the example 2 Absorption capacity graph.
FIG. 3 shows an X-ray diffraction pattern of the catalyst in the example.
FIG. 4 shows an infrared spectrum of the catalyst in the example.
FIG. 5 shows the nitrogen isothermal adsorption and desorption curves of the catalyst in the examples.
FIG. 6 shows CO absorption by a tertiary amine solution in examples 2 Schematic illustration of the apparatus.
Detailed Description
Example 1: preparation and catalytic performance test of Mg/Al-LDO (magnesium/aluminum) -Ca/Al-LDO (calcium/aluminum) -catalyst
(1) Preparing a catalyst: placing 5g of Mg/Al-LDH and Ca/Al-LDH catalysts in a crucible and placing the crucible in a muffle furnace, and roasting for 3h at 500 ℃ to obtain the Mg/Al-LDO and Ca/Al-LDO catalysts.
(2) Catalyst characterization: subjecting the obtained catalyst to X-ray diffraction analysis, infrared spectroscopy and N 2 Adsorption and desorption curves and the like.
(3) And (3) testing the catalytic performance: catalyst for catalyzing tertiary amine solution CO 2 The absorption experimental set-up is shown in FIG. 4. The experimental procedure is described below: weighing a certain amount of MDEA solution in a 1L volumetric flask for constant volume, and shaking the solution uniformly to obtain a 20% MDEA solution. 200ml of 20% MDEA solution was measured in a three-necked flask using a measuring cylinder, and 2.5g of Mg/Al-LDH was weighed in the MDEA solution using an electronic balance. Two mass flow devices are used and,separate control of CO 2 And N 2 The flow rate of (2) was 500mL/min, and the total flow rate was 1000 mL/min. The valve is opened to a double channel to introduce CO 2 And N 2 Mix for 5min and then pour into MDEA solution. The glass tube connected with the three-neck flask is a sand core glass tube, so that CO can be introduced 2 The MDEA solution was taken in as small dispersed bubbles while opening the magneton stirrer at 500rpm to more uniformly mix the solution and gas. The mixed gas passing through the MDEA solution passes through a drying tube to remove entrained water and prevent CO from being treated by the mixed gas 2 The measurement of the content has an influence. Introducing the dried mixed gas into CO 2 Detection apparatus, recording CO 2 The outlet volume fraction, the absorption temperature was set at 25 ℃ and the experimental duration was set at 1 h.
Example 2:
the difference from the catalytic performance test in example 1 is that the tertiary amine solution absorbs CO 2 The catalyst added in the process is Mg/Al-LDH.
Comparative example:
the difference from the catalytic performance test in example 1 is that the tertiary amine solution absorbs CO 2 No catalyst was added.
TABLE 1 catalysts of the examples and comparative examples catalyze the absorption of CO by tertiary amine solutions 2 Instantaneous ramp-up rate and CO 2 Instantaneous lift comparison
| Absorption time(s) | Catalyst and process for preparing same | Instantaneous Rate of Lift (%) |
| |
0 | |
| 545/1055 | Mg/Al-LDH | 102.0/38.6 |
| 2145/2560 | Mg/Al-LDO | 17.7/7.7 |
| 3385/3585 | Ca/Al-LDO | 23.0/0.5 |
As can be seen from Table 1, FIGS. 1 and 2, the ratio of CO to the blank MDEA solution is determined 2 In the absorption process, the addition of the alkaline catalyst obviously improves the CO content of the MDEA solution 2 Absorption rate and absorption capacity, wherein the addition of Mg/Al-LDH catalyst can promote CO 2 The instantaneous absorption rate was 102%.
Claims (6)
1. Rapid and low-energy-consumption CO capture 2 The process of (1) containing CO 2 Introducing the gas of (A) into an absorption system, CO 2 Is firstly dissolved and then is absorbed by catalytic hydration, and finally the CO is captured 2 The purpose of (1). Characterized in that the capture process comprises a catalyst and an aqueous solution of a tertiary amine. The catalyst can be one or more of magnesium aluminum hydrotalcite (Mg/Al-LDH) and corresponding composite oxide (Mg/Al-LDO), calcium aluminum hydrotalcite (Ca/Al-LDH) and corresponding composite oxide (Ca/Al-LDO), but Mg/Al-LDH is preferably used.
2. The capturing method according to claim 1, wherein the catalyst is used in an amount of 0 to 5 wt%, preferably 1 to 2 wt%, and more preferably 1.25 wt% based on the mass ratio of the tertiary amine aqueous solution.
3. The capture method of claim 1, wherein the temperature of the absorption reaction is 25-50 ℃.
4. The capturing method of claim 1, wherein the tertiary amine solvent is selected from the group consisting of MDEA, Dimethylaminoethanol (DMEA), 4-diethyl-2-butanol (DEAB), 1-diethylamino-2-propanol (1DEA2P), 1- (2-hydroxyethyl) pyrrolidine (1- (2-HE) PRLD), 1- (2-hydroxyethyl) piperidine (1- (2-HE) PP), 4-ethyl-methyl-amino-2-butanol (EMAB), Triethanolamine (TREA), Triethylamine (TEA), 4-diethylamino-2-butanol (DEAB), 3-dimethylamino-1-propanol (3DMA1P), 1-dimethylamino-2-propanol (1DMA2P), One or more kinds of amine mixed solvents such as N-methyl-4-piperidine (MPDL), Tetramethyldiethylamine (TMEDA), Tetramethyldipropylamine (TMPDA), Tetramethyldibutylamine (TMBDA), 4-amino-1-methylpiperidine (4-A1MPD), and N, N-Diethylethanolamine (DEEA), but the use of MDEA solvent is preferred.
5. The capturing method according to claim 1, wherein the mass ratio of the tertiary amine aqueous solution is 10 to 40 wt%.
6. The capture process of claim 1, wherein the capture process comprises CO 2 The gas is flue gas, CO, discharged from coal-fired power plants 2 The content of N is 10-20 vol% 2 The content is 85-90 vol%.
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| CN115805004A (en) * | 2022-11-15 | 2023-03-17 | 大唐环境产业集团股份有限公司 | Application of 4-amino-1-piperidinepropanol as carbon dioxide absorbent |
| CN117861410A (en) * | 2024-03-11 | 2024-04-12 | 中太海碳(上海)环保科技有限公司 | Carbon dioxide absorbent containing nanoscale hydrotalcite and application thereof |
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