CN117717877A - Porous carbon dioxide absorbent and carbon dioxide separation method - Google Patents
Porous carbon dioxide absorbent and carbon dioxide separation method Download PDFInfo
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- CN117717877A CN117717877A CN202410053626.2A CN202410053626A CN117717877A CN 117717877 A CN117717877 A CN 117717877A CN 202410053626 A CN202410053626 A CN 202410053626A CN 117717877 A CN117717877 A CN 117717877A
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- carbon dioxide
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- imidazole
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- 239000002250 absorbent Substances 0.000 title claims abstract description 83
- 230000002745 absorbent Effects 0.000 title claims abstract description 82
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 58
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 17
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000013043 chemical agent Substances 0.000 claims abstract description 15
- -1 alcohol amine Chemical class 0.000 claims abstract description 11
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 239000003623 enhancer Substances 0.000 claims abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 25
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 3
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 claims description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims 1
- 238000003795 desorption Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 31
- 239000006096 absorbing agent Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 238000007599 discharging Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a porous carbon dioxide absorbent and a carbon dioxide separation method. The composition of the absorbent comprises 1-10% of solid phase and 90-99% of liquid phase based on 100% of the total mass of the absorbent; wherein the solid phase is a particulate enhancer; the composition of the liquid phase comprises 5% -40% of a specific chemical agent and 60% -95% of water, based on 100% of the total mass of the liquid phase; the specific chemical agent comprises one or more than two of imidazole substances, imidazole ionic liquid, piperazine substances and alcohol amine substances. The porous absorbent provided by the invention is used for absorbing CO 2 Has better absorption heat/dynamics performance and lower desorption heat, and can realize the effect of absorbing CO in the water-containing mixed gas 2 And the components are trapped efficiently and with low consumption.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a porous carbon dioxide absorbent and a carbon dioxide separation method.
Background
CO 2 Trapping, utilization and sequestration (CCUS) are currently the only emission abatement technology that can achieve large-scale low-carbonization utilization. Currently, CO 2 The trapping technical route mainly comprises post-combustion trapping, pre-combustion trapping and oxygen-enriched fuel combustion trapping. Post-combustion capture is a relatively widely and mature technology in industry due to its simplicity of operation and the lack of excessive modification to existing power plants. Alcohol amine solution in CO 2 Can quickly absorb CO when partial pressure is low 2 And to CO 2 High selectivity, is the most widely used CO 2 The trapping agent is the most challenging to use, but is corrosive, easily degradable and energy-consuming to regenerate. Therefore, a low energy consumption and high efficiency CO is sought 2 Absorbent for reducing CO 2 The emission is of vital importance.
In recent years, metal Organic Frameworks (MOFs) have great development prospects in the field of gas separation due to the advantages of multiple active sites, large active surface area, controllable pore shape, adjustable porosity and the like, and Zeolite Imidazole Frameworks (ZIFs) as subclasses of MOFs have higher thermal stability, chemical stability and excellent separation capacity. Since ZIFs and other MOFs materials are finely divided powdered solids, and are in gaseous communication withIs easily blown off when touched, and thus cannot be directly used for CO 2 And continuously trapping the gas. The slurry method separation technology (absorption-adsorption coupling separation technology) proposed by the current Chen Guangjin subject group is to suspend the ZIF-8 material in a solvent containing a specific chemical agent to form porous slurry, so that continuous operation and heat integration can be realized while the separation selectivity is higher. However, because a single absorbent has the difficult requirements of high absorption capacity, high absorption rate, low reaction heat and the like, the combination of the compounding characteristics of the MOF material and a specific chemical agent is still needed at present so as to realize the high capacity and the selectivity of the solid absorbent while achieving low desorption heat.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a porous carbon dioxide absorbent.
The invention also aims to provide a method for separating carbon dioxide.
In order to achieve the above object, the present invention provides a porous carbon dioxide absorbent, wherein the composition of the absorbent comprises 1% -10% of solid phase and 90% -99% of liquid phase, based on 100% of the total mass of the absorbent; wherein the solid phase is a particulate enhancer; the composition of the liquid phase comprises 5% -40% of a specific chemical agent and 60% -95% of water, based on 100% of the total mass of the liquid phase.
In the absorbent, the specific chemical agent preferably includes one or a combination of two or more of an imidazole substance, an imidazole ionic liquid, a piperazine substance, and an alcohol amine substance.
In the above absorbent, preferably, the particle strengthening agent includes one or a combination of two or more of zinc carbonate, basic zinc carbonate, zinc oxide, zinc chloride, and zinc hydroxide.
In the above absorbent, the solid phase is preferably added in an amount of 1.5% to 5%.
In the above absorbent, preferably, the specific chemical agent forms a network porous structure in water.
The porous CO provided by the invention 2 The liquid phase in the absorbent is composed of water and waterThe self-assembled molecule is formed after the chemical agent is mixed, and the specific chemical agent can form a net-shaped porous structure. The porous CO 2 The absorbent can be stable at low temperature (0-50deg.C) and can make CO 2 Stably adsorbed in the porous structure, gradually decomposed at a higher temperature (above 60 ℃) and released the adsorbed CO 2 。
In the above absorbent, the specific chemical agent is preferably added in an amount of 20% to 40% based on 100% of the total mass of the liquid phase.
In the absorbent, preferably, the imidazole substance includes one or a combination of two or more of imidazole, 2-methylimidazole, 1-methylimidazole, 2-ethylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
In the above absorbent, preferably, the imidazole-based ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate [ BMIM ]][BF 4 ]1-hexyl-3-methylimidazole tetrafluoroborate [ HMIM ]][BF 4 ]1-hexyl-3-methylimidazole hexafluorophosphate [ HMIM ]][PF 6 ]1-ethyl-3-methyl imidazole chloride [ EMIM ]][Cl]1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt [ EMIM ]][TF 2 N]One or a combination of two or more of them.
In the above absorbent, preferably, the piperazine-based substance includes one or a combination of two or more of Piperazine (PZ), 1- (2-aminoethyl) piperazine (AEP), N- (2-hydroxyethyl) piperazine (HEPZ), 1-methylpiperazine (1-MPZ), and 2-methylpiperazine (2-MPZ).
In the above absorbent, preferably, the alcohol amine substance includes one or a combination of two or more of Diethanolamine (DEA), N-Methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), hydroxyethyl ethylenediamine (AEEA), diethylenetriamine (DETA), N-Methylcyclohexylamine (MCA), triethanolamine (TEA).
According to a specific embodiment of the present invention, the preparation method of the porous carbon dioxide absorbent comprises the following steps: mixing the particle strengthening agent, the specific chemical agent and water according to a certain proportion, and uniformly stirring to obtain dispersed and stable slurry.
The invention also provides a carbon dioxide separation method, wherein the method is to utilize the porous carbon dioxide absorbent to carry out CO 2 And (5) capturing.
In the above separation method, preferably, the separation method is to realize CO 2 And N 2 CO in a mixed gas of (a) 2 Is separated from the other components.
In the above separation method, it is preferable to perform CO 2 The absorption temperature at the time of trapping is 0-50 ℃.
In the above separation method, it is preferable to perform CO 2 The absorption pressure during trapping is 0.1-1MPa.
In the above separation method, preferably, the method further comprises capturing CO under vacuum heating 2 CO obtained thereafter 2 And desorbing the rich liquid, and then regenerating the lean liquid for recycling.
In the above separation method, preferably, the temperature of the heating is 60 to 100 ℃.
In the above separation method, preferably, the absolute pressure of the vacuum is 80kPa or less.
The porous absorbent of the invention is used for absorbing CO 2 The material has better heat absorption/dynamics performance (large absorption capacity and high absorption rate) and lower heat absorption; compared with the traditional MOF-based porous liquid, the prepared slurry absorbent has good dispersibility and stability and lower energy consumption for conveying, and can realize the CO in the aqueous mixed gas 2 And the components are trapped efficiently and with low consumption.
Drawings
FIG. 1 is a graph of CO in example 1 of the present invention 2 Solubility and absorption rate evaluation plots.
FIG. 2 is a graph of regeneration solution versus CO in example 2 of the present invention 2 Thermodynamic and kinetic experimental results of absorption.
FIG. 3 is a graph of CO in example 3 of the present invention 2 Desorption heat evaluation chart.
FIG. 4 is a pilot scale CO in example 5 of the present invention 2 /N 2 Schematic of the continuous separation apparatus.
FIG. 5 is a cryoelectron micrograph of absorber V of example 1.
Reference numerals illustrate:
401 CO 2 gas cylinder
402. Air compressor
403. Gas buffer tank
404. Absorption tower inlet infrared CO 2 Monitor device
405. Infrared CO at outlet of absorption tower 2 Monitor device
406. Water ring vacuum pump
407. Absorption tower
408. Desorption tower
409. Centrifugal pump
410. Liquid adding tank
411. Temperature sensor
412. Mass flowmeter
413. Metering pump
414. Pressure transmitter
415. Mixer
416. Liquid buffer tank
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The small test devices are all devices recorded in ZL201910327202.X and are used for thermodynamic and kinetic experiments of pure gas and mixed gas. For data processing of relevant gas solubility experiments and separation experiments, see paragraphs 0030-0048 of the specification of zl201910327202.X (CN 111821812 a).
Porous CO in embodiments of the invention 2 The preparation method of the absorbent comprises the following steps: mixing the granule strengthening agent, specific chemical agent and water at a certain ratio, stirringThe slurry is uniformly dispersed and stabilized.
Example 1
The present embodiment provides a set of porous CO 2 The absorbent is respectively as follows: an absorber I, an absorber II, an absorber III, an absorber IV, and an absorber V;
the porous CO is adopted 2 The absorbent is prepared by the preparation method of the absorbent, wherein the composition of the absorbent I is (30% of 1-methylimidazole and the balance of water) based on 100% of the total mass of the solution;
the composition of the absorbent II is (30% of 1-methylimidazole+5% of MDEA+the balance of water);
the composition of absorbent III was (30% 1-methylimidazole+5% hepz+balance water);
the composition of the absorbent IV was (2.5% basic zinc carbonate +97.5% liquid phase); wherein, based on 100% of the total mass of the liquid phase, the liquid phase comprises (30% of 1-methylimidazole+5% of MDEA+the balance of water);
the composition of the absorbent V is (2.5% basic zinc carbonate+97.5% liquid phase); wherein the liquid phase comprises (30% 1-methylimidazole+5% HEPZ+balance water) based on 100% of the total mass of the liquid phase.
The cryoelectron microscope of the absorbent V is shown in fig. 5, and a net-like porous structure is formed as seen in fig. 5.
At an absorption temperature of 30 ℃, pure CO is used 2 The gas was used as a raw material gas, and the absorption capacity (CO 2 Solubility) and absorption rate, and the results are shown in fig. 1. In fig. 1, (a) is an absorption capacity test result, (b) is an absorption rate test result, the abscissa is an absorption pressure, and the ordinate is a value of an absorption amount at the corresponding pressure. As can be seen from fig. 1, the addition of the particle reinforcement helps to increase the absorption capacity and absorption rate of the absorbent, with superior absorption heat/kinetics.
The following tests CO 2 The heat of desorption in the above-mentioned absorbent II, absorbent III, absorbent IV, and absorbent V, and the test results are shown in Table 1 and FIG. 3.
TABLE 1 mean heat of absorption for different absorbents
From the experimental results of table 1 and fig. 3, it can be seen that: the absorbent IV and the absorbent V to which the particle enhancer is added have lower heat of desorption than the absorbent II and the absorbent III to which the particle enhancer is not added.
Example 2
The present embodiment provides a porous CO 2 An absorbent VI;
the porous CO is adopted 2 Preparation method of absorbent VI the composition of absorbent VI was (1.5% basic zinc carbonate +98.5% liquid phase) based on 100% total mass of solution; wherein the liquid phase comprises (30% 1-methylimidazole+5% HEPZ+balance water) based on 100% of the total mass of the liquid phase.
To verify whether the absorbent in this example was reusable for CO 2 Trapping with pure CO 2 The gas was used as a raw gas, and the absorbent VI was used for CO multiple times 2 The absorption-desorption operation was performed to examine its recyclability. When CO 2 After the absorption experiment is completed, desorbing the rich solution for 20min at the temperature of 80 ℃ and the desorption pressure of 80kPa, and continuously carrying out CO on the obtained lean solution 2 The trapping experiment, the experimental results are shown in figure 2. In fig. 2, (a) is an absorption capacity test result, and (b) is an absorption rate test result.
Under the desorption condition, after repeated absorption-desorption cycle tests, the separation performance of the absorbent VI is slightly reduced compared with that of fresh solution, but the absorption capacity and the absorption rate after the 2 nd regeneration tend to be stable, the repeated cyclic utilization is not obviously reduced, and the absorbent VI has excellent repeated use performance.
Example 3
The present embodiment provides a set of porous CO 2 The absorbent is respectively as follows: absorber VII, absorber VIII, absorber IX;
the porous CO is adopted 2 Preparation method of absorbent the absorbent was prepared wherein the composition of absorbent VII was based on 100% of the total mass of the solutionIs (20% of [ HMIM ]][BF 4 ]+10% 1-methylimidazole+balance water);
absorbent VIII composition (20% HMIM][BF 4 ]+10% hepz+balance water);
absorbent IX consisted of (2.5% basic zinc carbonate +97.5% liquid phase); wherein the liquid phase composition is (20% of [ HMIM ] based on 100% of the total mass of the liquid phase][BF 4 ]+10% hepz+balance water).
At an absorption temperature of 30 ℃, pure CO is used 2 The gas was used as feed gas to test for CO in absorbent VII, absorbent VIII, absorbent IX 2 The absorption amounts and the experimental results are shown in Table 2.
TABLE 2 absorption test results for different absorbents
| Temperature (. Degree. C.) | Pressure (MPa) | Absorbent agent | Absorption capacity (mol/mol) |
| 40 | 3 | Absorbent VII | 0.79 |
| 40 | 3 | Absorbent VIII | 0.82 |
| 40 | 3 | Absorbent IX | 0.85 |
From the experimental results in table 2, it can be seen that: the absorbent IX with added particle enhancer has a larger CO 2 Absorption amount.
Example 4
The present embodiment provides a CO 2 Method for separating gas, which is to realize CO 2 /N 2 Continuous separation:
firstly, preparing a slurry, wherein the raw materials of the slurry comprise 30% of 1-methylimidazole, 5% of 1- (2-aminoethyl) piperazine and 2.5% of basic zinc carbonate, and the balance of water.
The slurry absorbent was used as a separation medium for continuous separation experiments. FIG. 4 is a schematic flow chart of a trapping liquid for continuous carbon trapping.
The device comprises CO 2 Gas cylinder 401, air compressor 402, gas buffer tank 403, absorber inlet infrared CO 2 Monitor 404, absorber outlet infrared CO 2 Monitor 405, water ring vacuum pump 406, absorption tower 407, desorption tower 408, centrifugal pump 409, liquid charging tank 410, temperature sensor 411, mass flowmeter 412, metering pump 413, pressure transmitter 414, mixer 415, liquid buffer tank 416.
Wherein CO 2 The gas cylinder 401 and the air compressor 402 are used for supplying raw gas, and are joined to the same pipe by the mixer 415 and then connected to the tank inlet of the absorption tower 407, and CO 2 A one-way valve and a gas buffer tank 403 are arranged between the gas cylinder 401 and the mixer 415, a pressure reducing valve and a liquid buffer tank 416 are arranged between the air compressor 402 and the mixer 415, and an infrared CO inlet of the absorption tower is arranged between the mixer 415 and the tower kettle inlet of the absorption tower 407 2 A monitor 404, a mass flow meter 412; the one-way valve is used for controlling the flow direction of the raw material gas and avoiding backflow; the pressure reducing valve is used for controlling the pressure of the raw material gas; absorption tower inlet infrared CO 2 Monitor 404 is used to monitor the CO in the mixed gas entering the absorber 2 Is a concentration of (2); quality of the bodyThe flowmeter 412 is used for measuring the amount of gas entering the absorption tower 407 and controlling parameters such as flow rate;
the inner diameter of the absorption tower 407 is 66mm, the height of the packing is 2.5m, the maximum working pressure is 1MPa, and the theta-ring random packing is placed in the tower; the tower bottom, the tower body and the tower top of the absorption tower 407 are respectively provided with a plurality of temperature sensors 411 for monitoring the temperatures of the corresponding positions; the top of the absorption tower 407 is also provided with an infrared CO at the outlet of the absorption tower 2 A monitor 405 for monitoring CO in the mixed gas leaving the absorption tower 2 Is a concentration of (2);
the tower bottom outlet of the absorption tower 407 is connected with the tower top inlet of the desorption tower 408, and a pressure transmitter 414, a liquid discharge valve and a centrifugal pump 409 are sequentially arranged on the connecting pipelines of the two; the pressure transmitter is used for measuring the pressure of the rich liquid leaving from the bottom of the absorption tower 407, and the liquid discharge valve is used for discharging the slurry in the absorption tower 407;
the inner diameter of the desorption tower 408 is 66mm, the height of the packing is 2.5m, the maximum working pressure is 0.5MPa, and the theta-ring random packing is placed in the tower; the upper section and the middle section of the desorption tower are provided with electric heating and heat preservation, the heating power is 1kW, and a plurality of temperature sensors 411 are arranged at proper positions of the desorption tower 408 and used for monitoring the temperatures at corresponding positions;
the top inlet of the desorber 408 is connected to the inlet of the water ring vacuum pump 406 to provide vacuum operating conditions for the desorber 408; a liquid discharge valve is arranged at the outlet of the desorption tower 408, the outlet is connected with the inlet of a metering pump 413, and a liquid adding tank 410 is arranged on the connecting pipeline of the outlet and the metering pump; wherein, the liquid adding tank 410 is used for pumping the trapping liquid into the absorption tower and replenishing new trapping liquid before the experiment starts, and the metering pump 413 is used for pumping the trapping liquid of the desorption tower into the absorption tower;
the outlet of the metering pump 413 is connected with the top inlet of the absorption tower 407, and a mass flowmeter 412 and the metering pump 413 are sequentially arranged on the connecting pipelines of the metering pump 413 and the absorption tower; wherein the mass flowmeter 412 is configured to measure the flow rate of the captured liquid;
the lean liquid after the desorption by the desorption column 408 is completed is returned to the absorption column 407 via a metering pump; through multiple circulation, the absorbent is used for absorbing CO 2 /N 2 And (3) separating the mixed gas.
The influence of gas-liquid ratio on separation was also examined in this example, and the specific results are shown in Table 3.
TABLE 3 separation test results for different gas-liquid ratios
In table 3:
V in-mix gas for the flow rate of the mixed gas,is a gas-liquid ratio, C out-CO2 For the outlet CO of the absorption tower 2 Concentration, deltaS V For cyclic absorption capacity, η is CO 2 Removal rate.
From the data in table 3, it can be seen that: the technical proposal of the invention can well realize CO 2 Is adsorbed and separated.
Claims (10)
1. A porous carbon dioxide absorbent, wherein the composition of the absorbent comprises, based on 100% of the total mass of the absorbent, 1% -10% of a solid phase, and 90% -99% of a liquid phase;
wherein the solid phase is a particulate enhancer;
the composition of the liquid phase comprises 5% -40% of a specific chemical agent and 60% -95% of water, based on 100% of the total mass of the liquid phase;
the specific chemical agent comprises one or more than two of imidazole substances, imidazole ionic liquid, piperazine substances and alcohol amine substances.
2. The absorbent of claim 1, wherein the particulate reinforcement comprises one or a combination of two or more of zinc carbonate, basic zinc carbonate, zinc oxide, zinc chloride, zinc hydroxide;
preferably, the solid phase is added in an amount of 1.5% -5%.
3. The absorbent of claim 1, wherein the specific chemical forms a network-like porous structure in water;
preferably, the specific chemical agent is added in an amount of 20% to 40% based on 100% of the total mass of the liquid phase.
4. The absorbent according to claim 1 or 3, wherein the imidazole-based substance comprises one or a combination of two or more of imidazole, 2-methylimidazole, 1-methylimidazole, 2-ethylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.
5. An absorbent according to claim 1 or 3, wherein the imidazole-based ionic liquid comprises one or a combination of two or more of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt.
6. The absorbent according to claim 1 or 3, wherein the piperazine-based substance comprises one or a combination of two or more of piperazine, 1- (2-aminoethyl) piperazine, N- (2-hydroxyethyl) piperazine, 1-methylpiperazine, and 2-methylpiperazine.
7. The absorbent according to claim 1 or 3, wherein the alcohol amine substance comprises one or a combination of two or more of diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, hydroxyethyl ethylenediamine, diethylenetriamine, N-methylcyclohexylamine, triethanolamine.
8. A method for separating carbon dioxide, wherein the method comprises CO using the porous carbon dioxide absorbent according to any one of claims 1 to 7 2 Capturing;
preferably, the separation method is to realize CO 2 And N 2 CO in a mixed gas of (a) 2 Is separated from the other components.
9. Root of Chinese characterThe separation method according to claim 8, wherein CO is carried out 2 The absorption temperature during trapping is 0-50 ℃;
preferably, CO is performed 2 The absorption pressure during trapping is 0.1-1MPa.
10. The separation method according to claim 8, wherein the method further comprises capturing the CO under vacuum heating 2 CO obtained thereafter 2 Desorbing the rich liquid, and then regenerating the lean liquid for recycling;
preferably, the temperature of the heating is 60-100 ℃;
preferably, the absolute pressure of the vacuum is 80kPa or less.
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