CN113856412A - Method and device for desorbing carbon dioxide by using alcohol amine rich solution - Google Patents
Method and device for desorbing carbon dioxide by using alcohol amine rich solution Download PDFInfo
- Publication number
- CN113856412A CN113856412A CN202110984809.2A CN202110984809A CN113856412A CN 113856412 A CN113856412 A CN 113856412A CN 202110984809 A CN202110984809 A CN 202110984809A CN 113856412 A CN113856412 A CN 113856412A
- Authority
- CN
- China
- Prior art keywords
- membrane
- carbon dioxide
- alcohol amine
- ceramic membrane
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 74
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 62
- -1 alcohol amine Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 193
- 239000000919 ceramic Substances 0.000 claims abstract description 103
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000012466 permeate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011973 solid acid Substances 0.000 claims description 22
- 230000002209 hydrophobic effect Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000005086 pumping Methods 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 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QUDBKQDNUJKSAM-UHFFFAOYSA-N 4-(diethylamino)butan-2-ol Chemical compound CCN(CC)CCC(C)O QUDBKQDNUJKSAM-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 abstract description 46
- 150000001412 amines Chemical class 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 22
- 230000008929 regeneration Effects 0.000 abstract description 18
- 238000011069 regeneration method Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 6
- 238000005259 measurement Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 38
- 239000007789 gas Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 230000004048 modification Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000004907 flux Effects 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000002715 modification method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 108091006146 Channels Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VZEZONWRBFJJMZ-UHFFFAOYSA-N 3-allyl-2-[2-(diethylamino)ethoxy]benzaldehyde Chemical compound CCN(CC)CCOC1=C(CC=C)C=CC=C1C=O VZEZONWRBFJJMZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01D53/1418—Recovery of products
-
- 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
-
- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The utility model relates to a method and a device for desorbing carbon dioxide by using an alcohol amine rich solution. The hydrophilicity and hydrophobicity of the surface of the ceramic membrane are regulated, the modified ceramic membrane is applied to the desorption regeneration process of the alcohol amine solution rich in carbon dioxide, the carbon dioxide desorbed from the raw material amine solution permeates through membrane pores in a steam form, and a gas-phase product is collected through the steps of condensation, drying and the like after being detected by permeation, so that the effects of solvent regeneration and carbon dioxide separation and purification are achieved. Filling catalyst into porous single-channel ceramic membrane tube, assembling membrane contactor with ceramic membrane tube as main element, and performing liquid-solid catalytic reaction under the action of catalyst in membrane tube to obtain vapor (mainly CO) at gas-liquid interface2And H2O) permeation measurement capable of entering membrane contactor through membrane pores to realize CO2And (4) desorbing at low temperature. Utilizes the advantages that the ceramic membrane tube can be filled with solid catalyst and provides great gas-liquid mass transfer area, and strengthens the coupling of reaction and mass transferAnd (6) carrying out the process.
Description
Technical Field
The utility model relates to a technology for controlling regeneration and desorption of an enhanced alcohol amine solution rich in carbon dioxide, in particular to a method and a device for desorbing carbon dioxide by using an alcohol amine rich solution, and belongs to the technical field of separation processes.
Background
Realizing "carbon peak reaching" in 2030 and "carbon neutralization" in 2060 is a major strategy being initiated in china. The CCUS (carbon capture, utilization and sequestration) is an important choice for realizing the targets of 'carbon peak reaching' and 'carbon neutralization' in China. Carbon dioxide (CO)2) Capture in CO reduction2Plays a key role in emissions. Amine scrubbing is considered the most mature technology among the current carbon dioxide capture technologies, dominating industrial applications in the medium and short term. However, the solvent regeneration process remains a key challenge, accounting for approximately two thirds of the operating cost. Thus, any improvement in reducing energy usage will help reduce capture costs. Therefore, the method for capturing the carbon dioxide by the amine method with low cost has very important significance for the development of industrial process and the maintenance of ecological environment in China.
Chinese patent (CN112933879A) discloses a method for using CO in flue gas2The membrane absorption/desorption coupling method for separation includes desorption step, which includes desorbing with microporous membrane of selected pore structure, and applying certain vacuum degree to the membrane contactor for permeation measurement to make CO be adsorbed2Through vacuum extraction and enrichment, the fact that CO with the concentration of more than 43-46% can be obtained at the desorption side by using a membrane contactor is introduced2Enriching the gas. Chinese patent (CN101830462A) discloses a method for using chemical absorption and membrane desorption to combine CO from high-pressure mixed gas2The trapping method can reduce the energy consumption by more than 10 percent and reduce the equipment investment by more than 30 percent.
Disclosure of Invention
The utility model aims to solve the problem of CO2The problems of high desorption temperature, high energy consumption, low energy utilization rate and the like in the regeneration process of the absorbent alcohol amine solution are solved, the conditions that the membrane material cannot resist high temperature and the like in a harsh system are solved, and the application development of the membrane material in the field of desorption process is expanded. The solid acid catalyst is adopted to reduce the activation energy of the reaction, and the ceramic membrane tube is adopted to provide a filling place for the catalyst and provide a large gas-liquid mass transfer area.
A method for desorbing carbon dioxide by using alcohol amine rich liquid comprises the following steps:
pumping the alcohol amine rich solution absorbing the carbon dioxide into a ceramic membrane element, wherein a catalyst for desorbing the carbon dioxide in the alcohol amine rich solution is filled in the ceramic membrane element;
desorbing the carbon dioxide in the alcohol amine rich solution under the action of the catalyst, and allowing the desorbed carbon dioxide to permeate through the membrane layer of the ceramic membrane element to obtain carbon dioxide; and discharging the desorbed alcohol amine lean solution from the ceramic membrane element.
The alcohol amine compound adopted in the alcohol amine rich solution is one or a mixture of more of monoethanolamine, N-diethylethanolamine, methyldiethanolamine, 1-dimethylamino-2-propanol, alcohol amines such as tetraethylenepentamine, triethylenetetramine and ethylenediamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, piperazine, 4- (diethylamino) -2-butanol, Diethylenetriamine (DETA) and Diethylaminoethanol (DEAE).
The concentration range of the alcohol amine compound is 2-6 mol/L.
The catalyst is a solid acid catalyst.
The solid acid catalyst is a molecular sieve catalyst or a metal oxide catalyst.
The molecular sieve catalyst is HZSM-5; the metal oxide catalyst is selected from gamma-Al2O3、TiO2Or V2O5。
The ceramic membrane is tubular or multi-channel, and the diameter of the channel is 0.5-30 mm.
The average pore diameter of the ceramic membrane is 2-500 nm.
The contact angle of the membrane surface of the ceramic membrane to water drops is larger than 130 degrees.
The temperature in the ceramic membrane tube is 90-110 ℃; the operating pressure range is 70-400 kPa.
An apparatus for desorbing carbon dioxide from alcohol amine rich liquid comprises:
a membrane contactor comprising a hydrophobic separation membrane having a catalyst on the membrane surface for desorbing carbon dioxide.
The membrane contactor is a ceramic membrane.
The ceramic membrane is in a tubular or multi-channel structure; and the catalyst is filled in the channel.
The contact angle of the surface water drop of the hydrophobic separation membrane is larger than 130 degrees.
The average pore diameter of the hydrophobic separation membrane is 2-500 nm.
Further comprising:
the raw material tank is used for storing the alcohol amine rich solution;
and the feed liquid pump is used for pumping the materials in the feed tank into the membrane contactor.
Further comprising: and a liquid flow meter for measuring the flow rate of the feed liquid from the feed tank into the membrane contactor.
Further comprising: and the condenser pipe is connected to the permeation side of the membrane contactor and is used for condensing the permeation gas.
Further comprising: and the drying pipe is connected with the condensing pipe and is used for drying the condensed gas.
The drying tube is filled with a drying agent.
Further comprising: and the gas mass flow meter is connected with the drying pipe and used for obtaining the gas measuring flow in the drying pipe.
Further comprising: and the vacuum pump is connected to the permeation side of the membrane contactor and is used for applying negative pressure.
Further comprising: and the heating device is used for heating the materials in the raw material tank.
Advantageous effects
The ceramic membrane used in the utility model is subjected to hydrophobic modification by an organic surface grafting method, and a series of characterization means such as contact angles prove that the ceramic membrane has good hydrophobic performance, keeps higher permeation flux and excellent desorption performance in a long-term stability experiment, and can reduce the energy load by more than 30%; during operation, the catalyst in the membrane tube can perform catalytic desorption on the rich liquid in real time to generate CO2Can be discharged in real time through the film layer, and water or water vapor is not easy to permeate the film layer due to the hydrophobicity of the surface of the film, thereby achieving the regeneration of rich solution and the desorption of CO2The purpose of (1).
The ceramic membrane adopted by the utility model has high mechanical strength, large specific surface area, chemical stability resistance and thermal stability, and can be applied to a desorption system to realize the purpose of high-efficiency mass transfer. The performance is higher than that of the traditional desorption tower and the common membrane desorption process.
The utility model uses the coupling of the solid acid catalyst and the ceramic membrane to reduce the desorption of CO in the alcohol amine solution2The solid acid catalyst has the obvious effects of reducing reaction activation energy, reducing desorption temperature, improving desorption rate and reducing desorption energy consumption.
In the conventional amine process CO2And the trapping process is slightly modified on the basis of the trapping process, so that the cost is low.
Drawings
Fig. 1 is a diagram of a control device for regenerating and desorbing an enhanced carbon dioxide-rich alcohol amine solution adopted by the utility model. Wherein, 1, a raw material tank; 2. a feed liquid pump; 3. a liquid flow meter; 4. a membrane contactor; 5. a condenser tube; 6. a drying tube; 7. a gas mass flow meter; 8. a vacuum pump.
Fig. 2 is a schematic view of a membrane contactor used in the present invention.
FIG. 3 is a graph comparing the cycle capacity obtained with the apparatus compared to conventional membrane desorption conditions under the same conditions.
Detailed Description
As shown in fig. 1, the utility model provides a desorption regeneration control device for strengthening a carbon dioxide-rich alcohol amine solution. Comprises the following steps: the device comprises a raw material tank, a raw material liquid pump and a liquid flowmeter, wherein the liquid flowmeter is connected with a raw material liquid inlet of a ceramic membrane contactor, and the permeation side of the ceramic membrane contactor is connected with a condensing pipe, a drying pipe, a gas mass flowmeter and a vacuum pump; the internal element of the ceramic membrane contactor is a single-channel ceramic membrane tube, the membrane layer of the ceramic membrane is hydrophobic, and a solid acid type catalyst is filled in the ceramic membrane tube. The surface hydrophilicity and hydrophobicity of the single-channel ceramic membrane is regulated by utilizing an organic matter surface grafting modification method, the modified ceramic membrane is applied to the desorption regeneration process of the alcohol amine solution rich in carbon dioxide, carbon dioxide (containing water molecules) desorbed from the raw material amine solution penetrates through membrane pores in a steam form, and a gas-phase product passes through the membrane pores from the raw material amine solutionAfter the permeation is detected, the solvent is collected through the steps of condensation, drying and the like, so that the effects of solvent regeneration and carbon dioxide separation and purification are achieved. The coupling of solid acid type catalyst and ceramic membrane is a new technology combining catalytic reaction and membrane process. And filling a catalyst into the porous single-channel ceramic membrane tube, and assembling the membrane contactor by using the ceramic membrane tube as a main element. The process occurring within the membrane contactor is: inputting the alcohol amine solution in the reboiler into a membrane contactor, and carrying out liquid-solid catalytic reaction under the action of a catalyst in a membrane tube; since the membrane has a porous structure, the vapor (mainly CO) at the gas-liquid interface2And H2O) can enter the membrane contactor through the membrane hole, and the permeation can be purified and collected along the pipeline to realize CO2And (4) desorbing at low temperature.
The desorption performance of the ceramic membrane contactor adopted by the method for the regeneration process of the alcohol amine solution is obviously superior to that of the treatment process adopting conventional tower equipment, and the permeation flux is improved by more than 67.2 percent compared with that of the conventional membrane desorption process. The method fully utilizes the advantages that the catalyst can reduce the reaction activation energy, reduce the regeneration temperature and improve the reaction rate, and utilizes the advantages that the ceramic membrane tube can be filled with the solid catalyst and provides a large gas-liquid mass transfer area, the coupling process of reaction and mass transfer is strengthened, and the effects of high efficiency and energy saving in the regeneration process of the alcohol amine solution rich in carbon dioxide are achieved.
The utility model provides a desorption regeneration control device for a reinforced alcohol amine solution rich in carbon dioxide, which is mainly used for desorbing and regenerating the alcohol amine solution rich in carbon dioxide by using a ceramic membrane filled with a solid acid catalyst and subjected to hydrophobic modification on a membrane layer, wherein a membrane contactor comprises at least 1 ceramic membrane tube or a plurality of pipelines, and the diameter range of a membrane channel is 0.5-30 mm. In order to increase the packing area of the device, the membrane layer of the ceramic membrane is preferably located on the inner wall of the channel. The average pore diameter of the ceramic film is 2 to 500nm, and more preferably 2 to 100 nm.
The ceramic material used for the ceramic film is not particularly limited, and can be appropriately selected from conventionally known ceramic materials. For example, oxide-based materials such as alumina, zirconia, magnesia, silica, titania, ceria, yttria, and barium titanate; composite oxide materials such as cordierite, forsterite, steatite, sialon, zircon, ferrite and the like. Among them, 1 or 2 or more kinds of ceramic materials are preferably composed mainly of alumina, zirconia, titania, magnesia and silica, and "mainly" herein means that 50 wt% or more (preferably 75 wt% or more, more preferably 80 to 100 wt%) of the entire ceramic powder is the ceramic material.
In one embodiment, the membrane layer material of the ceramic membrane is a ceramic material which is subjected to hydrophobic modification. The surface graft modification method disclosed in patent CN101280241A can be used for the preparation. The term hydrophobic in the present invention is generally understood to mean that the contact angle of a water droplet on a surface is greater than 130 °. The surface modification of the ceramic membrane is carried out by chemically modifying the ceramic membrane by adopting an organosilane coupling agent, the surface chemical modification of the ceramic membrane is carried out by adopting an immersion method, and the ceramic membrane is immersed in an organic solvent dissolved with a silane coupling agent for 12-20 hours; and after the treatment is finished, repeatedly cleaning the substrate with ethanol for many times, and finally drying the substrate in an oven at 110 ℃ for 24-48 hours for later use.
The alcohol amine rich liquid system capable of being treated by the method provided by the utility model is used for absorbing CO2Alcohol amine solution of (1). The alcohol amine solution is a monoethanolamine solution or a mixture of one or more other alcohol amines, and is not particularly limited as long as the rich alcohol amine solution can be desorbed by the method, and in some embodiments, the alcohol amine solution is selected from one or more of monoethanolamine, N-diethylethanolamine, methyldiethanolamine, 1-dimethylamino-2-propanol, tetraethylenepentamine, triethylenetetramine, ethylenediamine and other alcohol amine solutions, N-Methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP) and Piperazine (PZ) and other conventionally used and novel amine solvents, such as 4- (diethylamino) -2-butanol (DEAB), Diethylenetriamine (DETA), Diethylaminoethanol (DEAE) and other binary or ternary and multi-component mixed solvents of various amines, such as DEAB and MEA- AMP-PZ, and the like. The concentration range of the alcohol amine solution is not particularly limited, and may be 2 to 6 mol/L.
The solid acid type catalyst described herein is not particularly limited,the commonly used solid acid catalyst is a catalyst particle with the diameter of 1-2 mm, and comprises the following components: molecular sieve catalysts, e.g. HZSM-5, gamma-Al2O3Transition metal oxides such as TiO2，V2O5And the like, which are easy for solid-liquid separation and do not affect the absorption performance of the amine solvent, and mixtures thereof; the membrane tube element of the membrane contactor can be filled with single catalyst particles, or with a mixture of different catalysts, or with a mixture of catalyst particles and inert particles, wherein the inert particles can be inert particulate matters such as glass beads, quartz sand, inert ceramic balls and the like.
When experimental conditions are set, the regeneration temperature in the membrane contactor ranges from 90 ℃ to 110 ℃; the operating pressure within the membrane contactor may be in the range of 70 to 400 kPa. After desorption, the tested ceramic membrane tube can be preferably repeatedly washed by adopting absolute ethyl alcohol and deionized water, and then is placed in an oven for drying, so that the ceramic membrane which can be repeatedly used is obtained. In the test, the membrane flux can be recovered only by washing with deionized water after the ceramic membrane is used for desorption experiments; meanwhile, in order to increase the reliability of the experimental result, a new membrane tube can be replaced for carrying out a contrast test. By adopting the method, higher contact area can be obtained in the desorption process, low-temperature desorption is realized, the desorption energy consumption is obviously reduced, and compared with the common membrane desorption process, the permeation flux is improved by over 67.2 percent. The ceramic membrane used in the utility model is subjected to hydrophobic modification by an organic surface grafting method, and a series of characterization means such as contact angles prove that the ceramic membrane has good hydrophobic performance, keeps higher permeation flux and excellent desorption performance in a long-term stability experiment, and can keep the flux above 90%.
In addition, the present invention also provides a device used in the above method, as shown in fig. 1, including: the device comprises a raw material tank 1, a ceramic membrane contactor 4 filled with a solid acid catalyst, and a material liquid pump 2, wherein the material liquid pump 2 is connected with a raw material liquid inlet of a ceramic membrane through a liquid flow meter 3, and the permeation side of the ceramic membrane contactor 4 is connected with a condensing pipe 5, a drying pipe 6, a gas mass flow meter 7 and a vacuum pump 8; the device also comprises a heating sleeve, wherein the heating sleeve is tightly attached to the raw material tank 1 and is used for providing a heat source for the device; a feeding valve is also arranged on a connecting pipeline from a raw material liquid outlet of the ceramic membrane contactor 4 to the raw material tank 1; a sampling valve is arranged at the middle lower part of the raw material tank 1. In addition, the device is also provided with a temperature sensor and a pressure sensor at a raw material liquid inlet, a raw material liquid outlet, a permeation gas phase outlet of the ceramic membrane contactor 4 and the middle upper part of the raw material tank 1, and the data such as temperature, pressure and the like are monitored and recorded in real time through software.
Example 1:
(1) the single-channel ceramic membrane material is subjected to hydrophobic modification by a surface grafting modification method. Stirring at 35 deg.C and normal pressure. And after the modification solution reacts for 2 hours, placing the ceramic membrane in the prepared modification solution, and vacuumizing. After the reaction is finished and no bubbles are generated on the surface, repeatedly cleaning the ceramic membrane taken out by deionized water and ethanol for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the ceramic membrane with good hydrophobic property;
(2) filling 10g of HZSM-5 catalyst in the ceramic membrane element, assembling a membrane contactor, and connecting an experimental device;
(3) the used solution is prepared from deionized water and chemical reagents according to a certain proportion, and the used reagents are all prepared fresh. Preparing 5mol/L monoethanolamine solution, introducing carbon dioxide to CO in the solution2Loading capacity of about 0.45mol/mol amine, pouring 600ml of rich amine solution into a stainless steel raw material tank for heating;
(4) starting a feed liquid pump after the set temperature reaches 100 ℃, starting a vacuum pump after the temperature of the system is stable, and setting the pressure of a permeation side to be 80kPa (absolute pressure);
(5) the system starts to work, the flow rate of the feed liquid is 18L/h, the raw material liquid flows into the membrane contactor after being measured by the liquid flowmeter, and the desorbed amine solution flows back to the raw material tank; under the action of pressure difference on two sides of the membrane, carbon dioxide desorbed from the raw material liquid and water molecules vaporized on the surface of the membrane penetrate through membrane holes in a steam form to reach a permeation test, and enter a collecting bottle after being condensed and dried;
(6) and recording and detecting the condensed and dried carbon dioxide gas. CO measurement and recording by gas mass flowmeter2Flow rate accumulation of (2) recording CO every 2s2The volume amount of (a); to obtain CO2The gas permeation flux is 178.68L/(m)2H), sampling, recording and detecting the liquid phase loading in the raw material tank. Sampling is carried out once every 30min, and the loading capacity of the carbon dioxide in the liquid phase is obtained through a loading titration device. And calculating material balance and verifying the accuracy of experimental data. The average absolute deviation of the experimental data is calculated to be only 0.37 percent;
(7) after the experiment is finished, cleaning the ceramic membrane and the solid acid catalyst by adopting absolute ethyl alcohol and deionized water, repeatedly washing for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the recyclable ceramic membrane; drying the solid acid catalyst at 70 ℃ for 12h to obtain a reusable catalyst; after 3 times of membrane distillation operations are carried out according to the method, and then the desorption experiment is carried out according to the method, the desorption performance is not obviously changed, the gas permeation flux is maintained to be more than about 93.6 percent, and compared with the membrane desorption control example without the catalyst, the molar quantity of the carbon dioxide desorbed in the same time is improved by 171.75 percent.
After the experiment, the CO in the liquid phase in the membrane tube is measured2/H2The ratio of O is 2.17molCO2/L H2O, compared to CO in the starting liquid2/H2The O proportion is reduced by 26.9 percent, and CO in the distillate at the permeation side2/H2The ratio of O is approximately 0, which proves that the method aims at the regeneration process of the alcohol amine solution and CO2The desorption separation has obvious effect.
Example 2:
(1) the single-channel ceramic membrane material is subjected to hydrophobic modification by a surface grafting modification method. Stirring at 35 deg.C and normal pressure. And after the modification solution reacts for 2 hours, placing the ceramic membrane in the prepared modification solution, and vacuumizing. After the reaction is finished and no bubbles are generated on the surface, repeatedly cleaning the ceramic membrane taken out by deionized water and ethanol for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the ceramic membrane with good hydrophobic property;
(2) filling 10g of HZSM-5 catalyst in the ceramic membrane element, assembling a membrane contactor, and connecting an experimental device as shown in figure 1;
(3) the used solution is prepared from deionized water and chemical reagents according to a certain proportion, and the used reagents are all prepared fresh. Preparing 5mol/L monoethanolamine solution, introducing carbon dioxide to CO in the solution2The load is 0.45mol/mol amine, 600ml of rich amine solution is poured into a stainless steel raw material tank for heating;
(4) starting a feed liquid pump after the set temperature reaches 100 ℃, starting a vacuum pump after the temperature of the system is stable, and setting the pressure of a permeation side to be 60kPa (absolute pressure);
(5) the system starts to work, the flow rate of the feed liquid is 18L/h, the raw material liquid flows into the membrane contactor after being measured by a flowmeter, and the desorbed amine solution flows back to the raw material tank; under the action of pressure difference on two sides of the membrane, carbon dioxide desorbed from the raw material liquid and water molecules vaporized on the surface of the membrane penetrate through membrane holes in a steam form to reach a permeation test, and enter a collecting bottle after being condensed and dried;
(6) and recording and detecting the condensed and dried carbon dioxide gas. CO measurement and recording by gas mass flowmeter2Flow rate accumulation of (2) recording CO every 2s2The volume amount of (a); CO 22The gas permeation flux is 231.57L/(m)2H), sampling, recording and detecting the liquid phase loading in the raw material tank. Sampling is carried out once every 30min, the loading capacity of carbon dioxide in a liquid phase is obtained through a load titration device, material balance is calculated, and the accuracy of experimental data is verified. The average absolute deviation of the experimental data is calculated to be only 0.62 percent;
(7) after the experiment is finished, cleaning the ceramic membrane and the solid acid catalyst by adopting absolute ethyl alcohol and deionized water, repeatedly washing for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the recyclable ceramic membrane; drying the solid acid catalyst at 70 ℃ for 12h to obtain a reusable catalyst; the membrane distillation operation was performed 3 times according to the above method, and the desorption experiment was performed according to the above method, and the desorption performance was not significantly changed. The gas permeation flux was maintained above about 90.2%, and the molar amount of carbon dioxide desorbed over the same time period was 110.86% higher than that of the control example of membrane desorption without catalyst.
After the experiment, the CO in the liquid phase in the membrane tube is measured2/H2The ratio of O is 1.86molCO2/L H2O, compared to CO in the starting liquid2/H2The O proportion is reduced by 37.4 percent, and CO in the distillate at the permeation side2/H2The ratio of O is approximately 0, which proves that the method aims at the regeneration process of the alcohol amine solution and CO2The desorption separation has obvious effect.
Example 3:
(1) the single-channel ceramic membrane material is subjected to hydrophobic modification by a surface grafting modification method. Stirring at 35 deg.C and normal pressure. And after the modification solution reacts for 2 hours, placing the ceramic membrane in the prepared modification solution, and vacuumizing. After the reaction is finished and no bubbles are generated on the surface, repeatedly cleaning the ceramic membrane taken out by deionized water and ethanol for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the ceramic membrane with good hydrophobic property;
(2) filling 10g of HZSM-5 catalyst in the ceramic membrane element, assembling a membrane contactor, and connecting an experimental device as shown in figure 1;
(3) the used solution is prepared from deionized water and chemical reagents according to a certain proportion, and the used reagents are all prepared fresh. Preparing 5mol/L monoethanolamine solution, introducing carbon dioxide to CO in the solution2The loading amount is 0.45mol/mol amine, and the solution amount which is the same as that of the comparative example is taken and poured into a stainless steel raw material tank for heating;
(4) starting a feed liquid pump after the set temperature reaches 100 ℃, starting a vacuum pump after the temperature of the system is stable, and setting the pressure of a permeation side to be 50kPa (absolute pressure);
(5) the system starts to work, the flow rate of the feed liquid is 18L/h, the raw material liquid flows into the membrane contactor after being measured by the liquid flowmeter, and the desorbed amine solution flows back to the raw material tank; under the action of pressure difference on two sides of the membrane, carbon dioxide desorbed from the raw material liquid and water molecules vaporized on the surface of the membrane penetrate through membrane holes in a steam form to reach a permeation test, and enter a collecting bottle after being condensed and dried;
(6) and recording and detecting the condensed and dried carbon dioxide gas. CO measurement and recording by gas mass flowmeter2Flow rate accumulation of (2) recording CO every 2s2The volume amount of (a); CO 22The gas permeation flux is 244.58L/(m)2H), sampling, recording and detecting the liquid phase loading in the raw material tank. Sampling is carried out once every 30min, and the loading capacity of the carbon dioxide in the liquid phase is obtained through a loading titration device. And calculating material balance and verifying the accuracy of experimental data. The average absolute deviation of the experimental data is calculated to be only 0.51 percent;
(7) after the experiment is finished, cleaning the ceramic membrane and the solid acid catalyst by adopting absolute ethyl alcohol and deionized water, repeatedly washing for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the recyclable ceramic membrane; drying the solid acid catalyst at 70 ℃ for 12h to obtain a reusable catalyst; after 3 times of membrane distillation operations are carried out according to the method, and then the desorption experiment is carried out according to the method, the desorption performance is not obviously changed, the gas permeation flux is maintained to be more than about 97.7 percent, and compared with the membrane desorption control example without the catalyst, the molar quantity of the carbon dioxide desorbed in the same time is improved by 67.22 percent.
After the experiment, the CO in the liquid phase in the membrane tube is measured2/H2The ratio of O is 1.80molCO2/L H2O, compared to CO in the starting liquid2/H2The O proportion is reduced by 39.5 percent, and CO in the distillate at the permeation side2/H2The ratio of O is approximately 0, which proves that the method aims at the regeneration process of the alcohol amine solution and CO2The desorption separation has obvious effect.
Comparative example:
(1) the differences from examples 1 to 3 are: the method adopts a membrane component not filled with a solid acid catalyst to carry out desorption regeneration process of the rich amine solution, and each group of experiments begin to record data for 180min by taking gas phase generation at a permeation side as a time node;
(2) the ceramic membrane material is subjected to hydrophobic modification by adopting a surface grafting modification method, and a membrane contactor is assembled, and an experimental device is connected as shown in figure 1;
(3) the used solution is prepared from deionized water and chemical reagents according to a certain proportion, and the used reagents are all prepared fresh. Preparing 5mol/L monoethanolamine solution, introducing carbon dioxide to CO in the solution2The load is 0.45mol/mol amine, 600ml of rich amine solution is poured into a stainless steel raw material tank for heating;
(4) starting a feed liquid pump after the set temperature reaches 100 ℃, starting a vacuum pump after the temperature of the system is stable, and setting the pressures of the permeation side to be 80, 60 and 50kPa (absolute pressure) respectively;
(5) the system starts to work, the flow rate of the feed liquid is 18L/h, the raw material liquid flows into the membrane contactor after being measured by the liquid flowmeter, and the desorbed amine solution flows back to the raw material tank; under the action of pressure difference on two sides of the membrane, carbon dioxide desorbed from the raw material liquid and water molecules vaporized on the surface of the membrane penetrate through membrane holes in a steam form to reach a permeation test, and enter a collecting bottle after being condensed and dried;
(6) and recording and detecting the condensed and dried carbon dioxide gas. CO measurement and recording by gas mass flowmeter2The flow rate accumulation value of (1) is recorded every 2s to obtain CO2The volume amount of (a); and sampling, recording and detecting the liquid phase load in the raw material tank. Sampling is carried out once every 30min, and the loading capacity of the carbon dioxide in the liquid phase is obtained through a loading titration device. And calculating material balance and verifying the accuracy of experimental data.
(7) After the experiment is finished, cleaning the ceramic membrane and the solid acid catalyst by adopting absolute ethyl alcohol and deionized water, repeatedly washing for three times, placing the ceramic membrane in a drying oven, and drying the ceramic membrane for 12 hours at the temperature of 110 ℃ to obtain the recyclable ceramic membrane; drying the solid acid catalyst at 70 ℃ for 12h to obtain a reusable catalyst; the membrane distillation operation was performed 3 times according to the above method, and the desorption experiment was performed according to the above method, and the desorption performance was not significantly changed.
Claims (10)
1. The method for desorbing carbon dioxide by using alcohol amine rich liquid is characterized by comprising the following steps of:
pumping the alcohol amine rich solution absorbing the carbon dioxide into a ceramic membrane element, wherein a catalyst for desorbing the carbon dioxide in the alcohol amine rich solution is filled in the ceramic membrane element;
desorbing the carbon dioxide in the alcohol amine rich solution under the action of the catalyst, and allowing the desorbed carbon dioxide to permeate through the membrane layer of the ceramic membrane element to obtain carbon dioxide; and discharging the desorbed alcohol amine lean solution from the ceramic membrane element.
2. The method for desorbing carbon dioxide by using alcohol amine rich liquid according to claim 1, wherein the alcohol amine compound used in the alcohol amine rich liquid is one or more selected from monoethanolamine, N-diethylethanolamine, methyldiethanolamine, 1-dimethylamino-2-propanol, tetraethylenepentamine, triethylenetetramine, ethylenediamine and other alcohol amines, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, piperazine, 4- (diethylamino) -2-butanol, Diethylenetriamine (DETA), and Diethylaminoethanol (DEAE);
the concentration range of the alcohol amine compound is 2-6 mol/L.
3. The method for desorbing carbon dioxide from an alcohol amine rich liquid according to claim 1, wherein the catalyst is a solid acid catalyst;
the solid acid catalyst is a molecular sieve catalyst or a metal oxide catalyst;
the molecular sieve catalyst is HZSM-5; the metal oxide catalyst is selected from gamma-Al2O3、TiO2Or V2O5。
4. The method for desorbing carbon dioxide by using the alcohol amine rich solution according to claim 1, wherein the ceramic membrane is tubular or multi-channel, and the diameter of each channel is 0.5-30 mm;
the average aperture range of the ceramic membrane is 2-500 nm;
the contact angle of the membrane surface of the ceramic membrane to water drops is larger than 130 degrees.
5. The method for desorbing carbon dioxide by using alcohol amine rich liquid as claimed in claim 1, wherein the temperature in the ceramic membrane tube is 90-110 ℃; the operating pressure range is 70-400 kPa.
6. The device for desorbing carbon dioxide by using alcohol amine rich liquid is characterized by comprising the following components: the membrane contactor 4 comprises a hydrophobic separation membrane, and a catalyst for desorbing carbon dioxide is arranged on the surface of the membrane.
7. The device for desorbing carbon dioxide by using alcohol amine rich liquid as claimed in claim 6, wherein said membrane contactor (4) is a ceramic membrane;
the ceramic membrane is in a tubular or multi-channel structure; and the catalyst is filled in the channel;
the contact angle of a water drop on the surface of the hydrophobic separation membrane is larger than 130 degrees;
the average pore diameter of the hydrophobic separation membrane is 2-500 nm.
8. The device for desorbing carbon dioxide by using alcohol amine rich liquid as claimed in claim 6, further comprising:
the raw material tank (1) is used for storing the alcohol amine rich liquid;
the feed liquid pump (2) is used for pumping the material in the feed tank (1) into the membrane contactor 4;
further comprising: a liquid flow meter (3) for measuring the flow rate of the feed liquid entering the membrane contactor (4) from the raw material tank (1);
further comprising: the condenser pipe (5) is connected to the permeation side of the membrane contactor (4) and is used for condensing the permeation gas;
further comprising: a drying pipe (6) connected to the condensing pipe (5) for drying the condensed gas;
the drying pipe (6) is filled with a drying agent.
9. The device for desorbing carbon dioxide by using alcohol amine rich liquid as claimed in claim 6, further comprising: the gas mass flow meter (7) is connected with the drying pipe (6) and is used for obtaining the gas measuring flow in the drying pipe (6);
further comprising: and the vacuum pump (8) is connected to the permeation side of the membrane contactor (4) and is used for applying negative pressure.
10. The device for desorbing carbon dioxide by using alcohol amine rich liquid as claimed in claim 6, further comprising: a heating device for heating the material in the raw material tank (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110984809.2A CN113856412B (en) | 2021-08-25 | 2021-08-25 | Method and device for desorbing carbon dioxide by using alcohol amine rich solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110984809.2A CN113856412B (en) | 2021-08-25 | 2021-08-25 | Method and device for desorbing carbon dioxide by using alcohol amine rich solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113856412A true CN113856412A (en) | 2021-12-31 |
| CN113856412B CN113856412B (en) | 2022-10-25 |
Family
ID=78988382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110984809.2A Active CN113856412B (en) | 2021-08-25 | 2021-08-25 | Method and device for desorbing carbon dioxide by using alcohol amine rich solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113856412B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570178A (en) * | 2022-03-29 | 2022-06-03 | 上海交通大学 | Carbon dioxide absorbent and preparation method and application thereof |
| CN115282993A (en) * | 2022-09-28 | 2022-11-04 | 中国华电科工集团有限公司 | CO (carbon monoxide) 2 Regenerated catalyst and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB702907A (en) * | 1950-09-22 | 1954-01-27 | Ici Ltd | Improvements in and relating to reaction vessels and their operation |
| CN1962432A (en) * | 2006-12-01 | 2007-05-16 | 清华大学 | Circumfluence type film separation device for carbon dioxide recovery and condensation |
| CN101524613A (en) * | 2008-09-12 | 2009-09-09 | 江苏工业学院 | Method for regenerating absorbent |
| CN101822931A (en) * | 2010-05-11 | 2010-09-08 | 浙江大学 | Decompression regeneration system and method for hollow fiber membrane contactor of carbon dioxide enriched absorbent solution |
| CN101862625A (en) * | 2010-06-23 | 2010-10-20 | 湘潭大学 | Membrane reactor for use in hydrocarbon oxidization reaction-separation coupling process |
| CN103357248A (en) * | 2013-08-02 | 2013-10-23 | 北京交通大学 | Composite absorbent for capturing carbon dioxide in flue gas based on membrane contactor and use method thereof |
| CN103877828A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Absorption liquid regeneration method and special-purpose absorption liquid regeneration device |
| CN109351125A (en) * | 2018-09-20 | 2019-02-19 | 湖南大学 | One kind is for reducing rich CO2The new catalytic desorber of amine aqueous solution regeneration energy consumption |
-
2021
- 2021-08-25 CN CN202110984809.2A patent/CN113856412B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB702907A (en) * | 1950-09-22 | 1954-01-27 | Ici Ltd | Improvements in and relating to reaction vessels and their operation |
| CN1962432A (en) * | 2006-12-01 | 2007-05-16 | 清华大学 | Circumfluence type film separation device for carbon dioxide recovery and condensation |
| CN101524613A (en) * | 2008-09-12 | 2009-09-09 | 江苏工业学院 | Method for regenerating absorbent |
| CN101822931A (en) * | 2010-05-11 | 2010-09-08 | 浙江大学 | Decompression regeneration system and method for hollow fiber membrane contactor of carbon dioxide enriched absorbent solution |
| CN101862625A (en) * | 2010-06-23 | 2010-10-20 | 湘潭大学 | Membrane reactor for use in hydrocarbon oxidization reaction-separation coupling process |
| CN103877828A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Absorption liquid regeneration method and special-purpose absorption liquid regeneration device |
| CN103357248A (en) * | 2013-08-02 | 2013-10-23 | 北京交通大学 | Composite absorbent for capturing carbon dioxide in flue gas based on membrane contactor and use method thereof |
| CN109351125A (en) * | 2018-09-20 | 2019-02-19 | 湖南大学 | One kind is for reducing rich CO2The new catalytic desorber of amine aqueous solution regeneration energy consumption |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570178A (en) * | 2022-03-29 | 2022-06-03 | 上海交通大学 | Carbon dioxide absorbent and preparation method and application thereof |
| CN115282993A (en) * | 2022-09-28 | 2022-11-04 | 中国华电科工集团有限公司 | CO (carbon monoxide) 2 Regenerated catalyst and preparation method and application thereof |
| CN115282993B (en) * | 2022-09-28 | 2023-02-03 | 中国华电科工集团有限公司 | Regenerated catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113856412B (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113856412B (en) | Method and device for desorbing carbon dioxide by using alcohol amine rich solution | |
| Drage et al. | Materials challenges for the development of solid sorbents for post-combustion carbon capture | |
| CN102389686B (en) | Separating method for CO2-containing mixed gas | |
| Hu et al. | Analyzing the potential benefits of trio-amine systems for enhancing the CO2 desorption processes | |
| US10173167B2 (en) | Composite method of trapping carbon dioxide in gas mixture | |
| Lin et al. | Absorption of carbon dioxide by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol in PVDF membrane contactor | |
| US20070237695A1 (en) | Phase transitional absorption method | |
| CN101760270B (en) | Method for removing and recycling CO2 in natural gas | |
| CN110141935B (en) | Functionalized ionic liquid phase change system for carbon dioxide capture and application | |
| Lin et al. | Determination of mass transfer resistance during absorption of carbon dioxide by mixed absorbents in PVDF and PP membrane contactor | |
| Niknam et al. | Experimental and modeling study of CO2 absorption by L-Proline promoted potassium carbonate using hollow fiber membrane contactor | |
| CN101524613B (en) | Method for regenerating absorbent | |
| CN109351125A (en) | One kind is for reducing rich CO2The new catalytic desorber of amine aqueous solution regeneration energy consumption | |
| CN103755639A (en) | Aminoacetic acid functional ionic liquid and preparation method and application thereof | |
| Lee et al. | Integrated membrane contactor absorber/regeneration column process for CO2 capture with large scale module at various operating conditions | |
| Guo et al. | Integration of solid acid catalyst and ceramic membrane to boost amine-based CO2 desorption | |
| CN112892160B (en) | Phase change absorbent and application thereof in carbon dioxide capture | |
| CN216457915U (en) | Continuous rich amine solution regenerating unit | |
| Bhaumik et al. | Hollow‐fiber membrane‐based rapid pressure swing absorption | |
| CN116212591A (en) | Low-corrosiveness phase change absorbent and application thereof in carbon dioxide capturing | |
| CN114272726B (en) | Method for efficiently separating ammonia-containing gas based on ionic liquid mixed matrix membrane | |
| Ding et al. | Desorption research and energy consumption assessment of a porous liquids impregnated by monoethanolamine (MEA) | |
| Jiajia et al. | Characteristics of CO2 absorption by N, N-dimethylethanolamine (DMEA) in hollow fiber membrane contactor | |
| LU et al. | Membrane-based CO2 absorption into blended amine solutions | |
| Suda et al. | Countercurrent absorption of CO2 in a real flue gas into aqueous alkanolamine solutions in a wetted wall column |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |