CN117358016A - Liquid-liquid absorbent for capturing carbon dioxide - Google Patents
Liquid-liquid absorbent for capturing carbon dioxide Download PDFInfo
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- CN117358016A CN117358016A CN202311347526.2A CN202311347526A CN117358016A CN 117358016 A CN117358016 A CN 117358016A CN 202311347526 A CN202311347526 A CN 202311347526A CN 117358016 A CN117358016 A CN 117358016A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 230000002745 absorbent Effects 0.000 title claims abstract description 80
- 239000002250 absorbent Substances 0.000 title claims abstract description 80
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 64
- 238000010521 absorption reaction Methods 0.000 claims abstract description 62
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005191 phase separation Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- 238000003795 desorption Methods 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 115
- 230000008929 regeneration Effects 0.000 abstract description 16
- 238000011069 regeneration method Methods 0.000 abstract description 16
- 150000003141 primary amines Chemical class 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZYWUVGFIXPNBDL-UHFFFAOYSA-N n,n-diisopropylaminoethanol Chemical compound CC(C)N(C(C)C)CCO ZYWUVGFIXPNBDL-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- -1 ester ions Chemical class 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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
- B01D53/1456—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
- B01D53/1425—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
- B01D53/1493—Selection of liquid materials for use as absorbents
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)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a liquid-liquid absorbent for capturing carbon dioxide; the chemical components of the catalyst comprise 1, 3-propylene diamine, nonaqueous solvent and water; the operation steps are as follows: 1, 3-propanediamine (DAP), nonaqueous solvent and H 2 O is mixed and stirred to prepare the DAP/H 2 An O/nonaqueous solvent two-phase absorbent; absorbing the mixed gas by the two-phase absorbent in a constant-temperature water bath kettle; CO 2 Absorbing the mixture into a solution by a nonaqueous solvent, and then reacting the solution with primary amine to generate DAP-carbamate, deprotonated DAP and the nonaqueous solvent; and (3) separating the absorbed liquid by using a separating funnel to obtain an upper phase and a lower phase, and finally comparing the volume, the mass and the viscosity. The non-aqueous solvent is added, so that liquid-liquid phase separation can be spontaneously formed, and the viscosity of the solution after absorption is reduced; has great energy-saving advantage in regeneration; in addition, the two-phase absorbent has high absorption rate and high absorption load, and can solve the problems of slow absorption rate, high water evaporation latent heat and high regeneration energy consumption of the traditional absorption process.
Description
Technical Field
The invention belongs to the technical field of energy conservation and environmental protection, relates to a carbon trapping technology, and in particular relates to a liquid-liquid absorbent for trapping carbon dioxide.
Background
The rapid development of economy also brings serious environmental problems, the use of fossil energy causes a large amount of carbon dioxide emission, the greenhouse effect is increasingly serious, and the living of human beings is threatened for a long time. Aiming at the problem of carbon dioxide generated by burning fossil energy, the electric power industry is a main emission source, so that the problem of reducing the smoke emission of a power plant is emphasized.
The technology for reducing carbon dioxide emission of coal-fired power plants mainly comprises the following three types: trapping before combustion, trapping in combustion, trapping after combustion. According to the conditions of emission sources, each technology has respective advantages and disadvantages, and the chemical absorption method has the advantages of high carbon dioxide capturing efficiency, high recovery purity, mature technology and the like in consideration of large flow of coal-fired flue gas and low carbon dioxide concentration, so that the technology has the maximum large-scale application potential at the present stage. The traditional chemical absorbent 30% ethanolamine (MEA) is the most mature technology at present, but the absorbent has the defects of small absorption capacity, high corrosiveness and the like, and the high regeneration energy consumption can cause high technology investment cost, which also limits the large-scale use of the chemical absorption method.
The two-phase absorbent studied at present also has the problems of difficult regeneration after absorption, high absorption viscosity and the like. The Chinese patent (patent number: CN 103826723A) discloses two-phase absorbents DIPAE/MAPD, DIPAE/DAB, DEEA/DMPDA and the like, liquid-liquid two phases can be formed after absorption, and only a solution rich in phase is sent to a regeneration tower for desorption regeneration, but the patent also has the problems of high amine corrosiveness, high volatility and the like, and has higher cost and is not easy to apply in industry. The literature (Liang Huaiyong, zhou Xiao, yao Jing, etc.) discloses a two-phase absorbent, which uses hydroxyethyl ethylenediamine (AEEA) as absorbent and dimethyl sulfoxide (DMSO) as phase-splitting agent, and uses organic solvent to replace water, so that the specific heat and evaporation enthalpy can be reduced, and the energy consumption can be reduced.
Disclosure of Invention
The invention aims to: the invention aims to provide a liquid-liquid two-phase absorbent for capturing carbon dioxide, which has high absorption capacity and lower viscosity, and the non-aqueous solvent is used for replacing amine to reduce corrosion to instruments, so that the absorbent has the advantage of low specific heat in the aspect of regeneration.
The technical scheme is as follows: the liquid-liquid absorbent for capturing carbon dioxide comprises 1, 3-propylene diamine, water and a nonaqueous solvent;
wherein the 1, 3-propylene diamine is used for absorbing carbon dioxide, and the nonaqueous solvent is a phase-splitting agent;
the two-phase absorbent is divided into a lean phase and a rich phase after absorbing carbon dioxide, and the carbon dioxide is concentrated in the rich phase.
Further, the nonaqueous solvent is one selected from (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol), and N-propanol (N-pronol).
Further, the mass fraction is as follows: 1, 3-propanediamine: water: the ratio of the nonaqueous solvent is 30 percent, 30 percent to 40 percent and 30 percent to 40 percent respectively.
Further, an application method of the liquid-liquid absorbent for capturing carbon dioxide, which uses the two-phase absorbent to absorb carbon dioxide, comprises the following specific steps:
(1): mixing 1, 3-propylene diamine, water and a nonaqueous solvent according to the mass ratio of 30%, 30-40% and 30-40%, and uniformly stirring at room temperature to obtain a DAP/water/nonaqueous solvent two-phase absorbent;
(2): absorbing the mixed gas by the obtained two-phase absorbent in a constant-temperature water bath kettle;
(3): CO in mixed gas 2 Firstly, absorbing the primary amine DAP into a solution by a nonaqueous solvent, and then reacting the primary amine DAP with the solution to obtain an absorption liquid; wherein the non-aqueous solvent does not participate in the reaction, and is used as a phase-splitting agent to accelerate CO 2 The molecules react with DAP in contact and phase separate; primary amines DAP and CO 2 After the reaction, DAP-carbamate, deprotonated DAP and a nonaqueous solvent are generated;
the nonaqueous solvent is not involved in the reaction at all times, and thus may be present at all times;
(4): and (3) separating the absorbed liquid by using a separating funnel to obtain an upper phase and a lower phase, and respectively comparing the volume, the mass and the viscosity.
Further, in step (1), the temperature of the room temperature is 20 to 30 ℃.
Further, in the step (2), the mixed gas is composed of 88% N 2 And 12% CO 2 The total gas amount is 300ml/min, and the absorption time is 120min.
The beneficial effects are that: compared with the prior art, the invention has the characteristics that: 1. the two-phase absorbent can automatically split phases after absorbing carbon dioxide, the carbon dioxide enrichment phase is in the lower phase, the lean phase is in the upper phase, and only the rich phase is required to be sent to a regeneration tower for regeneration, and the lean phase can enter the absorption tower again for mixing after passing through a heat exchanger to form a new two-phase absorbent; 2. the two-phase absorbent of the invention has the phase separation time within 10min after absorbing carbon dioxide, the load of the rich phase after phase separation is more than 2.5mol/kg, the load of the lean phase is less than 0.2mol/kg, and the absorbent hardly absorbs carbon dioxide and can be recycled. The proportion can be further reduced by proportion adjustment; 3. according to the invention, the nonaqueous solvent is used as a phase-splitting agent, and has lower specific heat and evaporation enthalpy compared with water, so that the energy consumption can be reduced in the regeneration process; 4. the two-phase absorbent has high absorption rate and high absorption load, and can solve the problems of slow absorption rate, high water evaporation latent heat and high regeneration energy consumption of the traditional absorption process.
Drawings
FIG. 1 is a schematic diagram of the rich phase load and volume ratio of the two-phase absorbent obtained from different nonaqueous solvents in example 1 of the present invention after absorbing pure carbon dioxide;
FIG. 2 is a schematic diagram showing the rich phase load and the volume ratio of the two-phase absorbent obtained by different nonaqueous solvents in example 2 of the present invention after absorbing the mixed gas;
FIG. 3 is a graph showing the comparison of absorption rates of two-phase absorbents obtained with different nonaqueous solvents in example 2 of the present invention;
FIG. 4 is a graph comparing the desorption rates of two-phase absorbent obtained with different nonaqueous solvents in example 3 of the present invention.
Detailed Description
The invention is further illustrated by the following figures and specific examples:
the liquid-liquid absorbent for capturing carbon dioxide comprises 1, 3-propylene diamine, water and a nonaqueous solvent;
wherein the nonaqueous solvent is selected from one of N-methylpyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol) and N-propanol (N-propanol);
the two-phase absorbent is a uniform mixed solution before absorbing, liquid-liquid phase separation can be formed after absorbing carbon dioxide, and one phase for enriching carbon dioxide is generally arranged at the lower layer of the solution and is called a rich phase; the other phase is the upper phase because the carbon dioxide content is less called the lean phase; the primary amine can form hydrophilic acid ester ions after absorbing carbon dioxide, and the nonaqueous solvent does not participate in the reaction and is used as a phase-splitting agent for phase splitting; the rich phase after phase separation is sent to a regeneration tower for regeneration reaction, the lean phase reenters the absorption tower through a heat exchanger, the phase separation of the rich phase is reduced, and the quality of regenerated solution is reduced; the viscosity is reduced, and the regeneration energy consumption can be reduced.
Further, the method comprises the steps of selecting a nonaqueous solvent which can be separated after mixing and absorbing carbon dioxide with 1, 3-propylene Diamine (DAP) by taking the 1, 3-propylene Diamine (DAP) as a main carbon dioxide absorbent, wherein the nonaqueous solvent comprises 30% of 1, 3-propylene Diamine (DAP), 40% of nonaqueous solvent and 30% of water according to mass fraction.
Further, the nonaqueous solvent is selected from one or more of N-methylpyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol) and N-propanol (N-propanol).
Further, the concentration of carbon dioxide in the mixed gas is 12%, and the concentration of N2 is 88%; the total air quantity is 300ml/min; the temperature was 40 ℃.
Further, the specific steps of carbon dioxide capturing and absorbing by using the selected two-phase absorbent are as follows: mixing 1, 3-propylene Diamine (DAP), a nonaqueous solvent and water according to the mass ratio of 30%, 40-40% and 30-40%, and uniformly stirring at room temperature to obtain a DAP/nonaqueous solvent/water two-phase absorbent; wherein DAP is primary amine, and the nonaqueous solvent is one or more selected from N-methylpyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol) and N-propanol (N-propanol).
Further, the obtained two-phase absorbent is absorbed into a mixed gas in a constant-temperature water bath kettle, the water bath temperature is 40 ℃, and the mixed gas is formed by 88 percent of N 2 And 12% CO 2 The total gas amount is 300ml/min, and the absorption time is 120min. The two-phase absorbent is absorbed into solution by the nonaqueous solvent and then reacts with the primary amine to form DAP-carbamate, deprotonated DAP and tertiary amine.
And (3) separating the absorbed liquid by using a separating funnel to obtain an upper phase and a lower phase, and respectively comparing the volume, the mass and the viscosity.
Example 1:
preparing an absorbent: weighing 20-30g, 30-40g and 30-40g of 1, 3-propylene Diamine (DAP), non-aqueous solvent and water by a balance, and uniformly mixing the solutions by stirring to prepare 20-30wt% DAP+30-40wt% non-aqueous solvent+30-40wt% H 2 The O two-phase absorbent is 100g, wherein the tertiary amine is selected from one or more of N-methyl pyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-amyl alcohol (pentanol) and N-propanol (N-propanol).
Absorption reaction: after preparing the two-phase absorbent, absorbing in a water bath at constant temperature and normal pressure, wherein the water bath is at constant temperature of 40 ℃ and the gas is 500ml/min of pure carbon dioxide, and absorbing for 30min to obtain the split-phase absorbent.
And (3) phase separation: the absorbed two-phase absorbent is subjected to standing and cooling and then is subjected to phase separation by a phase separator, and DAP carbamate, carbonate and deprotonated DAP generated by the reaction are arranged at the lower layer, and are called as rich phases; the upper phase is a mixed liquid of a nonaqueous solvent and water, called a lean phase; the phase separation time of the absorbent, the carbon dioxide loading of the rich phase, the lean-rich liquid mass ratio, and the liquid viscosity of the absorbed rich phase are shown in table 1.
The phase separation time in table 1 is defined as: the time of the just-split phase of the two-phase absorbent; the load is defined as: molar amount of carbon dioxide absorbed per kilogram of amine and water in the absorbent in the rich phase liquid; the phase contrast is defined as: after saturation of the absorption, the mass of the rich phase is proportional to the total mass.
Table 1 shows the performance parameters of the absorbent obtained in example 1 for absorbing carbon dioxide
The phase separation mechanism of the physical two-phase absorbent is mainly salting-out effect, DAP and CO 2 The reaction product is hydrophilic, and as the absorption load increases, the physical solvent is discharged from the water phase, so that a liquid-liquid two-phase is formed; the proportion of phase separation is related to the hydrophobicity of the nonaqueous solvent, and the more hydrophilic the nonaqueous solvent, the more hydrophobic may result in a solution that is not uniformly mixed prior to formulation, thus requiring subsequent experiments by extensive screening of the appropriate nonaqueous solvent.
Table 1 shows the phase separation condition of the two-phase absorbent of different nonaqueous solvent systems after absorbing carbon dioxide, the property of the nonaqueous solvent greatly influences the phase separation characteristic, the phase separation time of the different two-phase absorbent is in the range of 4-8min, the phase-rich load after phase separation is in the range of 2.54mol/kg-3.09mol/kg, the phase separation ratio is in the range of 73% -77%, and the difference between the phase separation time and the phase separation ratio is not great; it can also be derived from the table that the higher the rich phase load, the greater the viscosity, mainly due to the rich phase CO 2 Absorption load increases, DAP and CO in the rich phase 2 The reaction product concentration of (2) will also increase and more nonaqueous solvent will be displaced to the upper phase, thus increasing the rich phase viscosity;
as particularly shown in fig. 1, it can be seen from fig. 1 that the two-phase absorbent formulation of the different nonaqueous solvents of example 1 absorbed carbon dioxide with a rich phase load and a split phase volume ratio; wherein DAP/DMF/H 2 O this group goes through 3The highest load of the rich phase after absorbing carbon dioxide for 0min is 3.09mol/kg, and the fractional phase is 0.74; the group with the lowest rich phase load is DAP/n-amyl alcohol/H 2 O, but the component is low compared to viscosity.
Example 2:
preparing an absorbent: weighing 12g, 12g and 16g of 1, 3-propylene Diamine (DAP), non-aqueous solvent and water by a balance, and uniformly mixing the solutions by stirring to prepare 30wt% DAP+30wt% non-aqueous solvent+40 wt% H 2 The two-phase absorbent of O is 40g, wherein the nonaqueous solvent is one or more selected from N-methylpyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol) and N-propanol (N-propanol).
Absorption reaction: after preparing the two-phase absorbent, absorbing in a water bath at constant temperature and normal pressure, wherein the water bath is at constant temperature of 40 ℃ and the mixed gas is prepared from 88% N 2 And 12% CO 2 The total gas amount is 300ml/min, and the absorption time is 120min.
And (3) phase separation: the absorbed two-phase absorbent is subjected to standing and cooling and then is subjected to phase separation by a phase separator, and DAP carbamate, carbonate and deprotonated DAP generated by the reaction are arranged at the lower layer, and are called as rich phases; the upper phase is a mixed liquid of a nonaqueous solvent and water, called a lean phase; the phase separation time of the absorbent, the carbon dioxide loading of the rich phase, the lean-rich liquid mass ratio, and the liquid viscosity of the absorbed rich phase are shown in table 2.
The phase separation time in table 2 is defined as: the time of the just-split phase of the two-phase absorbent; the load is defined as: molar amount of carbon dioxide absorbed per kilogram of amine and water in the absorbent in the rich phase liquid; the phase contrast is defined as: after saturation of the absorption, the mass of the rich phase is proportional to the total mass.
Table 2 shows the performance parameters of the absorbent obtained in example 1 for absorbing carbon dioxide
Table 2 shows that the different nonaqueous solvents absorb 12% of the mixturePerformance parameters of the in-vivo absorbent; the phase separation time of different nonaqueous solvents shows difference in the mixed gas absorption, and the DAP/DMF/H 2 O absorbs for 10min to form turbid liquid, and can be separated into liquid-liquid two phases after standing for 2 min; DAP/NMP/H 2 O is absorbed for 25min before, the solution is relatively clear, turbid liquid starts to appear after 25min, and the liquid is taken out and kept stand for 3min after 30min, so that liquid-liquid phase separation appears; the phase separation is related to molecular diffusion, the phase separation time influences the size of the regeneration tower, the longer the phase separation time is, the larger the height-diameter ratio of the reactor is, and the longer the molecular diffusion path is;
DAP/nonaqueous solvent/H 2 The rich phase load after O absorption is higher than 4mol/kg, wherein DAP/DMF/H 2 The O absorption load is as high as 4.45mol/kg, the ratio DAP/n-amyl alcohol/H 2 The load of the rich phase after O absorption is 10 percent higher; specifically, as shown in fig. 2, fig. 2 is a schematic diagram of the rich phase load and the volume ratio of the two-phase absorbent obtained by different nonaqueous solvents in example 2 after absorbing the mixed gas;
in addition, as can be seen from the absorption rate fig. 3, the absorption rates of different nonaqueous solvents are greatly different; DAP/H 2 Like the O system, the absorption rate of the system after the nonaqueous solvent is introduced is increased along with the time and the absorption rate is continuously reduced; in contrast, DAP/H 2 The O system starts to decline after absorbing for 40min, the absorption rate decline is very quick, and the decline of the absorption rate is obviously slowed down after introducing the nonaqueous solvent; there is a distinct inflection point in absorption, which may be related to the split phase of the system; the introduction of the nonaqueous solvent can improve the activity of the organic amine and CO 2 And thus can increase the absorption rate; the influence of different nonaqueous solvents on the absorption rate is related to the property of the nonaqueous solvents, and too high viscosity after absorption also influences the absorption rate and CO 2 Diffusion coefficient in the absorber; DAP/DMF/H 2 The initial absorption rate of O is the highest, the trend of decline only occurs after 60min, the declining amplitude is small, and the absorption rate is kept high all the time 100min before absorption; DAP/n-pentanol/H 2 The initial rate of O system is smaller than other nonaqueous solvents, and the rate is kept low all the time although the phase separation is fast, which is similar to the last absorptionThe load is also verified.
Example 3:
preparing an absorbent: DAP/nonaqueous solvent/H after absorption in example 2 2 Carrying out desorption experiments on the rich phase solution of the O system; wherein the nonaqueous solvent is selected from one or more of N-methylpyrrolidone (NMP), N-Butanol (Butanol), sulfolane (TMS), N-Dimethylformamide (DMF), diethylene glycol dimethyl ether (Diglyme), N-pentanol (pentanol) and N-propanol (N-propanol).
And (3) desorption reaction: absorbing the mixed gas for 120min, separating to obtain a phase-rich solution, performing desorption experiment in a magnetic stirring oil bath, keeping the temperature of the magnetic stirring oil bath at 90 ℃, placing the three-neck flask in the oil bath to heat, starting a magnetic stirrer, condensing outlet gas through cold water of a condensing tube under gas purging, washing the bottle to absorb volatilized amine, drying the volatilized water vapor by a drying tube, and then entering an infrared analyzer to measure CO at an outlet 2 Concentration. N with purge gas of 300ml/min 2 The desorption time was 120min.
Weighing: and weighing the desorbed solution to obtain the volume and mass of the solution.
In fig. 4, it can be seen that the desorption rate of the absorbent is increased and then decreased, because the desorption is an endothermic reaction, the three-necked flask needs a certain time to be heated in the oil bath pot, the desorption rate is increased by increasing the temperature, and the desorption rate reaches the maximum value after the temperature is increased to the domestic temperature of the oil bath; with time, the desorption rate gradually decreases and becomes stable.
Compared with 30% DAP solution, the desorption rate is greatly improved after the nonaqueous solvent is added; wherein DAP/DMF/H 2 The desorption rate of the O absorbent reaches the maximum value within 11min and is 47.87 mol/kg -1 *min -1 2.5 times the maximum absorption rate of 30% DAP; the desorption load was 1.75mol/kg, and the desorption load of 30% DAP was 0.45mol/kg, compared to 30% DAP, DAP/DMF/H 2 The desorption load of O is increased by 2.8 times.
Comparative example 1
Preparing an absorbent: weighing 12g of primary amine and 28g of deionized water by using a balance, and fully mixing to obtain 30wt.% absorption liquid which is 40g in total; primary amine selected ethanolamine (MEA) and 1, 3-propanediamine (DAP)
Absorption reaction: pouring the prepared absorbent into a three-neck flask in a water bath pot, absorbing 300ml/min of mixed gas at the constant temperature of 40 ℃ and the normal pressure, and obtaining the split-phase absorbent after the absorption is finished.
And (3) desorption reaction: absorbing the mixed gas for 120min, separating to obtain a phase-rich solution, performing desorption experiment in a magnetic stirring oil bath, keeping the temperature of the magnetic stirring oil bath at 90 ℃, placing the three-neck flask in the oil bath to heat, starting a magnetic stirrer, condensing outlet gas through cold water of a condensing tube under gas purging, washing the bottle to absorb volatilized amine, drying the volatilized water vapor by a drying tube, and then entering an infrared analyzer to measure CO at an outlet 2 Concentration. N with purge gas of 300ml/min 2 The desorption time was 120min.
The phase separation time, carbon dioxide loading of the rich phase, lean rich liquid volume ratio and loading after desorption of the obtained absorbent after absorption are shown in table 3.
Table 3 shows the carbon dioxide absorption performance parameters of the absorbent obtained in comparative example 1
As can be seen from Table 3, the classical formulation had a load of 1.51mol/kg for the rich phase after carbon dioxide absorption by 30% MEA and 3.06mol/kg for the 30% DAP, and neither was split phase, and the entire solution was regenerated in a regeneration column; while DAP/DMF/H 2 The load after O absorption was 4.45mol/kg, 2.9 times the load of 30% MEA absorption and 1.5 times the load of 30% DAP absorption.
Claims (10)
1. A liquid-liquid absorbent for capturing carbon dioxide, characterized by comprising the following chemical components: 1, 3-propanediamine, nonaqueous solvent and H 2 O。
2. The liquid-liquid absorbent for capturing carbon dioxide according to claim 1, wherein the nonaqueous solvent is a phase-splitting agent.
3. The liquid-liquid absorbent for capturing carbon dioxide according to claim 1, wherein the nonaqueous solvent is one or more selected from NMP, N-butanol, sulfolane, N-dimethylformamide, diethylene glycol dimethyl ether, N-pentanol and N-propanol.
4. The liquid-liquid absorbent for capturing carbon dioxide according to claim 1, wherein the 1, 3-propanediamine, a nonaqueous solvent and H 2 The mass ratio of O is as follows: 20% -30% to 30% -40% and 30% -40% of the total weight of the composite material.
5. A method of using a liquid-liquid absorbent for capturing carbon dioxide as claimed in any one of claims 1 to 4, characterized by the steps of:
(1): mixing the prepared 1, 3-propylene diamine, non-aqueous solvent and H according to the mass ratio 2 Mixing O, and uniformly stirring at room temperature to obtain a DAP/water/nonaqueous solvent two-phase absorbent;
(2): placing the prepared DAP/water/nonaqueous solvent two-phase absorbent in a constant-temperature water bath kettle to absorb mixed gas;
(3): CO in mixed gas 2 Absorbed by nonaqueous solvent and then reacts with DAP, DAP and CO 2 After the reaction, DAP-carbamate, deprotonated DAP and a nonaqueous solvent are generated;
wherein the non-aqueous solvent is used as phase-splitting agent only to accelerate CO 2 The molecules react with DAP in contact and phase separate;
(4): and (3) separating phases of the absorption liquid after the absorption reaction by using a separating funnel to obtain an upper phase and a lower phase, and finally respectively comparing the volume, the mass and the viscosity.
6. The method for using a liquid-liquid absorbent for capturing carbon dioxide according to claim 5, wherein in step (1), the room temperature is 20 to 30 ℃.
7. The method for using a liquid-liquid absorbent for capturing carbon dioxide according to claim 5, wherein in the step (2), the constant temperature water bath is kept at 40 ℃, the gas is 500ml/min of pure carbon dioxide, and the phase-separated absorbent is obtained after absorption for 30 min.
8. The method for using a liquid-liquid absorbent for capturing carbon dioxide according to claim 7, wherein the phase separation is specifically: the absorbed two-phase absorbent is subjected to standing and cooling and then is subjected to phase separation by a phase separator, and DAP carbamate, carbonate and deprotonated DAP generated by the reaction are arranged at the lower layer, and are called as rich phases; the upper phase is a mixed liquid of a nonaqueous solvent and water, called the lean phase.
9. The method of claim 5, wherein in step (2), the mixed gas is formed by 88% N 2 And 12% CO 2 The total gas amount is 300ml/min, and the absorption time is 120min.
10. The method of claim 9, wherein the mixed gas is absorbed for 120min, the phase-enriched solution is obtained through phase separation, a desorption experiment is performed in a magnetic stirring oil bath, the magnetic stirring oil bath is kept at a constant temperature of 90 ℃, a three-neck flask is put into the oil bath to be heated, a magnetic stirrer is started, under the condition of gas purging, outlet gas is condensed through cold water of a condensing pipe, the water washing bottle absorbs volatile amine, and the volatile water vapor is dried by a drying pipe and then enters an infrared analyzer to measure CO at an outlet 2 Concentration.
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