CN113457382A - Low-viscosity CO2Trapping mixed absorbent formulation - Google Patents
Low-viscosity CO2Trapping mixed absorbent formulation Download PDFInfo
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- 239000002250 absorbent Substances 0.000 title claims abstract description 75
- 230000002745 absorbent Effects 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 238000009472 formulation Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000013543 active substance Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 150000003335 secondary amines Chemical group 0.000 claims abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 34
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 14
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 8
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- -1 pentaerythritol ester Chemical class 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 38
- 230000008929 regeneration Effects 0.000 abstract description 22
- 238000011069 regeneration method Methods 0.000 abstract description 22
- 238000005265 energy consumption Methods 0.000 abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 238000003795 desorption Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000010525 oxidative degradation reaction Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CIAMOALLBVRDDK-UHFFFAOYSA-N 1,1-diaminopropan-2-ol Chemical compound CC(O)C(N)N CIAMOALLBVRDDK-UHFFFAOYSA-N 0.000 description 2
- 229910019501 NaVO3 Inorganic materials 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000695274 Processa Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- B01D53/1493—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
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- 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
-
- 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
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- 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
- B01D2252/60—Additives
-
- 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
- B01D2252/60—Additives
- B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
-
- 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
- B01D2252/60—Additives
- B01D2252/606—Anticorrosion agents
-
- 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)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to CO with low viscosity2A capture mixed absorbent formulation comprising: a main agent, an auxiliary agent, an active agent, an antidegradant and an anticorrosive agent; the main agent is organic amine containing a plurality of N atoms; the auxiliary agent is secondary amine, tertiary amine or steric hindrance amine; the active agent is a cyclic polyamino solvent. The invention has the beneficial effects that: the invention provides CO with low viscosity2The trapping mixed absorbent has the advantages of low viscosity, high absorption rate, difficult crystallization at low temperature, large absorption capacity and low regeneration energy consumption; the auxiliary agent or the auxiliary agent and the active agent are added on the basis of the main agent, so that the absorption rate and the desorption rate of the absorbent can be further improved, the energy consumption of the absorbent is reduced, and CO is absorbed by CO2The trapping field has great potential; can be widely applied to the removal and the capture of acid gas in mixed gas, such as the capture of CO from flue gas, synthesis gas and the like2And the like.
Description
Technical Field
The invention relates to the technical field of separation and purification of mixed gas, in particular to CO with low viscosity2Trapping the mixed absorbent formulation.
Background
In recent years, the atmospheric environment continues to deteriorate by the combustion of fossil fuels, and the greenhouse effect caused thereby becomes an ecological problem that seriously affects human survival on a global scale. CO 22、CH4、CFC11-12、NOXThe gases are the main cause of greenhouse effect, among which CO2Not only is a major contributor to the greenhouse effect, but the duration of the hazard is longest. To alleviate the greenhouse effect, the CO should be first solved2And the discharge and recycling problems of (2).
At present, CO can be realized2The main technical route for emission reduction is the CCUS technology, which mainly comprises pre-combustion capture, post-combustion capture and oxygen-enriched combustion. The post-combustion trapping technology is the most commonly adopted technology for power plant reconstruction and new power plant construction due to small power plant reconstruction and low initial investment. The post-combustion trapping technology relates to a chemical absorption technology, an adsorption technology, a membrane separation technology and a low-temperature distillation technology, the chemical absorption technology has good flue gas adaptability, the technology is mature, the application is wide, and an industrial demonstration platform is established. The single alcohol amine MEA is the earliest chemical absorbent for realizing commercial application, but has the advantages of small absorption capacity, low reaction rate, high regeneration energy consumption, high degradation rate, strong corrosivity, high operation cost and short operation life. Therefore, the development of a novel absorbent with low energy consumption, high capture rate, large circulation capacity, difficult degradation and volatilization and low corrosivity is a key for reducing the investment cost, the operation cost and the system energy consumption of the carbon capture system.
In recent years, some researchers have proposed the research idea of mixed absorbents, and combine the advantages of two or more absorbents to prepare the mixed absorbents, and a novel absorbent formula with high absorption rate, high absorption capacity, low regeneration energy consumption and low loss is expected to be obtained.
Chinese patent of invention (CN 1546207A) discloses a complex amine solvent, which is based on N-Methyldiethanolamine (MDEA) and adds a small amount of active agent such as Piperazine (PZ), 2-methyl-2-amino-1-propanol (AMP) and the like, and is suitable for places with lower partial pressure of carbon oxide (0.1MPa-0.25MPa), but the absorbent still has CO2Low partial pressure and low absorption rate of the absorbent.
The Chinese invention patent (CN 101804287A) discloses a mixed absorbent which uses sulfolane to replace most of water as a solvent, improves the desorption rate to a certain extent, and reduces the water content of the absorbent formula, so that the regeneration energy consumption is low, but the absorbent still has the problems of high solvent viscosity, is not beneficial to long-term operation of process equipment, has low service life of the equipment and increased operation cost, and therefore, large-scale industrial application is still not realized.
The european union published an absorbent formulation in the fifth post combustion capture conference: CESAR-1(23 wt% AMP +12 wt% PZ) has low regeneration energy consumption, but the absorbent still has poor solution crystallization, which easily causes the problems of absorption process pipeline blockage and the like.
Thus, there is a need for an absorbent formulation that has low viscosity, fast absorption rates, low tendency to crystallize at low temperatures, high absorption capacity, and low energy consumption for regeneration.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide CO with low viscosity2Trapping the mixed absorbent formulation.
CO of this low viscosity2A capture mixed absorbent formulation comprising: a main agent, an auxiliary agent, an active agent, an antidegradant and an anticorrosive agent; the main agent is organic amine containing a plurality of N atoms; the auxiliary agent is secondary amine, tertiary amine or steric hindrance amine; the active agent is a cyclic polyamino solvent; wherein the mass fraction of the main agent in the aqueous solution is 15 wt% -50 wt%, the mass fraction of the auxiliary agent in the aqueous solution is 1 wt% -20 wt%, and the active agent in the aqueous solutionThe mass fraction of (A) is 0 wt% -15 wt%; the mass concentration of the anti-degradation agent is 2 mmol/L-8 mmol/L, the mass concentration of the anti-corrosion agent is 2 mmol/L-8 mmol/L, and the balance is water, and the components are directly mixed and stirred to obtain the mixed amine absorbent.
Preferably, the main agent is one of hydroxyethyl ethylenediamine (AEEA), 1, 3-diamino-2-propanol (DAP), 2-methyl-1, 5-pentanediamine (DA2MP) and N, N-dimethyl-1, 3-Diaminopropane (DMAPA), and the mass fraction of the main agent in the aqueous solution is 20-40 wt%; diamines similar in structure to the main agent AEEA, such as 1, 3-diamino-2-propanol (DAP), 2-methyl-1, 5-pentanediamine (DA2MP), N-dimethyl-1, 3-Diaminopropane (DMAPA), and the like, have high absorption rate and high net circulation capacity, and can maintain high absorption capacity under high load, thus being capable of replacing AEEA as an absorbent main agent.
Preferably, the main agent is hydroxyethyl ethylenediamine (AEEA), the volatilization amount is far lower than that of ethanolamine (MEA) at the absorption temperature of 40-60 ℃ and the regeneration temperature of 100-130 ℃, the volatility is extremely low, the loss of an absorbent solvent can be reduced to a certain extent, and the cost is reduced; meanwhile, the reaction rate is higher than that of ethanolamine (MEA) under the same condition, the absorption capacity and the cyclic load are higher than those of ethanolamine (MEA) under the same concentration, and the reaction heat is lower than that of ethanolamine (MEA), so that the potential of hydroxyethyl ethylenediamine (AEEA) in the aspect of reducing energy consumption is higher.
Preferably, the adjuvant is one of 2-methyl-2-amino-1-propanol (AMP), Diethanolamine (DEA), and Methyldiethanolamine (MDEA); the mass fraction of the auxiliary agent in the aqueous solution is 10 wt% -20 wt%.
Preferably, the active agent is Piperazine (PZ) or 1-methylpiperazine (1-MPZ), and the mass fraction of the active agent in the aqueous solution is 0 wt% to 10 wt%.
Preferably, the antidegradant is disodium Ethylenediaminetetraacetate (EDTA) or sodium metavanadate (NaVO)3) Tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester (C)73H108O12) At least one of (1).
Preferably, the corrosion inhibitor is ethylenediamine tetra-n-ethyl acetateDisodium acetate (EDTA), sodium metavanadate (NaVO)3) Tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester (C)73H108O12) At least one of (1).
CO of this low viscosity2The binary mixed absorbent suitable for engineering provided by the trapping mixed absorbent formula comprises 20-35 wt% of main agent, 3-15 wt% of auxiliary agent and the balance of water according to mass fraction.
CO of this low viscosity2The ternary mixed absorbent suitable for engineering provided by the trapping mixed absorbent formula comprises, by mass, 20-35 wt% of a main agent, 3-15 wt% of an auxiliary agent, 1-5 wt% of an active agent and the balance of water.
Preferably, the adjuvant is one of 2-methyl-2-amino-1-propanol (AMP), Diethanolamine (DEA), and Methyldiethanolamine (MDEA); the active agent is one of cyclic polyamino solvents such as Piperazine (PZ) and 1-methylpiperazine (1-MPZ); the auxiliary agent or the auxiliary agent and the active agent are added on the basis of the main agent, so that the absorption rate and the desorption rate of the absorbent can be further improved, the energy consumption of the absorbent is reduced, and CO is absorbed by CO2The trapping field has great potential.
The invention has the beneficial effects that:
the invention provides CO with low viscosity2The trapping mixed absorbent has the advantages of low viscosity, high absorption rate, difficult crystallization at low temperature, large absorption capacity and low regeneration energy consumption; the auxiliary agent or the auxiliary agent and the active agent are added on the basis of the main agent, so that the absorption rate and the desorption rate of the absorbent can be further improved, the energy consumption of the absorbent is reduced, and CO is absorbed by CO2The trapping field has great potential.
The absorbent provided by the invention can be widely applied to removal and capture of acid gas in mixed gas, such as capture of CO from flue gas, synthesis gas and the like2And the like. In the field of flue gas capture, the absorbent formula is used, the absorption process can be a conventional one-section absorption tower or a two-section absorption tower containing interstage cooling, the regeneration process can be a tower regeneration tower or a supergravity bed and the like, and the heat integration processA conventional lean rich heat exchanger or a distributed heat exchanger may be selected. Based on the trapping process of the process, the optimal absorption temperature is generally controlled to be 30-50 ℃, the regeneration temperature is generally controlled to be 90-120 ℃, and the regeneration pressure is generally controlled to be 1-2 bar based on the cost.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Example one
The embodiment of the application provides a configuration and performance parameter detection method of an absorbent formula A, which comprises the following steps:
100g of hydroxyethyl ethylenediamine (AEEA), 40g of 2-methyl-2-amino-1-propanol (AMP) and 260g of deionized water are respectively taken and uniformly mixed to prepare 25 wt% of AEEA +10 wt% of AMP +65 wt% of H2400g of an absorbent solution of O, 3mmol/L of EDTA was added thereto, and the mixture was allowed to stand for further use.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosity of the lean-rich solution, the absorption capacity, the degree of regeneration, the circulation capacity, and the viscosity of the lean-rich solution at various temperatures were measured at 40 ℃, 50 ℃, 60 ℃, and 70 ℃ as shown in Table 1 below, and the solvent did not absorb CO2It did not crystallize at room temperature. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
Wherein the absorption capacity is defined as: 1kg of absorbent solution absorbs CO2Amount (mol); the degree of regeneration is defined as: desorption of CO from 1g of absorbent solution2Amount (mol) of (A) and 1g of absorbent solution to absorb CO2The amount (mol) of (A); the circulation capacity is defined as: CO absorption by amines per unit of substance in rich liquor2The amount of CO enriched with amine per unit of substance in the desorbed barren solution2The difference in the amount of (c).
TABLE 1 Table of Performance parameters for absorbent formulation A of this example
Example two
On the basis of the first embodiment, the second embodiment of the present application provides a configuration and performance parameter detection method for an absorbent formula B:
respectively taking 112g of hydroxyethyl ethylenediamine (AEEA), 28g of 2-methyl-2-amino-1-propanol (AMP) and 260g of deionized water, and uniformly mixing to prepare 28 wt% of AEEA +7 wt% of AMP +65 wt% of H2400g of an absorbent solution of O, 3mmol/L of EDTA as an antidegradant was added thereto, and the mixture was allowed to stand for further use.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosity of the lean and rich solution was measured at 40 ℃, 50 ℃, 60 ℃ and 70 ℃, the absorption capacity, regeneration degree, circulation capacity and the viscosity of the lean and rich solution at various temperatures were as shown in Table 2 below, and the solvent did not absorb CO2It did not crystallize at room temperature. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
TABLE 2 Table of Performance parameters for absorbent formulation B of this example
EXAMPLE III
On the basis of the first embodiment, the third embodiment of the present application provides a configuration and performance parameter detection method for an absorbent formula C:
100g of hydroxyethyl ethylenediamine (AEEA), 40g of Diethanolamine (DEA) and 260g of deionized water are respectively uniformly mixed to prepare 25 wt% of AEEA +10 wt% of DEA +65 wt% of H2400g of O absorbent solution, and 5mmol/L of NaVO3And standing for later use.
Then, the simulation was carried out at atmospheric pressure and at a temperature of 40 deg.CCO absorption at a flue gas concentration of 12%2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosity of the lean and rich liquids was measured at 40 ℃, 50 ℃, 60 ℃ and 70 ℃, the absorption capacity, regeneration degree, circulation capacity and the viscosity of the lean and rich liquids at different temperatures were as shown in Table 3 below, and the solvents did not absorb CO2It did not crystallize at room temperature. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
TABLE 3 Table of Performance parameters for absorbent formulation C of this example
Example four
On the basis of the first embodiment, the fourth embodiment of the present application provides a configuration and performance parameter detection method for an absorbent formula D:
respectively taking 128g of hydroxyethyl ethylenediamine (AEEA), 12g of Diethanolamine (DEA) and 260g of deionized water, and uniformly mixing to prepare 32 wt% of AEEA +3 wt% of DEA +65 wt% of H2400g of O absorbent solution, and 5mmol/L of NaVO3And standing for later use.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosities of the lean and rich liquids were measured at 40 ℃, 50 ℃, 60 ℃ and 70 ℃, the absorption capacity, regeneration degree, circulation capacity and viscosities of the lean and rich liquids at different temperatures are shown in table 4 below, and the solvents did not absorb CO2It did not crystallize at room temperature. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
TABLE 4 Table of Performance parameters for absorbent formulation D of this example
EXAMPLE five
On the basis of the first embodiment, the fourth embodiment of the present application provides a configuration and performance parameter detection method for an absorbent formula E:
respectively taking 128g of hydroxyethyl ethylenediamine (AEEA), 12g of Diethanolamine (DEA), 8g of Piperazine (PZ) and 252g of deionized water, and uniformly mixing to prepare 32 wt% of AEEA +3 wt% of DEA +2 wt% of PZ +65 wt% of H2400g of absorbent solution of O, and 7mmol/L of C73H108O12And standing for later use.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosity of the lean and rich liquids was measured at 40 ℃, 50 ℃, 60 ℃ and 70 ℃, the absorption capacity, regeneration degree, circulation capacity and the viscosity of the lean and rich liquids at different temperatures were as shown in Table 5 below, and the solvents did not absorb CO2It did not crystallize at room temperature. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
TABLE 5 Table of Performance parameters for absorbent formulation E of this example
EXAMPLE six
On the basis of the first embodiment, the fourth embodiment of the present application provides a configuration and performance parameter detection method for an absorbent formula F:
respectively taking 128g of hydroxyethyl ethylenediamine (AEEA), 12g of Diethanolamine (DEA), 16g of Piperazine (PZ) and 244g of deionized water, and uniformly mixing to prepare 32 wt% of AEEA +3 wt% of DEA +4 wt% of PZ +61 wt% of H2400g of absorbent solution of O, and 7mmol/L of C73H108O12And standing for later use. Meanwhile, the reaction kettle continuously operates in a closed oxidative degradation reaction kettle for 30 days, and no obvious degradation behavior is found.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2Measuring the viscosity, absorption capacity and regeneration of the lean and rich solution at 40 deg.C, 50 deg.C, 60 deg.C and 70 deg.CThe extent, circulation capacity and viscosities of the lean and rich solutions at different temperatures are shown in Table 6 below, and the solvents do not absorb CO2It did not crystallize at room temperature.
TABLE 6 Table of Performance parameters for absorbent formulation F of this example
Comparative example 1
Respectively taking 92g of 2-methyl-2-amino-1-propanol (AMP), 48g of Piperazine (PZ) and 260g of deionized water, and uniformly mixing to prepare 23 wt% AMP +12 wt% PZ +65 wt% H2400g of O absorbent solution, no antidegradant is added, and the solution is kept stand for later use.
Then absorbing CO at normal pressure, 40 ℃ and the simulated flue gas concentration of 12 percent2Desorbing CO at 25% of stirring speed and 130 ℃ of oil bath temperature2The viscosities of the lean and rich liquids were measured at 40 ℃, 50 ℃, 60 ℃ and 70 ℃, the absorption capacity, regeneration degree, circulation capacity and viscosities of the lean and rich liquids at different temperatures are shown in the following table 7, and the solvents did not absorb CO2Crystallization occurred at room temperature. Meanwhile, the catalyst is continuously operated in a closed oxidative degradation reaction kettle for 30 days, and obvious degradation behavior occurs.
TABLE 7 table of performance parameters for the absorbent formulation of comparative example one
To summarize:
according to the experimental results in comparative example 1, it was found that: without the use of the absorbent formulation of the invention in the absorption of unabsorbed CO2Crystallization occurred at room temperature. Meanwhile, the catalyst is continuously operated in a closed oxidative degradation reaction kettle for 30 days, and obvious degradation behavior occurs. From the experimental results in examples one to six, it can be seen that the absorbent formulations of the present invention have a large absorption load, a high regeneration level, a large circulation capacity, a low viscosity of the lean rich solution at different temperatures, and a non-absorbed CO by the solvent2Is not crystallized at room temperature and is denseThe closed oxidation degradation reaction kettle is continuously operated for 30 days, and no obvious degradation behavior is found. Compared with the prior art, the invention has the beneficial effects that: invention of low-viscosity CO2The trapping mixed absorbent has the advantages of low viscosity, high absorption rate, difficult crystallization at low temperature, large absorption capacity and low regeneration energy consumption.
Claims (10)
1. Low-viscosity CO2A capture mixed absorbent formulation, comprising: a main agent, an auxiliary agent, an active agent, an antidegradant and an anticorrosive agent; the main agent is organic amine containing a plurality of N atoms; the auxiliary agent is secondary amine, tertiary amine or steric hindrance amine; the active agent is a cyclic polyamino solvent;
wherein the mass fraction of the main agent in the aqueous solution is 15-50 wt%, the mass fraction of the auxiliary agent in the aqueous solution is 1-20 wt%, and the mass fraction of the active agent in the aqueous solution is 0-15 wt%; the mass concentration of the anti-degradation agent is 2 mmol/L-8 mmol/L, the mass concentration of the anti-corrosion agent is 2 mmol/L-8 mmol/L, and the balance is water.
2. CO of low viscosity according to claim 12The trapping mixed absorbent formula is characterized in that: the main agent is one of hydroxyethyl ethylenediamine, 1, 3-diamino-2-propanol, 2-methyl-1, 5-pentanediamine and N, N-dimethyl-1, 3-diaminopropane, and the mass fraction of the main agent in the aqueous solution is 20-40 wt%.
3. CO of low viscosity according to claim 22The trapping mixed absorbent formula is characterized in that: the main agent is hydroxyethyl ethylenediamine.
4. CO of low viscosity according to claim 12The trapping mixed absorbent formula is characterized in that: the auxiliary agent is one of 2-methyl-2-amino-1-propanol, diethanolamine and methyldiethanolamine; the mass fraction of the auxiliary agent in the aqueous solution is 10 wt% -20 wt%.
5. CO of low viscosity according to claim 12The trapping mixed absorbent formula is characterized in that: the active agent is piperazine or 1-methylpiperazine, and the mass fraction of the active agent in the aqueous solution is 0 wt% -10 wt%.
6. CO of low viscosity according to claim 12The trapping mixed absorbent formula is characterized in that: the antidegradant is disodium ethylene diamine tetraacetate, sodium metavanadate and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]At least one pentaerythritol ester.
7. CO of low viscosity according to claim 12The trapping mixed absorbent formula is characterized in that: the corrosion inhibitor is disodium ethylene diamine tetraacetate, sodium metavanadate and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]At least one pentaerythritol ester.
8. CO of low viscosity according to claim 12The binary mixed absorbent suitable for engineering provided by the trapping mixed absorbent formula is characterized by comprising 20-35 wt% of a main agent, 3-15 wt% of an auxiliary agent and the balance of water in percentage by mass.
9. CO of low viscosity according to claim 12The ternary mixed absorbent suitable for engineering provided by the trapping mixed absorbent formula is characterized by comprising 20-35 wt% of a main agent, 3-15 wt% of an auxiliary agent, 1-5 wt% of an active agent and the balance of water by mass.
10. The engineered ternary mixed absorbent of claim 9, wherein: the auxiliary agent is one of 2-methyl-2-amino-1-propanol, diethanolamine and methyldiethanolamine; the active agent is one of piperazine and 1-methylpiperazine.
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