CN102989295A - Absorbent which gathers carbon dioxide in flue gas or synthesis gas - Google Patents
Absorbent which gathers carbon dioxide in flue gas or synthesis gas Download PDFInfo
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- CN102989295A CN102989295A CN2012104842353A CN201210484235A CN102989295A CN 102989295 A CN102989295 A CN 102989295A CN 2012104842353 A CN2012104842353 A CN 2012104842353A CN 201210484235 A CN201210484235 A CN 201210484235A CN 102989295 A CN102989295 A CN 102989295A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention discloses an absorbent which gathers carbon dioxide in flue gas or synthesis gas, comprising the following components by weight percentage: 5-25wt% of 2- methylamino (ethanol), 5-25wt% of primary amine, secondary amine or tertiary amine and 60-90% of water. As the 2- methylamino (ethanol) is a secondary amine which has a higher boiling point compared than other secondary amine, the degradation loss of solvent is less. The absorbent of the invention can be used for gathering various normal-pressure gas mixture, such as carbon dioxide in flue gas or synthesis gas discharged by the enterprises of coal-fired power plants, petrochemical industry and the like. The absorbent has large absorbing volume for carbon dioxide at low partial pressure, the regeneration effect is good and the energy consumption for unit carbon dioxide gathering amount is low.
Description
Technical field
The present invention relates to GAS ABSORPTION and separation engineering technical field, be specifically related to a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas.
Background technology
CO
2Being a kind of in the greenhouse gases, is to cause Global Greenhouse Effect, causes the principal element of climate change.CO
2Trapping technique is one of effective way of alleviation greenhouse effects recognized in the world, reply climate change.From mist, capture CO
2Be exactly a kind of important method wherein, these mists comprise the flue gas, synthesis gas of enterprises' dischargings such as coal-burning power plant, oil plant, chemical plant etc., generally contain 3%～55% CO in these mists
2, other gas componant mainly contains N according to the difference of technique and different
2, CO
2, O
2, CO, H
2, CH
4, SO
2, H
2S etc.
Chemical absorption method is suitable for flue gas CO
2Dividing potential drop is lower, the demanding situation of degree of purification.At present chemical absorbent relatively more commonly used mainly contains: monoethanolamine (MEA), and N methyldiethanol amine (MDEA), diethanol amine (DEA) equal solvent or its mixture, but these solvent reclamation thermal energy consumptions are large, easily degraded.In order to reduce energy consumption, reduce the degraded of lyosoption, many improved pure amine solvents have appearred, and adopt in measures such as By Amine Solutions and adding activators and improve the hydramine absorbability.20 century 70s Germany BASF (BASF) company adds N methyldiethanol amine (MDEA) in monoethanolamine (MEA), develop a kind of solution that relatively has better absorbent properties and desorption performance, but do not solved regeneration energy consumption high and amine degradation and the problem strong to equipment corrosion.
The patent disclosures such as domestic 00126925.9, CN1546207 take N methyldiethanol amine (MDEA) or monoethanolamine (MEA) as main component, add therein the activators such as diethanol amine (DMEA), piperazine (PZ), sterically hindered amines or two or more mixture, be mainly used in the carbon dioxide that captures or remove in natural gas or the gas mixture.The absorbent of this class take N methyldiethanol amine (MDEA) or monoethanolamine (MEA) as main component exists that energy consumption is high, the easy shortcoming such as degraded of absorbent when being used for cigarette and capturing the low dividing potential drop gas capturing carbon dioxide such as road gas or synthesis gas.
Therefore exploitation is fit to the high absorptive capacity of the collecting carbonic anhydride of flue gas or synthesis gas, the absorbent of low energy consumption has the meaning of particular importance.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the purpose of this invention is to provide a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas, have the characteristics of high absorptive capacity, low energy consumption, low solvent consumption.
For achieving the above object the technical solution used in the present invention:
A kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas comprises the component of following mass percent: 2-(methylamino)-Ethanol: 5～25wt%; Amine: 5～25wt%; Water: 60%～90%, wherein said components is in the total amount of absorbent, and wherein said amine is selected from one or more in primary amine, secondary amine or the tertiary amine, and during for mixture, ratio is any.
Primary amine is selected from one or more in monoethanolamine (MEA) and the 2-amino-2-methyl-1-propanol (AMP), and during for mixture, ratio is any.
Described secondary amine is selected from one or more in diethanol amine (DEA) and the piperazine (PZ), and during for mixture, ratio is any.
Described tertiary amine is selected from N methyldiethanol amine (MDEA) and N, one or more in the N-dimethylethanolamine (DMEA), and during for mixture, ratio is any.
Described amine is preferably monoethanolamine (MEA), piperazine (PZ) or N methyldiethanol amine (MDEA).
The consumption of described 2-(methylamino)-Ethanol is preferably 8～20wt%, more preferably 10～15wt%.
The consumption of described amine is preferably 8～20wt%, more preferably 10～15wt%.
The most preferred absorbent of the present invention is selected from following combination:
(1) a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas, component is: 2-(methylamino)-Ethanol, N methyldiethanol amine, piperazine and water; Wherein component and content are preferably 2-(methylamino)-Ethanol 20wt%, N methyldiethanol amine 8.33wt%, piperazine 1.67wt%, water 70wt%.
(2) a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas, component is: 2-(methylamino)-Ethanol, N methyldiethanol amine, piperazine and water; Preferred component and content are 2-(methylamino)-Ethanol 15wt%, N methyldiethanol amine 12.5wt%, piperazine 2.5wt%, water 70wt%.
(3) a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas, component is: 2-(methylamino)-Ethanol, monoethanolamine, N methyldiethanol amine, diethanol amine and water; Preferred component and content are 2-(methylamino)-Ethanol 5wt%, monoethanolamine 15wt%, N methyldiethanol amine 5wt%, diethanol amine 5wt%, water 70%.
(4) a kind of absorbent that captures carbon dioxide in flue gas or the synthesis gas, component is: 2-(methylamino)-Ethanol, monoethanolamine, N methyldiethanol amine, piperazine and water; Preferred component and content are 2-(methylamino) ethanol 10wt%, monoethanolamine 11wt%, N methyldiethanol amine 6wt%, piperazine 3wt%, water 70wt%; Perhaps 2-(methylamino)-Ethanol 5wt%, monoethanolamine 15wt%, N methyldiethanol amine 5wt%, piperazine 5wt%, water 70wt%.
The preparation method of absorbent of the present invention is formed by directly mixing the 2-(methylamino)-Ethanol of 5～25wt%, 60%～90% water and each component of amine of 5～25wt%.
The application of absorbent of the present invention can be used for capturing the CO in the multiple gases mixture
2, comprise the flue gas of enterprise's dischargings such as various atmosphere gas mixtures such as coal-burning power plant, petrochemical industry or the carbon dioxide in the synthesis gas.
Absorbent of the present invention captures CO
2Process conditions be: operating pressure is normal pressure; The absorbent inlet temperature of stabilizer is 25～60 ℃; The regenerator low temperature is 100～120 ℃.
Different from existing absorbent, the present invention utilizes 2-(methylamino)-Ethanol as main component, adds simultaneously primary amine, secondary amine or tertiary amine, to the CO in low pressure and normal pressure lower flue gas or the synthesis gas
2Absorptive capacity is good greatly, and when concentration of absorbing 30%, clean absorptive capacity is at 1.0～2.0LCO
2Between/L the amine; The regeneration energy consumption of absorbent is low simultaneously, under the equal process conditions (such as flue gas condition, absorption and regeneration temperature, pressure etc.), compares the CO of unit with existing absorbent
2The consumption of the required steam of output and electric energy significantly reduces; Have higher boiling point owing to 2-(methylamino)-Ethanol with respect to other secondary amine simultaneously, thereby reduced the solvent loss in the collecting carbonic anhydride process, thereby reduced CO
2The operating cost of capturing device.
The specific embodiment
Following examples are used for explanation the present invention, but it will be appreciated by those skilled in the art that all embodiment must not be as limitation of the present invention.Any improvement of making within the scope of the invention or variation are all within protection scope of the present invention.
Embodiment 1
Get 20g 2-(methylamino)-Ethanol (NMEA), 8.33g N methyldiethanol amine (MDEA), 1.67g piperazine (PZ), 70g water is configured to 30% composite absorber, and wherein 2-(methylamino)-Ethanol accounts for 20wt%, N methyldiethanol amine accounts for 8.33%, and piperazine accounts for 1.67%, and water accounts for 70wt%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 3:
Table 1 2-(methylamino)-Ethanol 20wt%+N-methyl diethanolamine 8.33wt%+ piperazine 1.67wt%
Embodiment 2
Get 15g 2-(methylamino)-Ethanol (NMEA), 12.5g N methyldiethanol amine (MDEA), 2.5g piperazine (PZ), 70g water is configured to 30% composite absorber, and wherein 2-(methylamino)-Ethanol accounts for 15wt%, N methyldiethanol amine accounts for 12.5%, and piperazine accounts for 2.5%, and water accounts for 70%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 1:
Table 2 2-(methylamino)-Ethanol 15wt%+N-methyl diethanolamine 12.5wt%+ piperazine 2.5wt%
Embodiment 3
Get 15g monoethanolamine (MEA), the 5g2-(methylamino) ethanol (NMEA), 5g N methyldiethanol amine (MDEA), 5g diethanol amine (DEA), 70g water, be configured to 30% composite absorber, wherein monoethanolamine accounts for 15wt%, and 2-(methylamino)-Ethanol accounts for 5wt%, and N methyldiethanol amine accounts for 5wt%, diethanol amine accounts for wt5%, and water accounts for 70wt%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 3:
Table 3 30% monoethanolamine 15wt%+2-(methylamino) ethanol 5wt%+N-methyl diethanolamine 5wt%+ diethanol amine 5wt%
Can find out from embodiment 1, embodiment 2, main body concentration is the 2-(methylamino)-Ethanol+N methyldiethanol amine of two kinds of different proportions of 30%+piperazine composite absorber at 40 ℃, absorb under the normal pressure, at 110 ℃, back pressure is to regenerate under the condition of 0.1MPa, and the absorbent of 1 liter of 2-(methylamino)-Ethanol 15wt%+N-methyl diethanolamine 12.5wt%+ piperazine 2.5wt% can absorb CO
2Amount be 2.244 liters, simultaneously clean absorptive capacity (the volume absorptive capacity the during volume capacity during absorption equilibrium-regeneration balance) is 1.351(L CO
2/ L amine).1 liter of 2-(methylamino)-Ethanol 15wt%+N-methyl diethanolamine 7.5wt%+ piperazine 7.5wt% absorbent can absorb CO
2Amount be 2.417 liters, simultaneously clean absorptive capacity is 1.542(L CO
2/ Lamine).Can find out that from embodiment 3 under the condition of embodiment 1 and embodiment 2, main body concentration is 1 liter of monoethanolamine 15wt%+2-(methylamino of 30%) ethanol 5wt%+N-methyl diethanolamine 5wt%+ diethanol amine 5wt% absorbent can absorb CO
2Amount be 2.489 liters, simultaneously clean absorptive capacity is 1.221(L CO
2/ L amine).
Embodiment 4
Get the 10g2-(methylamino) ethanol (NMEA), 11g monoethanolamine (MEA), 6g N methyldiethanol amine (MDEA), 3g piperazine (PZ), 70g water, be configured to 30% composite absorber, wherein monoethanolamine accounts for 12wt%, and 2-(methylamino)-Ethanol accounts for 9wt%, and N methyldiethanol amine accounts for 3%, piperazine accounts for 3%, and water accounts for 70%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 4:
Table 4 2-(methylamino) ethanol 10wt%+ monoethanolamine 11wt%+N-methyl diethanolamine 6wt%+ piperazine 3wt%
Embodiment 5
Get 5g 2-(methylamino)-Ethanol (NMEA), 15g monoethanolamine (MEA), 5g N methyldiethanol amine (MDEA), 5g piperazine (PZ), 70g water, be configured to 30% composite absorber, wherein monoethanolamine accounts for 15wt%, and 2-(methylamino)-Ethanol accounts for 5wt%, and N methyldiethanol amine accounts for 5%, piperazine accounts for 5%, and water accounts for 70%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 5:
Table 5 2-(methylamino)-Ethanol 5wt%+ monoethanolamine 15wt%+N-methyl diethanolamine 5wt%+ piperazine 5wt%
Can find out from embodiment 4, embodiment 5, main body concentration is the monoethanolamine+2-(methylamino)-Ethanol of three kinds of different proportions of 30%+N methyldiethanol amine+piperazine absorbent at 40 ℃, absorb under the normal pressure, at 110 ℃, back pressure is to regenerate 1 liter of monoethanolamine 15wt%+2-(methylamino under the condition of 0.1MPa) absorbent of ethanol 5wt%+N-methyl diethanolamine 5wt%+ piperazine 5wt% can absorb CO
2Amount be 2.941 liters, simultaneously clean absorptive capacity (the volume absorptive capacity the during volume capacity during absorption equilibrium-regeneration balance) is 1.405(L CO
2/ L amine).1 liter of monoethanolamine 12wt%+2-(methylamino) ethanol 9wt%+N-methyl diethanolamine 6wt%+ piperazine 3wt% absorbent can absorb CO
2Amount be 2.724 liters, simultaneously clean absorptive capacity is 1.385(L CO
2/ L amine).
Embodiment 6
Get 10g 2-(methylamino)-Ethanol (NMEA), 4g N methyldiethanol amine (MDEA), 1g piperazine (PZ), 85g water is configured to 15% composite absorber, and wherein 2-(methylamino)-Ethanol accounts for 10wt%, N methyldiethanol amine accounts for 4%, and piperazine accounts for 1%, and water accounts for 85wt%.
Mixed gas flow is 2L/min, consists of 15vt% CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 6:
Table 6 2-(methylamino)-Ethanol 10wt%+N-methyl diethanolamine 4wt%+ piperazine 1wt%
Embodiment 7
Get the 15g2-(methylamino) ethanol (NMEA), 15g monoethanolamine (MEA), 5g N methyldiethanol amine (MDEA), 5g diethanol amine (DEA), 60g water, be configured to 40% composite absorber, wherein 2-(methylamino)-Ethanol accounts for 15wt%, and monoethanolamine accounts for 15wt%, and N methyldiethanol amine accounts for 5wt%, diethanol amine accounts for wt5%, and water accounts for 60wt%.
Mixed gas flow is 2L/min, consists of 15vt%CO
2And 85vt%N
2Mist passed in the above-mentioned composite absorber under normal pressure, 40 ℃ absorb, after gas-liquid two-phase reaches balance, liquid is finished in absorption placed 120 ℃, back pressure is to regenerate under the condition of 0.1MPa.Its volume absorptive capacity and clean absorptive capacity are as shown in table 7:
Table 7 30%2-(methylamino) ethanol 15wt%+ monoethanolamine 15wt%+N-methyl diethanolamine 5wt%+ diethanol amine 5wt%
Can find out from embodiment 6, embodiment 7, main body concentration is the 15%(2-(methylamino) ethanol 10wt%+N-methyl diethanolamine 4wt%+ piperazine 1wt%) and (30%2-(methylamino) ethanol 15wt%+ monoethanolamine 15wt%+N-methyl diethanolamine 5wt%+ diethanol amine 5wt% of 40%) two kinds of absorbents are at 40 ℃, absorb under the normal pressure, at 110 ℃, back pressure is to regenerate under the condition of 0.1MPa, and the absorbent of 1 liter of 2-(methylamino)-Ethanol 10wt%+N-methyl diethanolamine 4wt%+ piperazine 1wt% can absorb CO
2Amount be 2.632 liters, simultaneously clean absorptive capacity (the volume absorptive capacity the during volume capacity during absorption equilibrium-regeneration balance) is 1.624(L CO
2/ L amine).1 liter of 30%2-(methylamino) ethanol 15wt%+ monoethanolamine 15wt%+N-methyl diethanolamine 5wt%+ diethanol amine 5wt% absorbent can absorb CO
2Amount be 2.392 liters, simultaneously clean absorptive capacity is 1.205(L CO
2/ L amine).
Claims (10)
1. an absorbent that captures carbon dioxide in flue gas or the synthesis gas is characterized in that, described absorbent comprises: 2-(methylamino)-Ethanol: 5～25wt%; Amine: 5～25wt%; Water: 60%～90%, wherein said components is in the total amount of absorbent, and wherein said amine is selected from one or more in primary amine, secondary amine or the tertiary amine, and during for mixture, ratio is any.
2. absorbent according to claim 1, described amine is monoethanolamine (MEA), piperazine (PZ) or N methyldiethanol amine (MDEA).
3. absorbent according to claim 1, the consumption of described 2-(methylamino)-Ethanol is preferably 8-20wt%, 10-15wt% more preferably, during for mixture, ratio is any.
4. absorbent according to claim 1, the consumption of described amine is preferably 8-20wt%, more preferably 10-15wt%.
5. absorbent according to claim 1, described primary amine is selected from one or more in monoethanolamine (MEA) and the 2-amino-2-methyl-1-propanol (AMP), and during for mixture, ratio is any.
6. absorbent according to claim 1, described secondary amine is selected from one or more in diethanol amine (DEA) and the piperazine (PZ).
7. each described absorbent according to claim 1-3, described tertiary amine is selected from N methyldiethanol amine (MDEA) and N, one or more in the N-dimethylethanolamine (DMEA).
8. absorbent according to claim 1, described amine is monoethanolamine (MEA), piperazine (PZ) or N methyldiethanol amine (MDEA).
9. absorbent according to claim 1, the consumption of described 2-(methylamino)-Ethanol is 10-15wt%.
10. absorbent according to claim 1, the consumption of described amine is 10-15wt%.
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| CN2012104842353A CN102989295A (en) | 2012-11-23 | 2012-11-23 | Absorbent which gathers carbon dioxide in flue gas or synthesis gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190210A (en) * | 2014-08-26 | 2014-12-10 | 中国船舶重工集团公司第七一八研究所 | Composite organic alcohol amine absorbing agent for carbon dioxide |
| CN107158895A (en) * | 2017-07-13 | 2017-09-15 | 斯养武 | A kind of carbon-dioxide absorbent |
| CN113908662A (en) * | 2021-08-30 | 2022-01-11 | 浙江浙能技术研究院有限公司 | CO used for low-concentration flue gas2Trapped weakly polar amine-based absorbent |
| CN114870570A (en) * | 2022-05-31 | 2022-08-09 | 西南化工研究设计院有限公司 | Liquid-solid phase separation absorbent for carbon dioxide separation |
| CN115228247A (en) * | 2022-08-15 | 2022-10-25 | 北京石大油源科技开发有限公司 | Technological method and process suitable for capturing high-concentration carbon dioxide |
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| US3622267A (en) * | 1969-01-22 | 1971-11-23 | Basf Ag | Process for removing carbon dioxide from gas mixtures |
| CN1091332A (en) * | 1993-02-25 | 1994-08-31 | 南京化学工业(集团)公司研究院 | Polyamine process removes carbon dioxide and sulfide in the gas |
| CN1127156A (en) * | 1994-10-06 | 1996-07-24 | 关西电力株式会社 | Method for removing carbon dioxide from gas |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622267A (en) * | 1969-01-22 | 1971-11-23 | Basf Ag | Process for removing carbon dioxide from gas mixtures |
| CN1091332A (en) * | 1993-02-25 | 1994-08-31 | 南京化学工业(集团)公司研究院 | Polyamine process removes carbon dioxide and sulfide in the gas |
| CN1127156A (en) * | 1994-10-06 | 1996-07-24 | 关西电力株式会社 | Method for removing carbon dioxide from gas |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190210A (en) * | 2014-08-26 | 2014-12-10 | 中国船舶重工集团公司第七一八研究所 | Composite organic alcohol amine absorbing agent for carbon dioxide |
| CN107158895A (en) * | 2017-07-13 | 2017-09-15 | 斯养武 | A kind of carbon-dioxide absorbent |
| CN107158895B (en) * | 2017-07-13 | 2020-07-28 | 斯养武 | Carbon dioxide absorbent |
| CN113908662A (en) * | 2021-08-30 | 2022-01-11 | 浙江浙能技术研究院有限公司 | CO used for low-concentration flue gas2Trapped weakly polar amine-based absorbent |
| CN114870570A (en) * | 2022-05-31 | 2022-08-09 | 西南化工研究设计院有限公司 | Liquid-solid phase separation absorbent for carbon dioxide separation |
| CN114870570B (en) * | 2022-05-31 | 2023-10-03 | 西南化工研究设计院有限公司 | Liquid-solid phase-splitting absorbent for separating carbon dioxide |
| CN115228247A (en) * | 2022-08-15 | 2022-10-25 | 北京石大油源科技开发有限公司 | Technological method and process suitable for capturing high-concentration carbon dioxide |
| CN115228247B (en) * | 2022-08-15 | 2023-08-22 | 北京石大油源科技开发有限公司 | Technological method and process suitable for capturing high-concentration carbon dioxide |
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Application publication date: 20130327 |