CN105617819A - Method for absorbing carbon dioxide in synthesis gas at low temperature with ionic liquid - Google Patents
Method for absorbing carbon dioxide in synthesis gas at low temperature with ionic liquid Download PDFInfo
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- CN105617819A CN105617819A CN201610113722.7A CN201610113722A CN105617819A CN 105617819 A CN105617819 A CN 105617819A CN 201610113722 A CN201610113722 A CN 201610113722A CN 105617819 A CN105617819 A CN 105617819A
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- ionic liquid
- carbon dioxide
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- 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
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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
- 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
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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
- 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
Abstract
The invention relates to a method for absorbing carbon dioxide in synthesis gas at low temperature with ionic liquid, and belongs to the technical field of gas separation and purification. An absorbing agent can be single ionic liquid or a mixed solution of several kinds of ionic liquid. An absorption tower is operated at the temperature of minus 45 DEG C-0 DEG C and the pressure of 0.3-10 MPa, and the number of theoretical plates is 11-30. Raw material gas is fed from the bottom of the absorption tower, the ionic liquid serving as the absorbing agent is added from the top of the tower, raffinate which is rich in ionic liquid and located at the bottom of the tower enters a flash tank, and the carbon dioxide in the ionic liquid is removed. Compared with the prior art, when the ionic liquid and the mixed solvent are adopted to absorb CO2 in the synthesis gas, a good absorbing effect is achieved, the ionic liquid is neutral, compressor corrosion, high consumption and environment pollution caused when traditional solvent is used for absorbing gas can be avoided, equipment is simple, investments are few, and energy consumption is low.
Description
Technical field
The present invention relates to a kind of with ionic liquid for CO in absorbent low temperature absorption synthesis gas2Method, belong to gas separating and purifying technology field.
Background technology
Global air temperature warming, as a kind of greenhouse gases, is had important impact by carbon dioxide, in order to reduce the negative effect that greenhouse effect brings, CO to society and economy2Absorption is a pith in Gas-treating processes. And China CO2Industrial discharge be mainly derived from two classes: one is flue gas produced by the combustion of fossil fuel such as coal, a class be in chemical industry produce synthesis gas. Synthesis gas chemical industry occupies highly important status in modern chemical industry, as synthesized ammonia, synthesis alkene, F-T synthesis and hydrogen manufacturing etc. from synthesis gas. Difference according to subsequent technique, the industrial separation to synthesis gas requires also different with purification, sometimes very strict (must be removed to below 20ppm), for instance for synthetic ammonia process, CO2It is the poisonous substance of ammonia synthesis catalyst, can cause that again subsequent process produces NH4HCO3Or (NH4)2CO3Crystallization in turn results in the blocking of pipeline and equipment.
Ionic liquid refers to the organic salt being made up of organic cation or organic anion, typically exhibits liquid in room temperature or under room temperature. Ionic liquid has good heat stability, is difficult to volatilization, is easily isolated the characteristics such as recovery, renewable recycling and function designability. These special structures and physical property bring wide development space to the application of ionic liquid, and especially " non-" volatility of ionic liquid itself dissolves CO in a large number with unique2Ability, so as in fixing conversion with utilize CO2Aspect has great application potential.
Summary of the invention
It is an object of the invention to provide a kind of ionic liquid for the method that gas low temperature absorbs, the method uses ionic liquid as absorbent, the CO in low temperature absorption synthesis gas2, obtain CO in synthesis gas2Content is less than 2000ppm, and ionic liquid can recycle.
A kind of method of carbon dioxide in ionic liquid low temperature absorption synthesis gas, it is characterized in that, unstripped gas containing carbon dioxide is from absorption tower bottom feed, ionic liquid adds from tower top as absorbent, the operation temperature on absorption tower is-45-0 DEG C, operating under pressure 0.3-10MPa, theoretical cam curve is 11-30; Unstripped gas, from absorption tower bottom feed, enters flash tank rich in the raffinate phase of ionic liquid at the bottom of tower, and the carbon dioxide in elimination ionic liquid, the ionic liquid of extraction bottom flash tank recycles.
In unstripped gas containing carbon dioxide, the content of carbon dioxide is 0.02-0.30 (molar fraction), and solvent ratio is for 2.7-80 (solvent is than the ratio for entering the IL on absorption tower and unstripped gas mass flow).
Flash tank, at temperature 50-200 DEG C, operates when pressure 1atm.
The carbonated ionic liquid of richness flowed out bottom absorption tower is preferentially heated by heat exchanger, enters back into flash tank.
CO in unstripped gas containing carbon dioxide2Molar fraction content is 0.02-0.30, CO in the synthesis gas that tower top obtains2Content is less than 2000ppm.
Absorbent can be a kind of ionic liquid or the mixed solution of several ionic liquid, ionic liquid cation can be imidazoles, pyridines, quaternary ammonium salt etc., and anion can be bis-trifluoromethylsulfoandimide root, tetrafluoroborate, hexafluoro-phosphate radical, acetate, dithyl sulfate root etc. The glyoxaline ion liquid cation adopted is 1-octyl group-3-methylimidazolyl and 1-ethyl-3-methylimidazole base, and anion is bis-trifluoromethylsulfoandimide root, but is not limited to above-mentioned cation and anion.
Unstripped gas containing carbon dioxide is containing CO2Mixing gas, it is also possible to be pure CO2Gas.
Compared with prior art, ionic liquid low temperature absorption carbon dioxide ability is strong, effective, simultaneously ionic liquid is in neutrality, it is to avoid the corrosion of equipment, it is to avoid the problem such as high energy consumption that gas brings and environmental pollution that uses conventional solvent to absorb, equipment is simple, and small investment, energy consumption is low.
Accompanying drawing explanation
Accompanying drawing 1 is CO in ionic liquid absorption synthesis gas2Process chart.
Wherein: B1 absorption tower; B2 flash tank; S ionic liquid charging, F unstripped gas charging; D overhead product; G1 CO2Stripping gas; W reclaims ionic liquid.
Detailed description of the invention
Present invention following example illustrate to adopt the effect of carbon dioxide in ionic liquid elimination synthesis gas, but the present invention is not limited to following embodiment, and under the scope without departing from the described objective in front and back, alternate embodiment is included in the technical scope of the present invention.
As it is shown in figure 1, the present invention adopts the absorption technique including absorption tower, solvent flash tank. Absorbent enters from absorbing tower jacking, and synthesis gas enters from the bottom of absorbing tower. Entering flash tank from the logistics of extraction at the bottom of absorbing tower, the carbon dioxide in flash tank flash distillation elimination ionic liquid, highly purified ionic liquid is from extraction bottom flash tank, it is possible to recycle.
Embodiment 1
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-10 DEG C, pressure 3MPa, and absorption tower has 17 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [EMIM]+[Tf2N]-(1-ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 1000kg/h, and tower top obtains CO in synthesis gas2Content is 20ppm, rich in [EMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [EMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 18, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 11ppm.
Changing absorption tower number of theoretical plate is 19, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 6ppm.
Embodiment 2
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature 0 DEG C, pressure 3MPa, and absorption tower has 25 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [EMIM]+[Tf2N]-(1-ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 1000kg/h, and tower top obtains CO in synthesis gas2Content is 16ppm, rich in [EMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [EMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 26, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 11ppm.
Changing absorption tower number of theoretical plate is 27, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 7ppm.
Embodiment 3
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-45 DEG C, pressure 3MPa, and absorption tower has 12 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 2000kg/h, and tower top obtains CO in synthesis gas2Content is 13ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 13, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 6ppm.
Changing absorption tower number of theoretical plate is 14, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 5ppm.
Embodiment 4
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-30 DEG C, pressure 3MPa, and absorption tower has 11 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 2000kg/h, and tower top obtains CO in synthesis gas2Content is 12ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 12, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 5ppm.
Changing absorption tower number of theoretical plate is 13, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 3ppm.
Embodiment 5
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-20 DEG C, pressure 3MPa, and absorption tower has 13 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 2000kg/h, and tower top obtains CO in synthesis gas2Content is 12ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 14, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 6ppm.
Changing absorption tower number of theoretical plate is 15, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 3ppm.
Embodiment 6
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-10 DEG C, pressure 3MPa, and absorption tower has 14 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 2000kg/h, and tower top obtains CO in synthesis gas2Content is 12ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 15, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 7ppm.
Changing absorption tower number of theoretical plate is 16, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 3ppm.
Embodiment 7
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature 0 DEG C, pressure 3MPa, and absorption tower has 15 blocks of theoretical trays, CO in synthesis gas2Content is 0.3 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 2000kg/h, and tower top obtains CO in synthesis gas2Content is 13ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower number of theoretical plate is 16, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 8ppm.
Changing absorption tower number of theoretical plate is 17, and other conditions are constant, and tower top obtains CO in synthesis gas2Content is 4ppm.
Embodiment 8
Absorption flow process as shown in Figure 1. The operating condition on absorption tower is temperature-45 DEG C, pressure 0.3MPa, and absorption tower has 30 blocks of theoretical trays, CO in synthesis gas2Content is 0.02 (molar fraction), and from charging at the bottom of tower, mass flow is 100kg/h, with ionic liquid [OMIM]+[Tf2N]-(1-octyl group-3-Methylimidazole. bis-trifluoromethylsulfoandimide) adds from tower top for absorbent, and mass flow is 7600kg/h, and tower top obtains CO in synthesis gas2Content is 10ppm, rich in [OMIM] at the bottom of tower+[Tf2N]-Raffinate phase enter flash tank, bottom flash tank [OMIM] of extraction+[Tf2N]-Recycle.
Changing absorption tower pressure and be 10MPa and absorbent flow is 270kg/h, other conditions are constant, and tower top obtains CO in synthesis gas2Content is 10ppm.
Claims (7)
1. the method for carbon dioxide in an ionic liquid low temperature absorption synthesis gas, it is characterized in that, unstripped gas containing carbon dioxide is from absorption tower bottom feed, ionic liquid adds from tower top as absorbent, the operation temperature on absorption tower is-45-0 DEG C, operating under pressure 0.3-10MPa, theoretical cam curve is 11-30; Entering flash tank rich in the raffinate phase of ionic liquid at the bottom of tower, the carbon dioxide in elimination ionic liquid, the ionic liquid of extraction bottom flash tank recycles.
2. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterised in that in the unstripped gas containing carbon dioxide, the molar fraction content of carbon dioxide is 0.02-0.30, solvent is than for 2.7-80.
3. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterized in that, absorbent is a kind of ionic liquid or the mixed solution of several ionic liquid, ionic liquid cation is selected from imidazoles, pyridines or quaternary ammonium salt, and anion is selected from bis-trifluoromethylsulfoandimide root, tetrafluoroborate, hexafluoro-phosphate radical, acetate or dithyl sulfate root.
4. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterised in that flash tank temperature 50-200 DEG C, pressure 1atm when operation.
5. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterised in that the carbonated ionic liquid of richness flowed out bottom absorption tower is preferentially heated by heat exchanger, enters back into flash tank.
6. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterised in that CO in the unstripped gas containing carbon dioxide2Molar fraction content is 0.02-0.30, CO in the synthesis gas that tower top obtains2Content is less than 2000ppm.
7. the method for carbon dioxide in a kind of ionic liquid low temperature absorption synthesis gas described in claim 1, it is characterised in that the unstripped gas containing carbon dioxide is containing CO2Mixing gas or pure CO2Gas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159132A (en) * | 2017-06-07 | 2017-09-15 | 华中科技大学 | CO2/ CO selective absorbents and preparation method thereof |
| CN108911946A (en) * | 2018-06-04 | 2018-11-30 | 北京化工大学 | A kind of method that ionic liquid is used to remove HF in fluoric compound |
| CN108993098A (en) * | 2018-08-13 | 2018-12-14 | 中国地质大学（北京） | A kind of efficiently trapping CO2Eutectic solvent system and the preparation method and application thereof |
| CN109908706A (en) * | 2019-04-10 | 2019-06-21 | 南京大学 | Ion liquid microcapsule and preparation method thereof and except the application in light concentration gas |
| CN113265282A (en) * | 2021-06-11 | 2021-08-17 | 郑州轻工业大学 | CO in natural gas separated from mixed ionic liquid2Method (2) |
| CN114539202A (en) * | 2022-01-21 | 2022-05-27 | 中国科学院兰州化学物理研究所 | Method for preparing cyclic carbonate by catalyzing flue gas with imidazole type ionic liquid |
| CN108911946B (en) * | 2018-06-04 | 2024-05-07 | 阿科玛（常熟）氟化工有限公司 | Method for removing HF in fluoro-compound by using ionic liquid |
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| CN113265282A (en) * | 2021-06-11 | 2021-08-17 | 郑州轻工业大学 | CO in natural gas separated from mixed ionic liquid2Method (2) |
| CN114539202A (en) * | 2022-01-21 | 2022-05-27 | 中国科学院兰州化学物理研究所 | Method for preparing cyclic carbonate by catalyzing flue gas with imidazole type ionic liquid |
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