WO2011071150A1 - Carbon dioxide absorbent for use under high pressure, and method for absorption and collection of carbon dioxide under high pressure - Google Patents
Carbon dioxide absorbent for use under high pressure, and method for absorption and collection of carbon dioxide under high pressure Download PDFInfo
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- WO2011071150A1 WO2011071150A1 PCT/JP2010/072242 JP2010072242W WO2011071150A1 WO 2011071150 A1 WO2011071150 A1 WO 2011071150A1 JP 2010072242 W JP2010072242 W JP 2010072242W WO 2011071150 A1 WO2011071150 A1 WO 2011071150A1
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- 0 CC(C)(*O*C(*)(*)N(*)*)N(*)* Chemical compound CC(C)(*O*C(*)(*)N(*)*)N(*)* 0.000 description 1
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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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- 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
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- 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
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2023—Glycols, diols or their derivatives
- B01D2252/2025—Ethers or esters of alkylene glycols, e.g. ethylene or propylene carbonate
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- 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
- B01D2252/20431—Tertiary amines
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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
Definitions
- the present invention is directed to removing carbon dioxide from a gas stream having a high carbon dioxide partial pressure (indicating above 2 bar), in particular to remove carbon dioxide from exhaust gas from a coal gasification process, and absorption and absorption It relates to a collection method.
- CO2 contained in mixed gas is targeted for mixed gas discharged from thermal power plants, boilers in steelworks, kilns in cement factories, etc. that use coal, heavy oil, natural gas, etc., which are the sources of carbon dioxide as fuel.
- a series of carbon dioxide capture and storage (CCS) technologies, including carbon capture, compression, transportation, and injection, are attracting attention as bridging technologies to develop alternative energy alternatives to fossil fuels.
- Patent Document 1 discloses a method for removing carbon dioxide from a gas stream in which the partial pressure of carbon dioxide in the gas stream is less than 0.2 bar, and this gas stream is (A) at least 2 in the molecule.
- a method for removing carbon dioxide from a gas stream in contact with a liquid absorbent comprising an aqueous solution of an amine compound having three tertiary amino groups and an active agent selected from (B) a primary amine and a secondary amine is described. Has been.
- carbon dioxide separation and recovery technology using chemical absorption from high-pressure gas such as coal gasification product gas and mined natural gas has relatively few research examples compared to separation and recovery technology from atmospheric pressure exhaust gas.
- the pressure energy of the gas itself can be utilized for carbon dioxide separation recovery and compression, the cost during the carbon dioxide storage process, particularly in the separation recovery + compression process, may be significantly reduced. Therefore, the focus is on the development of chemical absorbents applicable to carbon dioxide separation from high pressure gas.
- the physical absorption method has attracted attention as a method for removing acidic gas containing carbon dioxide from gas having pressure.
- the higher the partial pressure of the target gas component the greater the amount of acid gas absorbed per unit absorption liquid compared to the chemical absorption method.
- Typical absorbents include cyclotetramethylene sulfone (sulfolane) and derivatives thereof, and absorbents composed of aliphatic amides, methanol, and polyethylene glycol dialkyl ethers (SELEXOL, Union Carbide).
- SELEXOL Polyethylene glycol dialkyl ethers
- Patent Document 2 relates to an acid gas regeneration method performed under a pressure exceeding 3.5 bar absolute pressure and not exceeding 20 bar absolute pressure, and the separated gas stream generated from the regenerator is compressed and underground. It is described that it is press-fitted during storage. Moreover, triethanolamine etc. are mentioned as an acidic gas absorptive chemical agent.
- the absorbent illustrated in the examples consists of 43% by weight N-methyldiethanolamine and 57% by weight water.
- an aqueous solution of N-methyldiethanolamine (MDEA) and an aqueous solution of triethanolamine are generally used.
- MDEA N-methyldiethanolamine
- triethanolamine aqueous solution of triethanolamine.
- concentrations up to 50% by weight in the region where the partial pressure of carbon dioxide assumed by IGCC (Coal Gasification Combined Cycle) is high, the dispersibility is poor, and the efficiency of carbon dioxide recovery and amine regeneration becomes poor, and carbon dioxide recovery. Increased energy and cost.
- MDEA is used in an amount of 60% by weight or more, it is difficult to put it to practical use because the handling property deteriorates due to the increase in viscosity and the absorption rate decreases.
- Patent Document 3 describes a method for removing acid gas from a gas supply stream including a regeneration method in which an absorbing liquid containing acid gas at a high concentration is heated at a pressure higher than atmospheric pressure.
- the absorbing liquid is a tertiary alkylamine selected from diamines, triamines and tetramines. It is described that it can be regenerated at a high pressure by using an aqueous amine solution at a high concentration (60 to 90% by weight).
- the present invention provides a high-efficiency carbon dioxide absorbent and absorption and recovery method capable of achieving separation of carbon dioxide in a gas at a higher carbon dioxide absorption rate and emission rate than in the past in a region where the carbon dioxide partial pressure is high.
- the purpose is to do.
- Patent Document 3 describes that in a region where the partial pressure of carbon dioxide is high, the amount of carbon dioxide recovered is improved by using an aqueous amine solution at a high concentration of 60% by weight or more.
- the absorption rate and the emission rate may be improved as well as the carbon dioxide recovery amount. I understood.
- the present inventors use a tertiary aliphatic amine aqueous solution that does not have a hydrogen bond group and has an ether group at a high concentration, thereby enabling a high absorption rate and high in a region where the partial pressure of carbon dioxide is high. It was possible to obtain an amine solution having a diffusion rate and a high carbon dioxide recovery amount, and obtained the knowledge that the above object could be achieved.
- the present invention has been completed based on these findings, and has been completed.
- the present invention provides the following carbon dioxide absorbent and absorption and recovery method.
- R 1 , R 2 , R 3 and R 4 are the same or different and represent an alkyl group
- R 5 and R 6 are the same or different and represent an alkylene group
- n 1 to 5 is there.
- Item 2 The water-containing liquid absorbent according to Item 1, wherein the tertiary aliphatic amine is bis (2-dimethylaminoethyl) ether.
- Item 3 A step of absorbing the carbon dioxide from the gas flow by contacting the water-containing liquid absorbent according to Item 1 or 2 with a gas flow having a carbon dioxide partial pressure of 2 bar or more, and (2) the above step ( Heating the water-containing liquid absorbent that has absorbed carbon dioxide obtained in 1) to desorb and recover carbon dioxide; Carbon dioxide absorption and recovery method comprising:
- Item 4. Item 4.
- the step (1) is performed at a carbon dioxide partial pressure of 2 to 40 bar, and the step (2) is performed at a carbon dioxide partial pressure of 2 bar or more. Carbon dioxide absorption and recovery method.
- Item 5 The method for absorbing and recovering carbon dioxide according to Item 3 or 4, wherein the step (1) is performed at a temperature of 25 to 60 ° C, and the step (2) is performed at a temperature of 70 to 120 ° C. .
- the absorbent of the present invention since the absorption rate and the emission rate of carbon dioxide are high in an environment where the partial pressure of carbon dioxide is high, a more compact separation device can be designed and an economical device can be obtained. Moreover, since the amount of carbon dioxide recovered increases in an environment where the carbon dioxide partial pressure is high, separation with low energy becomes possible.
- 6 is a graph showing the results of carbon dioxide absorption in Test Example 2.
- 7 is a graph showing the results of carbon dioxide absorption rate, emission rate, and CO 2 recovery amount in Test Example 3.
- Water-containing liquid absorbent for absorbing and recovering carbon dioxide The water-containing liquid absorbent of the present invention absorbs and recovers carbon dioxide from a gas stream in which the partial pressure of carbon dioxide in the gas stream is 2 bar or more, and in general 60 to 90% by weight of a tertiary aliphatic amine represented by the formula [1] is contained.
- R 1 , R 2 , R 3 and R 4 in the general formula [1] are the same or different and are an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. It is a group.
- alkyl group having 1 to 6 carbon atoms examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hexyl.
- alkyl group having 1 to 3 carbon atoms examples include methyl, ethyl, n-propyl, and isopropyl.
- R 5 and R 6 in the general formula [1] are the same or different and are an alkylene group, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
- alkylene group having 1 to 6 carbon atoms examples include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, and hexylene.
- alkylene group having 1 to 3 carbon atoms examples include methylene, ethylene, n-propylene, and isopropylene.
- n is an integer selected from 1 to 5, preferably 1 to 4, more preferably 1 to 2.
- Examples of the tertiary aliphatic amine represented by the general formula [1] include bis (2-dimethylaminoethyl) ether.
- the above-mentioned tertiary aliphatic amine can be produced as a known method according to the description in References 1 to 4 below, or is commercially available because it is commercially available.
- the tertiary aliphatic amine can be synthesized based on the following formula using diethylene glycol or polyethylene glycol as a raw material as described in the following documents 1 to 4.
- Document 1 International Publication No. 2005/110969
- Document 2 Japanese Patent Laid-Open No. 9-20735
- Document 3 European Patent Application Publication No. 300323
- Document 4 West German Patent Application Publication No. 3422610
- the heat of reaction of the tertiary aliphatic amine is desirably 40 to 70 kJ / mol-CO 2, particularly 45 to 60 kJ / mol-CO 2 .
- the reaction heat is used to mean the amount of heat generated when 1 mol of CO 2 is absorbed at 40 ° C. and atmospheric pressure.
- the tertiary aliphatic amine has an absorption rate of 2 to 5 times, an emission rate of 2 to 5 times, and a carbon dioxide recovery amount of 2 to 3 times that of MDEA.
- the water-containing liquid absorbent according to the present invention contains 60 to 90% by weight of the tertiary aliphatic amine. If it is this range, it will be excellent in the absorption rate and emission rate of a carbon dioxide. Preferably 60 to 80% by weight, more preferably 60 to 70% by weight.
- the water-containing liquid absorbent of the present invention may also contain an antioxidant, a corrosion inhibitor, a physical absorbent and the like as components other than the tertiary aliphatic amine.
- antioxidants examples include BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), sodium erythorbate, sodium sulfite, sulfur dioxide and the like.
- Examples of the physical absorbent include cyclotetramethylene sulfone (sulfolane) and derivatives thereof, aliphatic acid amide (acetylmorpholine, N-formylmorpholine), N-alkylated pyrrolidone and a corresponding piperidone such as N-methylpyrrolidone (NMP), And dialkyl ethers such as propylene carbonate, methanol, and polyethylene glycol.
- cyclotetramethylene sulfone sulfolane
- aliphatic acid amide acetylmorpholine, N-formylmorpholine
- N-alkylated pyrrolidone and a corresponding piperidone such as N-methylpyrrolidone (NMP)
- dialkyl ethers such as propylene carbonate, methanol, and polyethylene glycol.
- the partial pressure of carbon dioxide in the gas stream in which the water-containing liquid absorbent of the present invention absorbs and recovers carbon dioxide is 2 bar or more. If it is this range, it will be excellent in the absorption rate and emission rate of a carbon dioxide. It is preferably 10 bar or more, more preferably 10 to 40 bar.
- gas flow examples include exhaust gas from a coal gasification process, mined natural gas, and the like, and the concentration of carbon dioxide in the gas is usually about 20 to 50% by volume, particularly about 30 to 40% by volume. That's fine. In such a carbon dioxide concentration range, the effects of the present invention are suitably exhibited.
- the gas stream may contain gas such as water vapor, CO, H 2 S, COS, and H 2 in addition to carbon dioxide.
- Carbon dioxide absorption and recovery method comprises: (1) contacting the above-mentioned hydrated liquid absorbent with a gas stream having a partial pressure of carbon dioxide of 2 bar or more, thereby And (2) heating the hydrated liquid absorbent that has absorbed carbon dioxide obtained in the above step (1) to desorb and recover the carbon dioxide.
- step (1) carbon dioxide is absorbed from the gas stream by contacting the hydrated liquid absorbent with a gas stream having a carbon dioxide partial pressure of 2 bar or more.
- the method for bringing the gas flow into contact with the above-mentioned water-containing liquid absorbent there is no particular limitation on the method for bringing the gas flow into contact with the above-mentioned water-containing liquid absorbent.
- a method of bubbling a gas flow into the absorbent and absorbing it a method of dropping the absorbent into a gas stream (a spray or spray method), or a magnetic or metal mesh filler This is performed by a method in which the gas flow and the absorbent are brought into countercurrent contact in the absorption tower.
- Step (1) is preferably performed at a partial pressure of carbon dioxide of 2 to 40 bar, particularly 2 to 20 bar. Step (1) is preferably performed at a temperature of 25 to 60 ° C., particularly 40 to 60 ° C.
- Step (2) the water-containing liquid absorbent that has absorbed the carbon dioxide obtained in the step (1) is heated to desorb and recover the carbon dioxide.
- a method of desorbing carbon dioxide from a water-containing liquid absorbent that has absorbed carbon dioxide and recovering pure or high-concentration carbon dioxide a method of heating the absorbent and bubbling it in a kettle as in distillation, a shelf Examples thereof include a method in which a liquid interface is expanded and heated in a plate tower, a spray tower, a desorption tower containing a magnetic or metal mesh filler. Thereby, carbon dioxide is released from the absorbent and released.
- Step (2) is preferably performed at a carbon dioxide partial pressure of 2 to 8 bar or more, particularly 2 to 80 bar.
- Step (2) is preferably performed at a temperature of 70 to 120 ° C., particularly 90 to 120 ° C.
- the upper temperature limit is not limited to 120 ° C., and it can be used even at a temperature higher than 120 ° C.
- step (2) The absorbent after desorbing carbon dioxide is sent again to step (1) and recycled. During this time, the heat applied in the step (2) is effectively used for raising the temperature of the absorbent by heat exchange with the absorbent in the circulation process, and the energy of the entire recovery process is reduced.
- the purity of carbon dioxide recovered in this way is usually extremely high, about 95 to 99.9% by volume.
- This pure carbon dioxide or high-concentration carbon dioxide is used as a chemical, a raw material for synthesizing a high-molecular substance, or a cooling agent for freezing food.
- Reagents and gas types used in the reagent examples and comparative examples are as follows.
- the pressure adjustment valve was adjusted so that the pressure in the high-pressure vessel reached the specified pressure (0.2 to 40 bar), and the nitrogen gas flow rate controller was set to 3 minL / min and pressure increase was started.
- a 40 ° C. oil bath was circulated around the high pressure vessel to maintain the temperature of the high pressure vessel at 40 ° C.
- the temperature of the condenser is kept at 5 ° C, and it plays the role of returning the volatilized water-containing liquid absorbent into the high-pressure vessel.
- carbon dioxide was absorbed by setting the carbon dioxide flow rate controller to 0.3 to 2.7 L / min and the nitrogen gas flow rate controller to 0.3 to 2.7 L / min.
- the amount of carbon dioxide absorbed by the water-containing liquid absorbent was calculated from the difference between the flow rate at the inlet, the gas composition and the flow meter at the outlet, and the CO 2 concentration meter.
- the temperature of the high-pressure vessel is raised to 120 ° C by switching the oil bath at 40 ° C circulating around the high-pressure vessel to an oil bath at 120 ° C. went.
- the amount of carbon dioxide released from the water-containing liquid absorbent was calculated from the difference between the inlet flow rate, gas composition, outlet flow meter, and CO 2 concentration meter.
- the absorption rate of carbon dioxide with respect to the water-containing liquid absorbent was defined as the amount of absorption per unit time at the start of carbon dioxide absorption.
- the emission rate of carbon dioxide with respect to the water-containing liquid absorbent was defined as the amount of absorption per unit time at the start of carbon dioxide emission.
- the amount of carbon dioxide recovered with respect to the water-containing liquid absorbent was defined as a value obtained by subtracting the amount of carbon dioxide absorbed at 120 ° C. from the amount of carbon dioxide absorbed at 40 ° C.
- Test example 1 An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown).
- the composition of the water-containing liquid absorbent used in this test example was 30% by weight and 60% by weight of Bis (2DMAE) ER, and 35% by weight of MDEA.
- Absorption conditions and emission conditions in this test example are absorption conditions of 40 ° C., 16 bar (CO 2 partial pressure), emission conditions of 120 ° C., 16 bar (CO 2 partial pressure), and absorption conditions of 40 ° C., 0.2 bar (CO 2 Partial pressure) and emission conditions were 120 ° C. and 0.2 bar (CO 2 partial pressure).
- Table 3 shows the results of carbon dioxide absorption rate, emission rate, and CO 2 recovery in this test example.
- Bis (2DMAE) ER had a low absorption rate and a high release rate at 0.2 bar, and the amount of carbon dioxide recovered was small. However, the absorption rate and the emission rate improved at 16 bar, and the absorption rate and the emission rate were large when the amine concentration was 60% by weight, and the CO 2 recovery was also large. For MDEA, the higher the partial pressure of CO 2 , the higher the absorption rate, the emission rate and the CO 2 recovery, but no significant increase was observed as much as 60% by weight of Bis (2DMAE) ER.
- Test example 2 An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown).
- the composition of the water-containing liquid absorbent used in this test example was 30% and 60% by weight of Bis (2DMAE) ER, 35% and 60% by weight of MDEA, and 30% and 60% by weight of PMDETA.
- Absorption conditions and emission conditions in this test example were absorption conditions of 40 ° C. and 16 bar (CO 2 partial pressure), and emission conditions of 120 ° C. and 16 bar (CO 2 partial pressure).
- MDEA corresponds to the absorbent of the invention of Patent Document 2 (International Publication No. 2005/009692)
- PMDETA corresponds to the absorbent of the invention of Patent Document 3 (International Publication No. 2004/082809).
- the value obtained by subtracting the carbon dioxide concentration in liquid at 120 ° C. from the carbon dioxide concentration in liquid at 40 ° C. indicates the amount of carbon dioxide recovered.
- MDEA showed no significant change in carbon dioxide recovery at 35 wt% and 60 wt%, while Bis (2DMAE) ER recovered carbon dioxide at 60 wt% compared to 30 wt%. The amount increased.
- Bis (2DMAE) ER has a higher absorption rate and emission rate at 60% by weight than that of PMDETA and MDEA, and also shows a large value for carbon dioxide recovery. From this, it can be seen that the absorbent of the present invention has particularly high absorption rate and emission rate as compared with the absorbents of Patent Documents 2 and 3.
- Test example 3 An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown).
- the composition of the water-containing liquid absorbent used in this test example was Bis (2DMAE) ER 30, 50, 60, 70, 80 and 90% by weight.
- Absorption conditions and emission conditions in this test example were absorption conditions of 40 ° C. and 16 bar (CO 2 partial pressure), and emission conditions of 120 ° C. and 16 bar (CO 2 partial pressure).
- Table 5 and FIG. 2 show the results of carbon dioxide absorption rate, emission rate, and CO 2 recovery amount according to this test example.
- the absorption rate increased greatly from 60 to 90% by weight compared to 30 to 50% by weight. Further, the emission rate and the carbon dioxide recovery amount reached the maximum at 60% by weight. From the above results, it was found that the Bis (2DMAE) ER concentration showed high performance at 60 to 90% by weight.
- Test example 4 An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown).
- the composition of the water-containing liquid absorbent used in this test example was Bis (2DMAE) ER 60% by weight.
- Absorption conditions and emission conditions in this test example were absorption conditions of 40 ° C., emission conditions of 120 ° C., and pressures during absorption and emission were 0.2, 2, 16, and 40 bar (CO 2 partial pressure).
- Table 6 shows the results of the carbon dioxide absorption rate, the emission rate, and the CO 2 recovery amount according to this test example.
- the absorption rate and the release rate were 100 g / L hr or more at 2 bar or more, and showed larger values as the CO 2 partial pressure increased.
- the amount of carbon dioxide recovered was 100 g / L or more at 2 bar or more. From the above results, it was found that the CO 2 partial pressure was 2 bar or more and high performance was exhibited. Further, it was confirmed that the carbon dioxide recovery amount was 100 g / L or more under the absorption conditions of 40 ° C., the CO 2 partial pressure of 40 bar, the emission conditions of 120 ° C., the CO 2 partial pressure of 80 bar.
- the water-containing liquid absorbent having two or more ether groups has the same absorption rate, emission rate, and recovery amount as bis (2-dimethylaminoethyl) ether, but the vapor pressure is reduced, so that the volatilization amount can be reduced.
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Abstract
Description
一般式〔1〕: Item 1. A hydrous liquid absorbent for absorbing and recovering carbon dioxide from a gas stream having a partial pressure of carbon dioxide in the gas stream of 2 bar or more, comprising a tertiary aliphatic amine represented by the general formula [1] A hydrous liquid absorbent comprising -90% by weight.
General formula [1]:
(2)上記工程(1)で得られた二酸化炭素を吸収した含水液状吸収剤を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 Item 3. (1) A step of absorbing the carbon dioxide from the gas flow by contacting the water-containing liquid absorbent according to Item 1 or 2 with a gas flow having a carbon dioxide partial pressure of 2 bar or more, and (2) the above step ( Heating the water-containing liquid absorbent that has absorbed carbon dioxide obtained in 1) to desorb and recover carbon dioxide;
Carbon dioxide absorption and recovery method comprising:
本発明の含水液状吸収剤は、ガス流中の二酸化炭素分圧が2 bar以上であるガス流から二酸化炭素を吸収及び回収すること、及び一般式〔1〕で表される3級脂肪族アミンを60~90重量%含むことを特徴とする。
一般式〔1〕: Water-containing liquid absorbent for absorbing and recovering carbon dioxide The water-containing liquid absorbent of the present invention absorbs and recovers carbon dioxide from a gas stream in which the partial pressure of carbon dioxide in the gas stream is 2 bar or more, and in general 60 to 90% by weight of a tertiary aliphatic amine represented by the formula [1] is contained.
General formula [1]:
Me2NH + HO-CH2-(CH2-O-CH2)n-CH2-OH → Me2N-CH2-(CH2-O-CH2)n-CH2-NMe2
文献1:国際公開第2005/110969号
文献2:特開平9-20735号公報
文献3:欧州特許出願公開300323号明細書
文献4:西独国特許出願公開3422610号明細書 Specifically, the tertiary aliphatic amine can be synthesized based on the following formula using diethylene glycol or polyethylene glycol as a raw material as described in the following documents 1 to 4.
Me 2 NH + HO-CH 2- (CH 2 -O-CH 2 ) n -CH 2 -OH → Me 2 N-CH 2- (CH 2 -O-CH 2 ) n -CH 2 -NMe 2
Document 1: International Publication No. 2005/110969 Document 2: Japanese Patent Laid-Open No. 9-20735 Document 3: European Patent Application Publication No. 300323 Document 4: West German Patent Application Publication No. 3422610
本発明の二酸化炭素の吸収及び回収方法は、(1)上記含水液状吸収剤を二酸化炭素分圧が2 bar以上であるガス流と接触させることで、ガス流から二酸化炭素を吸収させる工程、及び(2)上記工程(1)で得られた二酸化炭素を吸収した含水液状吸収剤を加熱して、二酸化炭素を脱離して回収する工程を含むことを特徴とする。 Carbon dioxide absorption and recovery method The carbon dioxide absorption and recovery method of the present invention comprises: (1) contacting the above-mentioned hydrated liquid absorbent with a gas stream having a partial pressure of carbon dioxide of 2 bar or more, thereby And (2) heating the hydrated liquid absorbent that has absorbed carbon dioxide obtained in the above step (1) to desorb and recover the carbon dioxide.
工程(1)では、上記含水液状吸収剤を二酸化炭素分圧が2 bar以上であるガス流と接触させることで、ガス流から二酸化炭素を吸収させる。 Process (1)
In step (1), carbon dioxide is absorbed from the gas stream by contacting the hydrated liquid absorbent with a gas stream having a carbon dioxide partial pressure of 2 bar or more.
工程(2)では、上記工程(1)で得られた二酸化炭素を吸収した含水液状吸収剤を加熱して、二酸化炭素を脱離して回収する。 Step (2)
In the step (2), the water-containing liquid absorbent that has absorbed the carbon dioxide obtained in the step (1) is heated to desorb and recover the carbon dioxide.
実施例及び比較例で使用した試薬及びガス種は以下の通りである。 Reagents and gas types used in the reagent examples and comparative examples are as follows.
含水液状吸収剤に対する二酸化炭素の吸収速度、放散速度及び回収量の測定は、炭酸ガスボンベ、窒素ボンベ、炭酸ガス流量コントローラー、窒素ガス流量コントローラー、高圧容器(600 cc)、コンデンサー、圧力調整弁、流量計、CO2濃度計を順次接続した装置を用いて行った。高圧容器の周りには温度が40℃と120℃に制御された2つの油浴が接続された。 Experimental method Measurement of carbon dioxide absorption rate, emission rate and recovery amount for water-containing liquid absorbent is carbon dioxide cylinder, nitrogen cylinder, carbon dioxide flow controller, nitrogen gas flow controller, high pressure vessel (600 cc), condenser, pressure regulating valve This was performed using a device in which a flow meter and a CO 2 concentration meter were sequentially connected. Two oil baths with temperatures controlled at 40 ° C and 120 ° C were connected around the high-pressure vessel.
図示しない吸収装置を用いて、二酸化炭素の吸収放散試験を行った。本試験例で用いた含水液状吸収剤の組成はBis(2DMAE)ER 30重量%及び60重量%、MDEA 35重量%であった。本試験例における吸収条件及び放散条件は、吸収条件40℃、16 bar(CO2分圧)、放散条件120℃、16 bar(CO2分圧)、及び吸収条件40℃、0.2 bar(CO2分圧)、放散条件120℃、0.2 bar(CO2分圧)であった。 Test example 1
An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown). The composition of the water-containing liquid absorbent used in this test example was 30% by weight and 60% by weight of Bis (2DMAE) ER, and 35% by weight of MDEA. Absorption conditions and emission conditions in this test example are absorption conditions of 40 ° C., 16 bar (CO 2 partial pressure), emission conditions of 120 ° C., 16 bar (CO 2 partial pressure), and absorption conditions of 40 ° C., 0.2 bar (CO 2 Partial pressure) and emission conditions were 120 ° C. and 0.2 bar (CO 2 partial pressure).
図示しない吸収装置を用いて、二酸化炭素の吸収放散試験を行った。本試験例で用いた含水液状吸収剤の組成はBis(2DMAE)ER 30重量%及び60重量%、MDEA 35重量%及び60重量%、PMDETA 30重量%及び60重量%であった。本試験例における吸収条件及び放散条件は、吸収条件40℃、16 bar(CO2分圧)、放散条件120℃、16 bar(CO2分圧)であった。 Test example 2
An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown). The composition of the water-containing liquid absorbent used in this test example was 30% and 60% by weight of Bis (2DMAE) ER, 35% and 60% by weight of MDEA, and 30% and 60% by weight of PMDETA. Absorption conditions and emission conditions in this test example were absorption conditions of 40 ° C. and 16 bar (CO 2 partial pressure), and emission conditions of 120 ° C. and 16 bar (CO 2 partial pressure).
図示しない吸収装置を用いて、二酸化炭素の吸収放散試験を行った。本試験例で用いた含水液状吸収剤の組成はBis(2DMAE)ER 30、50、60、70、80及び90重量%であった。本試験例における吸収条件及び放散条件は、吸収条件40℃、16 bar(CO2分圧)、放散条件120℃、16 bar(CO2分圧)であった。 Test example 3
An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown). The composition of the water-containing liquid absorbent used in this test example was Bis (2DMAE)
図示しない吸収装置を用いて、二酸化炭素の吸収放散試験を行った。本試験例で用いた含水液状吸収剤の組成はBis(2DMAE)ER 60重量%であった。本試験例における吸収条件及び放散条件は、吸収条件40℃、放散条件120℃、吸収、放散時の圧力は0.2、2、16、40 bar(CO2分圧)であった。 Test example 4
An absorption / dissipation test of carbon dioxide was performed using an absorption device (not shown). The composition of the water-containing liquid absorbent used in this test example was Bis (2DMAE)
Claims (5)
- ガス流中の二酸化炭素分圧が2 bar以上であるガス流から二酸化炭素を吸収及び回収するための含水液状吸収剤であって、一般式〔1〕で表される3級脂肪族アミンを60~90重量%含むことを特徴とする含水液状吸収剤。
一般式〔1〕:
[式中、R1, R2, R3及びR4は、同一又は異なって、アルキル基を表し、R5及びR6は、同一又は異なって、アルキレン基を表し、n = 1~5である。] A hydrous liquid absorbent for absorbing and recovering carbon dioxide from a gas stream having a partial pressure of carbon dioxide in the gas stream of 2 bar or more, comprising a tertiary aliphatic amine represented by the general formula [1] A hydrous liquid absorbent comprising -90% by weight.
General formula [1]:
[Wherein R 1 , R 2 , R 3 and R 4 are the same or different and represent an alkyl group, R 5 and R 6 are the same or different and represent an alkylene group, and n = 1 to 5 is there. ] - 前記3級脂肪族アミンがビス(2-ジメチルアミノエチル)エーテルである、請求項1に記載の含水液状吸収剤。 The water-containing liquid absorbent according to claim 1, wherein the tertiary aliphatic amine is bis (2-dimethylaminoethyl) ether.
- (1)請求項1に記載の含水液状吸収剤を二酸化炭素分圧が2 bar以上であるガス流と接触させることで、ガス流から二酸化炭素を吸収させる工程、及び
(2)上記工程(1)で得られた二酸化炭素を吸収した含水液状吸収剤を加熱して、二酸化炭素を脱離して回収する工程、
を含む二酸化炭素の吸収及び回収方法。 (1) A step of absorbing carbon dioxide from a gas flow by contacting the water-containing liquid absorbent according to claim 1 with a gas flow having a carbon dioxide partial pressure of 2 bar or more, and (2) the step (1) Heating the water-containing liquid absorbent that has absorbed carbon dioxide obtained in step 2) to desorb and recover carbon dioxide,
Carbon dioxide absorption and recovery method comprising: - 前記工程(1)が、二酸化炭素分圧が2~40 barの圧力で行われ、且つ、前記工程(2)が、二酸化炭素分圧が2 bar以上の圧力で行われる、請求項3に記載の二酸化炭素の吸収及び回収方法。 The step (1) is performed at a carbon dioxide partial pressure of 2 to 40 bar, and the step (2) is performed at a carbon dioxide partial pressure of 2 bar or more. Of carbon dioxide absorption and recovery.
- 前記工程(1)が、25~60℃の温度で行われ、且つ、前記工程(2)が、70~120℃の温度で行われる、請求項3に記載の二酸化炭素の吸収及び回収方法。 The method for absorbing and recovering carbon dioxide according to claim 3, wherein the step (1) is performed at a temperature of 25 to 60 ° C, and the step (2) is performed at a temperature of 70 to 120 ° C.
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JP2014036933A (en) * | 2012-08-17 | 2014-02-27 | Research Institute Of Innovative Technology For The Earth | Liquid absorbent and separation-recovery method for separating-recovering carbon dioxide from gas flow containing high pressure carbon dioxide |
WO2015159546A1 (en) * | 2014-04-16 | 2015-10-22 | 千代田化工建設株式会社 | System and method for liquefying natural gas |
CN105664672A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid decarbonizing agent for removing high-concentration CO2 in gas |
JP2017189726A (en) * | 2016-04-11 | 2017-10-19 | 川崎重工業株式会社 | Carbon dioxide separation recovery system |
JP2017189727A (en) * | 2016-04-11 | 2017-10-19 | 川崎重工業株式会社 | Carbon dioxide separation recovery system |
JP2018134604A (en) * | 2017-02-23 | 2018-08-30 | 川崎重工業株式会社 | Carbon dioxide separation recovery system |
WO2019163867A1 (en) * | 2018-02-23 | 2019-08-29 | 公益財団法人地球環境産業技術研究機構 | Absorbent for carbon dioxide, and method for separating/collecting carbon dioxide |
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EP3527695A1 (en) * | 2018-02-14 | 2019-08-21 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Integrated electrochemical capture and conversion of carbon dioxide |
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JP2014036933A (en) * | 2012-08-17 | 2014-02-27 | Research Institute Of Innovative Technology For The Earth | Liquid absorbent and separation-recovery method for separating-recovering carbon dioxide from gas flow containing high pressure carbon dioxide |
WO2015159546A1 (en) * | 2014-04-16 | 2015-10-22 | 千代田化工建設株式会社 | System and method for liquefying natural gas |
CN105664672A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid decarbonizing agent for removing high-concentration CO2 in gas |
JP2017189726A (en) * | 2016-04-11 | 2017-10-19 | 川崎重工業株式会社 | Carbon dioxide separation recovery system |
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JP2018134604A (en) * | 2017-02-23 | 2018-08-30 | 川崎重工業株式会社 | Carbon dioxide separation recovery system |
WO2019163867A1 (en) * | 2018-02-23 | 2019-08-29 | 公益財団法人地球環境産業技術研究機構 | Absorbent for carbon dioxide, and method for separating/collecting carbon dioxide |
JPWO2019163867A1 (en) * | 2018-02-23 | 2021-03-04 | 公益財団法人地球環境産業技術研究機構 | Carbon dioxide absorber and carbon dioxide separation and recovery method |
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