Complex amine absorbent, and device and method for removing one or both of CO2 and H2S

Abstract

An absorbent is prepared by dissolving in water 1) monoethanolamine (MEA) and 2) a primary amine represented by the following formula (1) and having high steric hindrance. Releasability of CO.sub.2 or H.sub.2S during regeneration of the absorbent is thereby improved, and the amount of water vapor used during regeneration of the absorbent in a facility for recovering CO.sub.2 or H.sub.2S can be reduced. ##STR00001##
R.sub.1 to R.sub.3: H or a hydrocarbon group having 1 to 3 carbon atoms, at least one of R.sub.1 to R.sub.3 being a hydrocarbon.

Claims

1. A complex amine absorbent for absorbing one or both of CO.sub.2 and H.sub.2S in a gas, the complex amine absorbent comprising 1) monoethanolamine (MEA), 2) 2-amino-2-methyl-1-propanol, and 3) at least one selected from the group consisting of N,N-dimethylethylenediamine, N,N-diethylethylenediamine, and N,N-dimethylpropanediamine.

2. The complex amine absorbent according to claim 1, wherein the component 3) is N,N-dimethylethylenediamine or N,N-dimethylpropanediamine.

3. A device for removing one or both of CO.sub.2 and H.sub.2S, the device comprising: an absorber for removing one or both of CO.sub.2 and H.sub.2S by bringing a gas containing one or both of CO.sub.2 and H.sub.2S in contact with the complex amine absorbent of claim 1; and a regenerator for regenerating a solution containing the one or both of CO.sub.2 and H.sub.2S absorbed therein, the absorbent regenerated by removing the one or both of CO.sub.2 and H.sub.2S in the regenerator being reused in the absorber.

4. A method of removing one or both of CO.sub.2 and H.sub.2S, the method comprising: bringing a gas containing one or both of CO.sub.2 and H.sub.2S in contact with the complex amine absorbent of claim 1 to remove the one or both of CO.sub.2 and H.sub.2S; regenerating a solution containing one or both of CO.sub.2 and H.sub.2S absorbed therein; and reusing, in an absorber, the absorbent regenerated by removing the one or both of CO.sub.2 and H.sub.2S in a regenerator.

5. The method for removing one or both of CO.sub.2 and H.sub.2S according to claim 4, wherein an absolute pressure inside the regenerator is 130 to 200 kPa, an absorption temperature in the absorber is 30 to 80 C., and a regeneration temperature in the regenerator is 110 C. or higher.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic diagram illustrating the configuration of a CO.sub.2 recovery unit according to a first embodiment.

(2) FIG. 2 is a graph showing the relation between relative saturated CO.sub.2 absorption capacity and the weight ratio of a sterically hindered primary amine to MEA in Test Example 1 when the total concentration of amines is 45% by weight.

(3) FIG. 3 is a graph showing the relation between relative saturated CO.sub.2 absorption capacity and the weight ratio of a sterically hindered primary amine to MEA in Test Example 1 when the total concentration of amines is 35% by weight.

(4) FIG. 4 is a graph showing the relation between relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2 when the total concentration of amines is 35% by weight.

(5) FIG. 5 is a graph showing the relation between relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2 when the total concentration of amines is 40% by weight.

(6) FIG. 6 is a graph showing the relation between relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2 when the total concentration of amines is 45% by weight.

(7) FIG. 7 is a graph showing the relation between reaction rate indicator and the weight ratio of a polyamine to a primary amine in Test Example 3.

DESCRIPTION OF EMBODIMENTS

(8) The present invention will next be described in detail with reference to the drawings. However, the present invention is not limited by this embodiment. When there are a plurality of embodiments, any combinations of the embodiments are included in the invention. Components in the following embodiments include those that can be easily devised by persons skilled in the art or that are substantially the same.

EMBODIMENTS

(9) A complex amine absorbent according to an embodiment of the present invention is an absorbent that absorbs one or both of CO.sub.2 and H.sub.2S in gas and is obtained by dissolving 1) monoethanolamine (MEA) and 2) a primary amine represented by the following formula (1) and having high steric hindrance, in water.

(10) ##STR00004##

(11) Herein, R.sub.1 to R.sub.3 are each hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and at least one of the functional groups R.sub.1 to R.sub.3 is a hydrocarbon.

(12) The total concentration of amine in the complex amine absorbent is preferably 30 to 70% by weight and more preferably 40 to 70% by weight.

(13) In the present invention, 1) monoethanolamine (MEA) and 2) the primary amine represented by the above-mentioned formula (1) and having high steric hindrance are dissolved in water to prepare the absorbent. These amines are entangled in a complex manner, and the synergistic effect of these amines provides high ability to absorb one or both of CO.sub.2 and H.sub.2S and high ability to release absorbed CO.sub.2 or H.sub.2S during regeneration of the absorbent, so that the amount of water vapor used in a CO.sub.2 recovery facility during regeneration of the absorbent can be reduced.

(14) The primary amine represented by the above-mentioned formula (1) and having high steric hindrance may be, for example, any one of 2-amino-1-propanol (2A1P), 2-amino-1-butanol (2A1B), 2-amino-3-methyl-1-butanol (AMB), 1-amino-2-propanol (1A2P), 1-amino-2-butanol (1A2B), and 2-amino-2-methyl-1-propanol (AMP).

(15) A combination of the above amines may be used.

(16) When a combination of amines is used, it is preferable to use an absorbent containing 2-amino-2-methyl-1-propanol (AMP) as a base amine and another amine added thereto.

(17) The total concentration of amines in the complex amine absorbent is preferably 30 to 70% by weight. This is because, when the total concentration of amines falls outside this range, the complex amine absorbent does not favorably function as an absorbent.

(18) The weight ratio of 2) the primary amine having high steric hindrance to 1) monoethanolamine (MEA) is within the range of 0.3 to 2.5, preferably within the range of 0.3 to 1.2, and more preferably within the range of 0.3 to 0.7.

(19) This is because, as described in Test Examples later, absorption performance becomes lower than reference absorption performance, i.e., the absorption performance when the concentration of MEA is 30% by weight, which is a concentration generally used in conventional absorbents.

(20) The above ratio is changed according to the total amine concentration. When the total amine concentration is 30% by weight, the ratio is a value close to 0.3.

(21) Any one of at least one amine selected from linear poly primary and secondary amines and at least one selected from cyclic polyamines may be further contained as an assistant.

(22) The addition of the assistant improves the rate of reaction, so that energy saving can be achieved.

(23) Preferably, the linear poly primary and secondary amines are ethylenediamine (EDA), N,N-dimethylethylenediamine (DMEDA), N,N-diethylethylenediamine (DEEDA), propanediamine (PDA), and N,N-dimethylpropanediamine (DMPDA), and the cyclic polyamines are piperazine (PZ), 1-methylpiperazine (1MPZ), 2-methylpiperazine (2MPZ), 2,5-dimethylpiperazine (DMPZ), 1-(2-aminoethyl)piperazine (AEPRZ), and 1-(2-hydroxyethyl)piperazine (HEP).

(24) Preferably, the weight ratio of at least one amine selected from the linear poly primary and secondary amines or at least one amine selected from the cyclic polyamines to the complex primary amine absorbent containing monoethanolamine and at least one amine selected from primary amines having high steric hindrance (the weight ratio of the polyamine/the complex primary amine) is 1 or less.

(25) In the present invention, absorption temperature in an absorber during contact with flue gas containing CO.sub.2 etc. is generally within the range of preferably 30 to 80 C. If necessary, an anti-corrosive agent, an anti-degradant, etc. are added to the absorbent used in the present invention.

(26) In the present invention, regeneration temperature in a regenerator in which CO.sub.2 etc. are released from the absorbent containing CO.sub.2 etc. absorbed therein is preferably 110 C. or higher when the pressure inside the regenerator is 130 to 200 kPa (absolute pressure). This is because, when regeneration is performed below 110 C., the amount of the absorbent circulating in the system must be increased, and this is not preferred in terms of regeneration efficiency.

(27) More preferably, regeneration is performed at 120 C. or higher.

(28) Examples of the gas treated by the present invention include coal gasification gases, synthesis gases, coke-oven gases, petroleum gases, and natural gases, but the gas treated is not limited thereto. Any gas may be used so long as it contains an acid gas such as CO.sub.2 or H.sub.2S.

(29) No particular limitation is imposed on a process that can be used in a method of removing one or both of CO.sub.2 and H.sub.2S in the gas in the present invention. An example of a removing device for removing CO.sub.2 will be described with reference to FIG. 1.

(30) FIG. 1 is a schematic diagram illustrating the configuration of a CO.sub.2 recovery unit according to embodiment 1. As shown in FIG. 1, a CO.sub.2 recovery unit 12 according to embodiment 1 includes: a flue gas cooling unit 16 for cooling, with cooling water 15, flue gas 14 containing CO.sub.2 and O.sub.2 discharged from an industrial combustion facility 13 such as a boiler or a gas turbine; a CO.sub.2 absorber 18 including a CO.sub.2 recovery section 18A for removing CO.sub.2 from the flue gas 14 by bringing the cooled flue gas 14 containing CO.sub.2 into contact with a CO.sub.2 absorbent 17 (hereinafter may be referred to as an absorbent) that absorbs CO.sub.2; and an absorbent regenerator 20 for regenerating the CO.sub.2 absorbent by causing the CO.sub.2 absorbent 19 containing CO.sub.2 absorbed therein (hereinafter, this absorbent may also be referred to as a rich solution) to release CO.sub.2. In the CO.sub.2 recovery unit 12, the regenerated CO.sub.2 absorbent 17 from which CO.sub.2 has been removed in the absorbent regenerator 20 (hereinafter, this absorbent may also be referred to as a lean solution) is reused in the CO.sub.2 absorber 18 as the CO.sub.2 absorbent.

(31) In FIG. 1, reference numeral 13a represents a flue gas duct, 13b represents a stack, and 34 represents steam-condensed water. The CO.sub.2 recovery unit may be retrofitted to an existing flue gas source to recover CO.sub.2 therefrom or may be installed together with a new flue gas source. An open-close damper is disposed in a line for the flue gas 14 and is opened during operation of the CO.sub.2 recovery unit 12. When the flue gas source is in operation but the operation of the CO.sub.2 recovery unit 12 is stopped, the damper is set to be closed.

(32) In a CO.sub.2 recovery method using the CO.sub.2 recovery unit 12, the flue gas 14 containing CO.sub.2 and supplied from the industrial combustion facility 13 such as a boiler or a gas turbine is first increased in pressure by a flue gas blower 22, then supplied to the flue gas cooling unit 16, cooled with the cooling water 15 in the flue gas cooling unit 16, and then supplied to the CO.sub.2 absorber 18.

(33) In the CO.sub.2 absorber 18, the flue gas 14 comes into countercurrent contact with the CO.sub.2 absorbent 17 serving as an amine absorbent according to this embodiment, and the CO.sub.2 in the flue gas 14 is absorbed by the CO.sub.2 absorbent 17 through a chemical reaction.

(34) The CO.sub.2-removed flue gas from which CO.sub.2 has been removed in the CO.sub.2 recovery section 18A comes into gas-liquid contact with circulating wash water 21 containing the CO.sub.2 absorbent and supplied from a nozzle in a water washing section 18B in the CO.sub.2 absorber 18, and the CO.sub.2 absorbent 17 entrained in the CO.sub.2-removed flue gas is thereby recovered. Then a flue gas 23 from which CO.sub.2 has been removed is discharged to the outside of the system.

(35) The rich solution, which is the CO.sub.2 absorbent 19 containing CO.sub.2 absorbed therein, is increased in presser by a rich solution pump 24, heated by the lean solution, which is the CO.sub.2 absorbent 17 regenerated in the absorbent regenerator 20, in a rich-lean solution heat exchanger 25, and then supplied to the absorbent regenerator 20.

(36) The rich solution 19 released into the absorbent regenerator 20 from its upper portion undergoes an endothermic reaction due to water vapor supplied from the bottom portion, and most CO.sub.2 is released. The CO.sub.2 absorbent that has released part or most of CO.sub.2 in the absorbent regenerator 20 is referred to as a semi-lean solution. The semi-lean solution becomes the CO.sub.2 absorbent (lean solution) 17 from which almost all CO.sub.2 has been removed when the semi-lean solution reaches the bottom of the absorbent regenerator 20. Part of the lean solution 17 is superheated by water vapor 27 in a regeneration superheater 26 to supply water vapor to the inside of the regenerator 20.

(37) CO.sub.2-entrained gas 28 accompanied by water vapor produced from the rich solution 19 and semi-lean solution in the absorbent regenerator 20 is discharged from the vertex portion of the absorbent regenerator 20. The water vapor is condensed in a condenser 29, and water is separated by a separation drum 30. CO.sub.2 gas 40 is discharged to the outside of the system, compressed by a separate compressor 41, and then recovered. A compressed and recovered CO.sub.2 gas 42 passes through a separation drum 43 and then injected into an oil field using Enhanced Oil Recovery (EOR) or reserved in an aquifer to address global warming.

(38) A reflux water 31 separated from the CO.sub.2-entrained gas 28 accompanied by water vapor in the separation drum 30 and refluxed therethrough is supplied to the upper portion of the absorbent regenerator 20 through a reflux water circulation pump 35 and also supplied to the circulating wash water 21 through a line *1.

(39) The regenerated CO.sub.2 absorbent (lean solution) 17 is cooled by the rich solution 19 in the rich-lean solution heat exchanger 25, then increased in pressure by a lean solution pump 32, cooled in a lean solution cooler 33, and then supplied to the CO.sub.2 absorber 18. In the embodiment, their outlines have been described, and part of attachments is omitted in the description.

(40) Preferred Test Examples showing the effects of the present invention will next be described, but the present invention is not limited thereto.

Test Example 1

(41) An unillustrated absorption device was used for absorption of CO.sub.2. FIGS. 2 and 3 are graphs showing the relation between relative saturated CO.sub.2 absorption capacity and the weight ratio of a sterically hindered primary amine to MEA in Test Example 1.

Comparative Example

Reference

(42) A Comparative Example is a conventionally used absorbent containing monoethanolamine (MEA) alone.

(43) An absorbent containing MEA at a concentration of 30% by weight was used as a reference absorbent, and a relative saturated CO.sub.2 absorption capacity was shown.

(44) The relative saturated CO.sub.2 absorption capacity is determined as follows.
Relative saturated CO.sub.2 absorption capacity=saturated CO.sub.2 absorption capacity of an absorbent in the subject application (at a concentration in the Test Example)/saturated CO.sub.2 absorption capacity of the MEA absorbent (30 wt %)

Test Example 1

(45) In Test Example 1, one of 2-amino-1-propanol (2A1P), 2-amino-1-butanol (2A1B), 2-amino-3-methyl-1-butanol (AMB), 1-amino-2-propanol (1A2P), and 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance at a mixing ratio shown in a lower part of FIG. 2. The amines were dissolved in water and mixed to prepare respective absorbents.

(46) The total amine concentration in Test Example 1 was 45% by weight.

(47) The absorption conditions in this test were 40 C. and 10 kPa CO.sub.2.

(48) The results are shown in FIG. 2.

(49) In FIG. 2, the saturated CO.sub.2 absorption capacity of the 30 wt % MEA absorbent was used as a reference value of 1, and the relative saturated CO.sub.2 absorption capacity of each absorbent was shown.

(50) As shown in FIG. 2, for all the four primary amines having high steric hindrance (2-amino-1-propanol (2A1P), 2-amino-1-butanol (2A1B), 1-amino-2-propanol (1A2P), and 2-amino-2-methyl-1-propanol (AMP)), the relative saturated CO.sub.2 absorption capacity was higher than the reference value 1, and the absorption performance was found to be good.

(51) Of these, 2-amino-2-methyl-1-propanol (AMP), in particular, showed a very high value for the absorption performance.

(52) As shown in FIG. 3, even when the total amine concentration was changed from 45% by weight to 35% by weight, the relative saturated CO.sub.2 absorption capacity of the amine solution using a combination of monoethanolamine (MEA) and 2-amino-2-methyl-1-propanol (AMP) was higher than a reference value of 1, and the absorption performance was found to be good.

Test Example 2

Comparative Example

Reference

(53) A Comparative Example is a conventionally used absorbent containing monoethanolamine (MEA) alone.

(54) An absorbent containing MEA at a concentration of 30% by weight was used as a reference absorbent, and a relative saturated CO.sub.2 concentration difference was shown.

(55) The relative saturated CO.sub.2 concentration difference is determined as follows.
Relative saturated CO.sub.2 concentration difference=saturated CO.sub.2 concentration difference of an absorbent in the subject application (at a concentration in the Test Example)/saturated CO.sub.2 concentration difference of the MEA absorbent (30% by weight)

(56) The saturated CO.sub.2 concentration difference is determined as follows.

(57) Saturated CO.sub.2 concentration difference=saturated CO.sub.2 concentration under absorption conditionssaturated CO.sub.2 concentration under recovery conditions

Test Example 2

(58) In Test Example 2, 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance at a mixing ratio shown in a lower part of each of FIGS. 4 to 6. The amines were dissolved in water and mixed to prepare respective absorbents.

(59) The total amine concentration in Test Example 2-1 was 35% by weight (see FIG. 4).

(60) The total amine concentration in Test Example 2-2 was 40% by weight (see FIG. 5).

(61) The total amine concentration in Test Example 2-3 was 45% by weight (see FIG. 6).

(62) The absorption conditions in the test were 40 C. and 10 kPa CO.sub.2.

(63) The recovery conditions were 120 C. and 10 kPa CO.sub.2.

(64) The results are shown in FIGS. 4 to 6. FIG. 4 is a graph showing the relation between the relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2-1 in which the total amine concentration is 35% by weight. FIG. 5 is a graph showing the relation between the relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2-2 in which the total amine concentration is 40% by weight. FIG. 6 is a graph showing the relation between the relative saturated CO.sub.2 concentration difference and the weight ratio of AMP to MEA in Test Example 2-3 in which the total amine concentration is 45% by weight.

(65) In FIG. 4 to FIG. 6, the saturated CO.sub.2 absorption capacity of the 30 wt % MEA absorbent was used as a reference value of 1, and the relative saturated CO.sub.2 absorption capacity of each absorbent was shown.

(66) As shown in FIG. 4, in Test Example 2-1 in which 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance, the relative saturated CO.sub.2 concentration difference was higher than a reference value of 1 when the weight ratio was about 0.5 or less, and the absorption performance was found to be good.

(67) As shown in FIG. 5, in Test Example 2-2 in which 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance, the relative saturated CO.sub.2 concentration difference was higher than a reference value of 1 when the weight ratio was about 1.2 or less, and the absorption performance was found to be good.

(68) When the weight ratio was about 0.7 or less, the relative saturated CO.sub.2 concentration difference was significantly higher than a reference value of 1 (an improvement of about 10%), and the absorption performance was found to be better.

(69) As shown in FIG. 6, in Test Example 2-3 in which 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance, the relative saturated CO.sub.2 concentration difference was higher than a reference value of 1 when the weight ratio was about 2.5 or less, and the absorption performance was found to be good.

Test Example 3

Comparative Example

Reference

(70) A Comparative Example is a conventionally used absorbent containing monoethanolamine (MEA) alone.

(71) An absorbent containing MEA at a concentration of 30% by weight was used as a reference absorbent, and a reaction rate indicator was shown.

(72) The reaction rate indicator is determined as follows.
Reaction rate indicator=reaction rate index of an absorbent in the subject application (at a concentration in the Test Example)/reaction rate index of the MEA absorbent (30% by weight)

(73) The reaction rate index is determined as follows.
Reaction rate index=(reaction rate constantamine concentrationdiffusion coefficient of CO.sub.2).sup.0.5

Test Example 3

(74) In Test Example 3, 2-amino-2-methyl-1-propanol (AMP) was used as the primary amine having high steric hindrance, and a polyamine used as an assistant was added at a mixing ratio shown in a lower part of FIG. 7. These were dissolved in water and mixed to prepare an absorbent.

(75) Ethylenediamine (EDA), N,N-dimethylethylenediamine (DMEDA), N,N-diethylethylenediamine (DEEDA), propanediamine (PDA), N,N-dimethylpropanediamine (DMPDA), piperazine (PZ), 1-methylpiperazine (1MPZ), 2-methylpiperazine (2MPZ), 2,5-dimethylpiperazine (DMPZ), 1-(2-aminoethyl)piperazine (AEPRZ), and 1-(2-hydroxyethyl)piperazine (HEP) were used as the assistant added.

(76) In Test Example 3, the total amine concentration was 40% by weight.

(77) The absorption conditions in this test were 40 C. and 10 kPa CO.sub.2.

(78) The results are shown in FIG. 7. FIG. 7 is a graph showing the relation between the reaction rate indicator and the weight ratio of a polyamine to the primary amine in Test Example 3.

(79) In FIG. 7, the reaction rate index of the 30 wt % MEA absorbent was used as a reference vale of 1, and the reaction rate indicator of each absorbent was shown.

(80) As shown in FIG. 7, when any of the assistants (ethylenediamine (EDA), N,N-dimethylethylenediamine (DMEDA), N,N-diethylethylenediamine (DEEDA), propanediamine (PDA), N,N-dimethylpropanediamine (DMPDA), piperazine (PZ), 1-methylpiperazine (1MPZ), 2-methylpiperazine (2MPZ), 2,5-dimethylpiperazine (DMPZ), 1-(2-aminoethyl)piperazine (AEPRZ), and 1-(2-hydroxyethyl)piperazine (HEP)) was added to the complex primary amine composed of monoethanolamine (MEA) and the primary amine having high steric hindrance (2-amino-2-methyl-1-propanol (AMP)), the reaction rate indicator was higher than a reference value of 1, and the absorption performance was found to be good.

(81) Of these, N,N-dimethylethylenediamine (DMEDA) and N,N-dimethylpropanediamine (DMPDA), in particular, showed high reaction rate values.

REFERENCE SIGNS LIST

(82) 12 CO.sub.2 recovery unit 13 Industrial combustion facility 14 Flue gas 16 Flue gas cooling unit 17 CO.sub.2 absorbent (lean solution) 18 CO.sub.2 absorber 19 CO.sub.2 absorbent containing CO.sub.2 absorbed therein (rich solution) 20 Absorbent regenerator 21 Wash water